STP 1491 Engine Coolant Technologies PDF

STP 1491
Engine Coolant Technologies: 5th

Volume
William N. Matulewicz, editor
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Foreword
This ASTM international publication contains manuscripts from The Fifth International
Symposium on Engine Coolant Technology sponsored by ASTM Committee D15 on
Engine Coolants. Held in Toronto, Canada, May 2006, this symposium provided a forum
for the presentation and exchange of information on advances in engine coolant system
components, experimental testing, uses and users experience of both automotive and
heavy-duty applications. These papers presented and contained in this publication,
focused on areas of 1 international coolant development 2 field testing of coolant
additives 3 engine coolant recycling 4 engine component and coolant additive compatibility 5 alternate coolant base technology 6 extended life oxidation and thermal
stability 7 new testing methods of cavitation, erosion and localized corrosion. These
presentations offered a view of the unique and ongoing research current in engine coolant technology. Much of the work presented is part of continued support offered to ASTM
D15 to modify existing and to establish new standards for engine coolants.
Fifth International Symposium on Engine Coolant

Technology
Opening Comments by William Matulewicz
This meeting marks my 20th anniversary in the ASTM D15 Engine Coolant Committee.
I now qualify as one of the Old Guards at D15. Certainly not as high a level of Old Guard as Jess
Starke and Frank Duffy, who are both at the Master Old Guard level, but certainly I have been
in D15 long enough to be at the entry level of Old Guard.
When I attended my first D15 meeting I considered myself an expert in engine coolant
technology. I was well versed in all of the ASTM D15 standards, which were all of those used in
D3306, plus one or two additional standards. I knew how to formulate a high performance engine
coolant. Basically, mix ethylene glycol together with phosphate/borate, silicone/silicate, nitrate/
nitrite, tolyltriazole, a little dye preferably uranine and a little antifoam. Make sure to add
enough caustic to yield the proper pH and RA, balance the DEG and water content and you had
a very good engine coolant.
Dont forget the 12 months/12,000 mile rule. I still love the sound of that phrase, 12
months, 12,000 miles. If you turned the TV on and heard that phrase, you knew the air was
getting crisp, the leaves were changing color and most importantly, it was time for football. Oh,
and change your coolant. Thats right, back then you actually changed your own coolant.
Those were good times, all you needed to know was phosphate/borate, silicone/silicate,
nitrate/nitrite, tolyltriazole, dye yellow and antifoam. Sure, I had heard that there were some
exotic formulas in Europe and a TEA/borate fluid in Asia, but we didnt pay much attention.
I walked into my first meeting and soon began my education in engine coolants.
Apparently there were two sides to this engine coolant coin, coolants used in trucks and coolants
used in cars. I also learned a new acronym, SCA. The truck guys actually added inhibitors to
extend the service life of coolants, they did not honor the 12/12 rule.
The D15 committee was clearly divided with truck coolant on one side and car coolant
on the other. The truck coolant side claimed that there was a problem with phosphate and silicate,
something about inhibitor fallout, overheating, pump failures and green goo. What would you
expect from a group that does not follow the 12/12 rule? D15 eventually constructed standards for
these truck folk and established new definitions, such as, Heavy Duty and Light Duty. Both sides
learned to reach across the line, embrace each other and work together to establish D15 standards.
Thank goodness for recyclers!
OK, I could live with Heavy Duty standards, but I did not see the tempest of new
standards to come in the following years. Little did D15 know that events in CT and TX were
going to result in numerous new standards, definitions and debates.
The Lime, CT area was host to 2 historical events. The first was the disease traced back
to a tick bite, hence the name Lymes disease. The second occurred at the same race track where
Paul Neuman was known to race. A race team in Lime Rock was experimenting with reversing
the coolant flow in an engine and using concentrated propylene glycol. Claims of better heat
transfer, better gas mileage, better corrosion control and lower toxicity soon surfaced.
Over a number of years and much debate, D15 established standards and definitions for
propylene glycol based coolants.
At about the same time down in TX, a man with a star was promoting engine coolants
based on an additive that is used to make monofilament fishing line. It was claimed that this new
longer, life fluid could last 30, 50 maybe even 100,000 miles. They wanted to totally trash the
12/12 rule!
This sebacic acid additive, long life concept grew in popularity, caught root, and landed
in D15. Long Life standards and definitions were established and continue to be established today
and include the Organic Acid Technology or OAT fluids.
By the mid-90s recycling engine coolants became a major issue in D15. Both OEM and
the States were demanding performance and chemical standards for recycled coolants. Recycling
technology at that time ran the gamut from passing used coolant through a machine with gauges
and blinking lights coming out the other end virtually unchanged, to add packs that raised the pH,
to reverse osmosis, to distilling and then adding inhibitors and buffers.
This recycle technology led to D15 standards for recycled coolants plus a host of new
definitions such as; Recycled Coolant, Prediluted Coolant, Recycled Ethylene Glycol and Virgin
Ethylene Glycol.
Along the development of OAT and long life fluids, not to be confused with extended
service fluids, it was found that blending traditional coolant technology with OAT fluids could
improve performance. This was the start of Hybrid fluids. I have heard the term HOAT to
describe these hybrid organic acid technology fluids. I have heard the term NOAT to describe
nitrite containing OAT fluids and MOAT to describe mixed OAT fluids. New research is now
investigating developmental organic acid nitate technology, or DONT.
More standards, more research, more definitions, more challenges. Compatibility issues,
oxidation stability issues, new technology issues. Being an expert in engine coolant technology
in 2006 is a little more demanding than the 1986 expertise of phosphate/borate, silicone/silicate,
nitrate/nitrite, tolyltriazole, a little dye preferably uranine and a little antifoam.
But being a new member of the Old Guard at D15 I am entitled to long for days past,
meetings with no cell phones or lap tops and breaks with long lines at the pay phone. Days when
blackberry was a fruit, blue tooth meant a trip to the dentist and yahoo meant you were really
excited.
20 years ago was a simpler time when 12 months and 12,000 miles ruled.
Contents
Overview
ix
Coolant Development in AsiaH. EGAWA, Y. MORI, AND M. L. ABEL
Heavy Duty Diesel Engine Coolant Technology: Past, Present, and Future
H. J. DEBAUN AND F. C. ALVERSON
Field Test for Carboxylate Inhibitor Levels in OAT CoolantsR. J. PELLET,

L. S. BARTLEY, JR. AND P. O. FRITZ
17
A Comparison of Membrane Technologies for Engine Coolant RecyclingR. HUDGENS,

E. SCHMIDT, AND M. WILLIAMS
26
New Electrochemical Methods for the Evaluation of Localized Corrosion in Engine

CoolantsB. YANG, F. J. MARINHO, AND A. V. GERSHUN
45
Compatibility Testing of Multi-Vehicle Coolant ChemistriesA. P. SKROBUL,

S. L. BALFE, AND F. C. ALVERSON
59
Investigation of Interaction Between Coolant Formulations and Flux Loading/

Compositions in Controlled Atmosphere Brazed (CAB) Aluminum Surfaces in Heat
Exchanger Applications
C. JEFFCOATE, M. RANGER, J. GRAJZL, B. YANG, P. WOYCIESJES, AND A. GERSHUN
69
Effect of Fluoride on Corrosion of Cooling System Metals in Ethylene Glycol-Based

Antifreeze/CoolantsB. YANG, A. V. GERSHUN, F. J. MARINHO, AND P. M.
WOYCIESJES
77
Heavy-Duty Diesel Engine Cavitation Test

G. DAVIS AND M. SARLO
87
Component Durability and High Mileage Performance of a Full Carboxylate Coolant

in Heavy Duty Diesel (HDD) EnginesP. O. FRITZ, L. S. BARTLEY, JR.,
R. PELLET, V. MOSER, AND C. ULABARRO
96
Cavitation Protection Performance of Nitrite-Free Organic Acid Based Coolant

for Heavy-Duty EnginesY. MORI, M. L. ABEL, AND Y. MIYAKE
109
Accelerated Oxidation and Corrosion Testing of Engine Coolants Using a Rotary

Pressure Vessel Oxidation TestF. C. ALVERSON, S. L. BALFE, AND A. P. SKROBUL
119
Coolants at Elevated TemperaturesS. CLAEYS AND S. LIEVENS
129
Comparison of Bench Test Methods to Elevate Heavy Duty Coolant Thermal

StabilityY. CHEN, R. D. HUDGENS, AND E. R. EATON
139
vii
Overview
In May of 2006, the ASTM D15 Committee on Engine Coolants sponsored the Fifth International Symposium on Engine Coolant Technology in Toronto, Canada. The advances in coolant
system components and construction continue to impact the modern automotive, heavy-duty,
locomotive and free standing engine design and performance. The expanding use of lighter
metals, advances in non-metallics, changes in fluid control technologies and coolant filtration in
todays engines, plus advancing discoveries in EGR and fuel cell technologies in engines of the
future are a few of the challenges facing the experts in engine coolant formulating. Challenges of
today include extended service life, liner pitting, the impact of EGR, advances in turbo charging
and component compatibility. Research areas must consider state and local regulatory requirements for increasing the use of recycled fluids and efforts for global standardization of test
methods.
The symposium presented an open forum for the presentation of new research in modern engine
coolant formulating addressing the complex issues mentioned above. The symposium was well
attended by international technical representatives from OEM and engine coolant producers. The
presentations were followed by open comments and questions from the attendees resulting in a
robust, professional exchange of ideas.
The contents of this STP are the fourteen papers presented at the Fifth International Symposium
on Engine Coolant Technology after the completion of a thorough peer review, which included
authors/editors exchange of comments and suggested revisions, according to the guidelines of
the ASTM Editorial Staff. These papers include current overviews of heavy duty coolant technology and coolant development in Asia, new testing methods, both in field and at the bench,
designed to help determine localized corrosion by electrochemistry, erosion corrosion, degradation of coolant components at elevated temperatures and under accelerated oxidation, and depletion of corrosion inhibitor additives. Compatibility issues are also presented addressing both
multi-fluids mixing and affects of fluid composition on engine components.
I want to thank the reviewers that volunteered their valuable time to complete the critique of the
papers presented. I also wish to thank the ASTM Editorial staff for providing the guidance and
expertise that enabled the successful completion of the Fifth International Symposium on Engine
Coolant Technology and the construction of this STP.
William N. Matulewicz
Wincom, Inc.
Blue Ash, Ohio
Symposium co-chairman and STP editor
ix
Journal of ASTM International, Vol. 4, No. 6

Paper ID JAI100368
Available online at www.astm.org
Hiroshi Egawa,1 Yasuaki Mori,1 and Michael L. Abel2
Coolant Development in Asia

ABSTRACT: Historically speaking, there have always been three major regions, North America, Europe,
and Asia, where antifreeze/coolant developments take place independently. These developments were
based on the perceived needs of the engine manufacturers, influenced by governmental/regulatory authorities, and heavily influenced by the requirements geography placed upon automobile manufacturers 13.
In the early days of ethylene glycol based engine coolants, simple inhibitor systems based on borates,
phosphates, etc., and utilizing a soft metal inhibitor were sufficient to satisfy the needs of a cast iron engine
and copper brass radiator. With the advent of aluminum engines and their rapid usage growth throughout
the 1980s and 1990s, engine manufacturers of the regions began to place more stringent requirements on
the anticorrosion performance of the OEM coolants. Based on the specific strategies utilized by the cooling
system component manufacturers, divergent requirements began to be placed upon the coolant makeup.
This paper will speak generally to the regional history of coolant trends and specifically on the activity for
coolant development in Asia.
KEYWORDS: coolant, automobile, engine, Asia, Japan, anticorrosion, inhibitor, technology,
aluminum
Technical Direction of Engine Coolant in Asia

Japan
In the 1960s European/North American regions used ethylene glycol based coolants and borate was the
main anticorrosion inhibitor for the antifreeze/coolant as cast iron engines and iron-containing components
were used. On the other hand, in Japan, representing the Asian region, usage of borate inhibited coolant
was recorded; however, the main antifreeze/coolant became ethylene glycol based with ethanolamine, and
phosphate inhibitor system coolant was adopted due to the BS3150 standard existence and the believed
superiority of aluminum metals corrosion protection by amine and phosphate versus borate as a main
reason 4. The engine antifreeze/coolant chart for each region since the 1970s is shown in Fig. 1.
Silicates were being increasingly used as an inhibitor in the 1970s to protect aluminum metals in
European/North American regions. The usage of silicates was avoided in Japan due to silicates having a
negative effect on the mechanical seal material of the water pump at that time and the stability performance related to gelling was an issue 5,6. Then the engine antifreeze/coolant trend became amine
phosphate based to protect aluminum, and borate usage was discontinued. This is the point when differences in the direction of inhibitor technology developed between European/North American regions and
the Asian/Japanese region. In the late 1970s, Japanese automotive manufacturers avoided nitrite antifreeze/
coolants due to Northern Europes Sweden countermeasure towards nitrosamine. The movement to
nonamine antifreeze/coolant was due to Norways 1987 regulations on triethanolamine, thus phosphate and
organic acid salt antifreeze/coolant P-OAT were developed. The phosphate and organic acid salt
antifreeze/coolants resulted in increased durability and a five year change interval for antifreeze/coolants
by certain car manufacturers and heavy duty truck company recommendations converting from a semiannual antifreeze/antirust change interval to long life coolant being used 710.
The organic acid technology OAT movement began in European/North American regions in the
1990s to take advantage of the increased durability of the antifreeze/coolant. Development of organic acid
Manuscript received January 27, 2006; accepted for publication November 7, 2006; published online July 2007. Presented at
ASTM Symposium on Engine Coolant Technologies: 5th Volume on 17 May 2006 in Toronto, Canada;
W. Matulewicz, Guest Editor.
1
CCI Corporation, 12 Shin-hazama, Seki City, Gifu, Japan.
2
CCI Manufacturing IL Corporation, P.O. Box 339, Lemont, IL60439.
Copyright 2007 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959.
2 ENGINE COOLANT TECHNOLOGY
FIG. 1Current status of engine coolant.

technology antifreeze/coolant occurred in Japan as well; however, due to insufficient aluminum corrosion
protection under severe operating conditions, the OAT technology was not widely applied.
Since 2000 in Japan, the main-stream antifreeze/coolant developed and utilized is organic acid salt,
low phosphate, long-life coolant LP-OAT 11,12.
Korea
The market is composed of Japanese type phosphate and organic acid salt antifreeze/coolant and European/
North American type silicate/borate type coolants due to the Korean automotive industry receiving technological assistance from auto manufacturers in all of the European/American/Japanese regions.
Southeast Asia Countries
Throughout the 1980s and into the early 1990s, water-based antirusts were mainly used due to the regions
warm climate as the antifreeze function was not necessary. Then came the issue of cooling system
corrosion problems apparent in the marketplace because antirust is inferior to antifreeze/coolant in the area
of anticorrosion performance.
In the late 1990s, the number of aluminum radiators increased and antirust usage was converted to
antifreeze/coolant which was determined to be important to maintain aluminum anticorrosion performance. As for antifreeze/coolant types, European/American/Japanese formulas are mixed in this region.
Also, in order to maintain proper dilution ratio instructed by automotive manufacturers, as well as quality
assurance of dilution water, an increased usage of prediluted antifreeze/coolant in the marketplace is
apparent.
China
The Chinese antifreeze/coolant market is a mixture of European/American/Japanese formulations, the
same situation as in Korea and Southeast Asian, due to technical assistance from parent and cooperative
companies from the various worldwide regions and the historically newness of the industry in China
compared to European/North American/Japanese regional companies. However, the recent automotive
industry growth in China is rapid and well documented and it will be interesting to see what the technological growth pattern will eventually be.
EGAWA ET AL. ON COOLANT DEVELOPMENT IN ASIA 3

TABLE 1Corrosion test in glassware.
Item
Test Solution Concentration
Specific Value
Appearance of After Test Specimen
Weight Change, mg/ cm2
Copper
Solder
Brass
Steel
Cast iron
Cast aluminum
Weight Loss, mg/specimen
Copper
Solder
Brass
Steel
Cast iron
Cast aluminum
JIS K2234 LLC

30 vol %
ASTM D 3306
33 vol %
No Corrosion
0.15
0.30
0.15
0.15
0.15
0.30
0.37
1.12
0.37
0.37
0.34
1.04
4
9
4
4
4
9
10
30
10
10
10
30
Note: data have been converted.
Direction of Japanese Coolant Specifications

The Japanese antifreeze/coolant specification was established in 1965, as the Japanese Industrial Specification JIS JIS K2234 13 Engine Antifreeze Coolant. The current specification is a modified version of
ASTM D 3306 14, and has typical performance as well as the glassware corrosion test, simulated service
testing, and cast aluminum heat exchange corrosion testing.
Several characteristics of the specification, per Table 1, are more strict when compared to ASTM
D 3306 for glassware corrosion test and simulated service test, as the test solution is at 30 % volume and
the test specimen appearance no corrosion is added and the weight change of the test specimens is more
narrow. However, it does not contain sections on cavitation durability performance and compatibility with
nonmetallic parts, thus these issues will be future topics.
Current Japanese Coolant Technology
Antifreeze/coolant development in Japan is derived from the close relationship between the automotive
manufacturer, parts supplier, and the antifreeze/coolant supplier. The antifreeze/coolant performance has
been improved consistent with the objectives of the automobile company vehicle advancement, resulting
in vehicle weight reduction, faster warm-up to optimum engine operating temperature, less fuel consumption, and a contribution to lower emissions.
The first major change was the nonamine antifreeze/coolant P-OAT movement of the 1990s and,
especially important, the movement of the heavy duty truck manufacturer to the usage of long-life
antifreeze/coolant technology 810. The addition of phosphate and organic acid salt inhibitors as main
components allowed for the increased durability of nonamine coolants. Since then, modified phosphate
antifreeze/coolant for the protection towards aluminum corrosion under very high temperature operating
conditions have improved due to new anticorrosion inhibitor formulation selections and have been necessitated by the engine components and heat exchanger becoming more aluminum alloy intensive.
The second major recent change was that since about the year 2000 the new antifreeze/coolant technology has changed from phosphates being the dominant inhibitor component to organic acid salts being
the predominant component with phosphate acting as one of the supporting components resulting in this
technology increasing the durability of antifreeze/coolant LP-OAT.
Such long-life engine coolants LP-OAT are being used worldwide, Japan, Europe and the Americas,
and have over five years of actual usage in the marketplace. Not only meeting the general specifications of
ASTM D 3306, per Tables 24, it has yielded good results in the European FVV testing method test as
well.

TABLE 2Vibration test results.
Property
Weight loss mg/h
AlCuMg2
New state
20 v / v %
40 v / v %
Aged for 120 h
40 v / v %
GG 25
New state
20 v / v %
40 v / v %
Aged for 120 h
40 v / v %
FVV R476
Specific Values
LP-OAT A
OAT LLC
10.08 max
10.08 max
8.3
7.2
7.3
8.0
12.60 max
10.2
8.5
5.30 max
5.30 max
4.1
4.9
3.2
3.6
7.95 max
4.0
4.0
TABLE 3Heat test results.
Property
Weight loss mg
G-AlSi10Mg
New State/Deionized Water
40 v / v %
New State/10dGH
20 v / v %
40 v / v %
Aged for 120 h
40 v / v %
GG 25
New State/Deionized Water
40 v / v %
New State/10dGH
20 v / v %
40 v / v %
Aged for 120 h
40 v / v %
FVV R476
Specific Values
LP-OAT A
OAT LLC
50 max
3.3
19.9
50 max
50 max
100 max
1.4
2.1
5.8
28.3
36.3
70.9
20 max
9.1
6.0
20 max
20 max
7.8
9.1
6.2
6.8
40 max
13.0
9.4
Characteristics of Coolant Technology in Japan

Main components of coolant in each area are shown in Table 5. In European/North American regions, OAT
LLC which contains organic acids as the main inhibitor but does not contain borate, silicate, or phosphate,
TABLE 4Corrosion test results.
Property
Weight loss g / m2
G-AlSi10Mg
AlMn
AlCuMg2
GG 25
Steel RRSt 14.05
E-Cu
CuZn
Solder L-PbSn 40 Sb
FVV R476
Specific Values
LP-OAT A
OAT LLC
10 max
8 max
8 max
2 max
2 max
3 max
3 max
6 max
1.17/1.27
1.03/0.77
1.59/1.62
+1.07/ + 0.17
0.55/0.28
0.24/0.20
0.87/0.83
1.50/1.77
2.28/2.48
3.18/3.52
2.95/2.91
0.71/1.22
0.47/0.39
0.67/0.67
0.79/0.83
2.00/2.00
Note: After final cleaning Pack 1/Pack 2.
FIG. 2Aging tendency of LLCs.

TABLE 5Main components of currently used coolants.
Japan
Component
Organic acid
Phosphate
Borate
Silicate
Triazole
Nitrate
Nitrite
LP-OAT
OO
O
O
O
USA
P-OAT
O
OO
O
O
OAT
OO
O
O
Europe
B,SiOAT
O
O
O
O
O
O
B,Si-AF
O
O
O
O
O
O
OAT
OO
O
O
B,SiOAT
O
O
O
O
O
O
Note: OOContained as a Main Component; OContained;; Not Used.
and B,Si-OAT which contains organic acids, borate, and silicate are used most prevalently by the OEM.
On the other hand, in Japan, P-OAT and LP-OAT which contain organic acids and phosphate but do not
contain borate and silicate are typically used, as it is a characteristic for coolants in Japan to contain
phosphate.
LP-OAT have not only superior durability see Fig. 2 but also excellent anticorrosive property against
aluminum due to suitable selection and quantity of organic acids and phosphate. Test results of the
European evaluation method CEC C-23 Dynamic Corrosion Test are shown in Figs. 3 and 4. LP-OAT has
excellent anticorrosive property against aluminum when compared to P-OAT and OAT LLC.
Also, the latest generation of Japanese antifreeze/coolant technology, even while containing a low
level stabilized phosphate inhibitor, gives excellent results in the GFC L-106-A-90 hard water stability test
see Fig. 5. Therefore, LP-OAT that was developed utilizing the latest Japanese coolant technology is a
global coolant that is being used, without reservation, all over the world.
Technical Direction of Next Generation Coolant

The world automotive manufacturers are consolidating engines and platforms and utilizing architecture
developed in one region throughout their globalized distribution system and the next generation of
antifreeze/coolant will be an antifreeze/coolant that possesses performance that any automotive manufacturer can use. Such antifreeze/coolant will be influenced by local/regional regulations as well as automotive manufacturers specification.
Last but not least, automotive manufacturers will be influenced by LOHAS Lifestyles of Health and
Sustainability consumers; such consumers will be more demanding and not settle for current technology,
as concern for the environment has increased. As a result, automotive manufacturers will bring new
technology vehicles for the new world and new long-life coolant must be developed with new technology.
FIG. 3Dynamic corrosion test results.
FIG. 4Appearance of test specimen (cast aluminum) after chemical treatment.
FIG. 5Appearance of after hard water compatibility test.

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1
2
3
4
5
6
7
8
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Paper ID JAI100336
Heather J. DeBaun1 and Fred C. Alverson2
Heavy Duty Diesel Engine Coolant Technology: Past,

Present, and Future
ABSTRACT: Significant advances have been made in heavy duty diesel engine technology to meet increasingly stringent environmental regulations for emissions. Todays heavy duty diesel engines are being
designed with lighter and softer metals, greater turbocharging, increased combustion controls, and new
emission reduction equipment. The cooling systems contained in these vehicles are similarly being impacted by smaller designs, new cooling system configurations, and increased usage of lighter, softer
metals. Vehicle thermal loads have significantly increased due to increased power densities, higher engine
temperatures, and greater metal-coolant fluxes which places greater emphasis on oxidation/thermal stability, and high temperature corrosion protection performance of the coolant. Other operating conditions
coolant flow rates, turbulence, pressure drops, deaeration are also becoming more severe calling for
improved erosion-corrosion protection, cavitation protection, and elastomer, seal, hose compatibility. This
paper reviews the changes in heavy duty diesel engine technology and provides information on coolant
performance in 2002-4 emission compliant engines. Predictions are also made on future engine technology
and next generation engine coolants.
KEYWORDS: heavy duty engine coolants, cooling system trends, oxidation stability, erosion
corrosion, cavitation, elastomer compatibility, traditional fully-formulated coolants, extended service
coolants, extended life coolants, supplemental coolant additives
Introduction
Diesel engines continue to be the work horse engines of industry. Advances in diesel engine technology are
being driven by needs for increased power, emission reductions, improved fuel economy, and longer
reliability. Todays modern diesel engines include turbochargers with intercoolers, electronic timed fuel
injection, computerized combustion controls, and emission reduction equipment which are all placing
greater thermal loads on the coolant. Recent advances in engine cooling and the cooling system have not
been as significant. The cooling system still utilizes an engine-driven water pump and fan controlled by
engine speed r/min and a mechanical thermostat controlled by radiator bulk coolant temperature. This
paper will review some of the changes in heavy duty diesel engine technology and the impacts on the
cooling system and coolant along with future trends in the cooling system and coolant technology.
Modern Diesel Engines
Emission Compliant Equipment
In 2002, heavy duty diesel engine manufacturers were faced to meet lower emissions standards for nitrous
oxides NOx and hydrocarbons. The NOx regulation lowered from 4 to 2 g / bhp-h Fig. 1. In order to
meet these regulations, most engine manufacturers have employed the use of cooled exhaust gas recirculation EGR because it offers better fuel economy than retarded timing 1. The exhaust gas is cooled and
the turbocharger boost pressures must increase to increase the air into the cylinder.
In meeting the lower NOx requirements, the recirculated exhaust gas is cooled. Stainless steel EGR
coolers are used to cool the exhaust gas with engine coolant. The use of EGR involves diluting the air/fuel
Manuscript received June 8, 2006; accepted for publication October 19, 2006; published online November 2006. Presented at
ASTM Symposium on Engine Coolant Technologies: 5th Volume on 17 May 2006 in Toronto, Canada; W. Matulewicz, Guest
Editor.
1
Senior Project Engineer, International Truck and Engine Corporation, 10400 West North Avenue, Melrose Park, IL 60160.
2
Coolant Advisor, Shell Global Solutions, 3333 Highway 6 South, Houston, TX 77082.
DEBAUN AND ALVERSON ON HEAVY DUTY DIESEL TECHNOLOGY
FIG. 1U.S. emissions regulations.

mixture entering the engine with a small amount of exhaust gas 5 15 % . The addition of the exhaust
gas lowers the oxygen content and lowers the combustion temperature which reduces the high temperature
formation of NOx. The EGR cooler uses the engine coolant to cool the exhaust gas down from 1300 to
325 F which results in significant heat rejection to the coolant. Heat rejection of the coolant increases by
25 35 % 2 due to the cooling of exhaust gas. In some cases, bulk coolant temperatures increase if
radiator size cannot be increased in order to make up for increased coolant heat rejection. The high
temperatures in the EGR cooler led to localized boiling, increased degradation of the coolant, and reduced
coolant life.
Cooling System Changes
The OEMs and cooling system component suppliers are using multiple approaches to handle the increased
heat loads on the coolant including increasing the boiling point of the coolant by raising the pressure limit
on the radiator cap 7 to 10 psi and higher in some applications, using higher performance fans and fan
clutches, increasing water pump size or speeds, or both i.e., coolant flow rates, and using larger and more
efficient heat exchangers. With regard to heat exchangers, the trend is toward the use of lighter, softer
metals with narrower clearances/tolerances that improve heat transfer efficiency. The use of the lighter,
softer metals often have maximum flow rate limitations which must be considered during system design.
Overall bulk coolant temperatures have risen to meet the 2004 emission requirements and are expected
to further increase to meet 20072010 emission regulations Fig. 2. Along with the overall bulk coolant
temperature rise, the coolant is exposed to significantly high metal-coolant heat fluxes in regions around
the cylinder heads and liners, and exhaust gas recirculation if equipped. In some of these regions, heat
transfer is accomplished by nucleate boiling which places additional stress and demands on the coolant.
In addition to the increased thermal loads on the coolant, the newer engine designs, under the hood
configurations, and severe operating conditions of higher water pump speeds/coolant flow rates are making
it more difficult to achieve satisfactory deaeration of the coolant. Residual air bubbles in the cooling
FIG. 2Heat rejection history [3].
system contribute to oxidation and thermal degradation of the coolant. Vehicle and engine deaeration
systems and characteristics must also be taken into consideration during cooling system design.
Charge Air Coolers
Diesel engine OEMs are achieving higher power through the use of turbochargers or superchargers. The
use of a turbocharger allows more air to be forced into the engine which allows more fuel to be burned
resulting in increased power. To achieve even more power, the air may be cooled through an air-to-air or
air-to-liquid charge air intercooler which increases the density and makes more oxygen available for
combustion. For air-to-liquid charge air intercoolers, the intercooler adds an additional thermal load on the
coolant. For air-to-air charge air intercoolers, the challenge is locating and achieving sufficient air flow
under the hood without adversely affecting air flow for the radiator 4.
Direct Fuel Injection and Combustion Control
Todays diesel engines inject the fuel directly into the cylinders using engine control modules ECMs that
deliver precisely the right amount of fuel when needed. The ECM communicates with an elaborate array
of sensors placed at strategic locations to monitor engine speed to coolant and oil temperatures. The
electronic controls mean that the fuel burns more thoroughly, delivers more power, greater fuel economy,
and fewer emissions 5. With regards to engine cooling, the increase in power output for given cylinder
volume during combustion results in increased heat rejection to the coolant.
Auxiliary Equipment
The addition of auxiliary equipment air conditioning, transmissions, oil coolers, etc. is also increasing
heat loads on the engine coolant. The air conditioning compressor adds an additional thermal load on
engine cooling, particularly under heavy load and idle conditions. Transmissions are operating at higher
temperatures resulting in additional heat rejection to the coolant through the transmission fluid cooler.
Automatic transmissions with torque converters used in bus applications and package van service place
additional heat rejection requirements on the coolant due to significant energy loss heat generation during
operation. In addition, these vehicles may operate with numerous starts and stops, often resulting in hot
soaking of the coolant which raises the coolant temperature and can cause boiling. In some cases, engine
coolant service intervals for extended life and extended service coolants used in these vehicles are being
lowered to automotive service intervals.
Elastomers, Seals, and Hoses
Elastomers, seals, and hoses are extremely important since they are widely used throughout the engine and
cooling system. Common elastomer materials used in the engine and cooling system include nitrile rubber
NBR, hydrogenated nitrile rubber HNBR, ethylene propylene terpolymer EPDM, tetrafluoroethylenepropylene copolymer FEPM, and silicone. Previous studies have been conducted on comparing the
performance of these materials in laboratory aging studies 6. In one study on ethylene glycol and
propylene glycol-based coolants containing silicates, it was shown that significant amounts of precipitate
may form which may represent leached hose components or destabilization of the silicate from hose and
coolant interactions, or both 7. A recent study conducted on a hybrid OAT coolant containing borate,
nitrite, nitrate, and silicate with three different EPDM sulfur-cured hose materials in a plugged hosecoolant compatibility test at 168 h at 104 C 220 F showed similar test results Table 1.
The more severe operating conditions higher coolant temperatures, higher under the hood temperatures, greater amount of hot regions in the engine may be having effects on both elastomer/hose and
coolant life. In some cases where coolant passages are extremely narrow almost filter size such as oil
cooler or water pump seal faces, or both, hose-coolant interaction products or other contaminants, or both,
can plug the passages resulting in reduced heat transfer, severe oxidation of the coolant, or equipment
failure, or a combination thereof.
There also have been some problems in the field with certain engines containing silicone seals in high
temperature regions using OAT-based coolants which resulted in loss of compression set and leakage. The
field problems were corrected by the addition of a silicate field fix or change in elastomer seal material, or
11
TABLE 1Plugged hose-coolant compatibility results.

Coolant Result
Sediment, vol %
pH
Silicon, ppm
Sulfate, ppm
Oxidation, ppm
Zinc, ppm
New
Nil
8.1
130
Nil
Nil
Nil
Hose 1
1.6
7.8
51
325
170
15
Hose 2
1.6
7.8
48
335
120
55
Hose 3
2.0
8.0
51
370
130
13
both. Additional cooperative work is required between the OEM, elastomer supplier, and coolant supplier
to extend the temperature limitations of elastomers and to improve coolant and elastomer compatibility.
Impacts on the Engine Coolant
The more severe operating conditions and environments in which heavy duty diesel engines operate have
an impact on coolant formulations and performance. Ethylene glycol-based engine coolants are still the
predominantly used heat transfer fluid for heavy duty applications. Several different types of engine
coolants are used in heavy duty applications, which may be classified by the type of corrosion inhibitors
contained in the formulation. In the United States, conventional coolants with the addition of supplemental
coolant additives SCAs, traditional fully formulated coolants, extended service interval coolants, and
extended life coolants are all used in heavy duty applications. In Europe, Asia Pacific, and other parts of
the world, conventional, hybrid, and extended life coolants are used in heavy duty applications. However,
there is less distinction between light duty and heavy duty coolants and less usage of SCAs outside the
United States. A description of the various types of heavy duty HD coolants is provided in Table 2.
Engine coolants used in heavy duty applications must provide satisfactory performance in the areas of
oxidation-thermal stability, high temperature corrosion protection, cavitation corrosion protection, erosionTABLE 2Type of HD engine coolants.
Conventional coolant
HD Extended life
coolant
HD Extended service
interval coolant
Hybrid coolant
Organic Additive
Technology OAT
Supplemental Coolant
Additive SCA
Traditional fully
formulated coolant
Contains inorganic corrosion inhibitors such as

borate, molybdate, nitrate, nitrite, phosphate, silicate.
In Europe, phosphate is generally not used due to
potential hard water compatibility problems. In Asia,
silicates are generally not used due to gel and water
pump seal abrasion concerns.
An engine coolant containing OAT providing long
service life. These products may contain nitrites or
molybdate, or both, and may be refortified
with an extender at typical service intervals of
300 000 miles or longer.
An engine coolant also providing extended service
life. SCAs are typically added at 100 000 150 000
mile intervals.
An engine coolant containing a combination of
inorganic and organic corrosion inhibitors. Europe
hybrids are phosphate free. Asia hybrids are silicate
free.
Any group of carboxylic acids including aliphatic
mono and diacids and aromatic acids applicable as
corrosion inhibitors in coolants.
A chemical additive that is periodically added to the
coolant to maintain protection against general
corrosion, cylinder liner pitting, and scaling in heavy
duty engines.
A conventional coolant containing an initial dosage
of SCA. These coolants require periodic addition of
SCAs typically at 20 000 mile 32 000 km
intervals.
FIG. 3Engine coolant nitrite results.

corrosion protection, elastomer compatibility, hard water stability, anti-scaling properties, and preferably
nondepleting coolant chemistry. As discussed in the preceding paragraphs, the advances in heavy duty
engine technology are placing greater demands on the coolant in all of these performance areas.
Oxidation-thermal Stability
Since engine coolants are hydrocarbon based, the ethylene glycol-based fluid is susceptible to oxidation
which involves reaction of ethylene glycol with oxygen to form glycol degradation acids glycolic acid:
HO-CH2-COOH, formic acid: HCOOH, oxalic acid: HOOCCOOH, etc.. Certain additives in coolants
such as nitrites, which are used to protect cast iron/cylinder liners from corrosion, may also undergo
oxidation to form nitrates. The increased thermal loading and more severe operating conditions higher
temperatures, aeration, pressure, and any cooling system contaminants/corrosion metals occurring in
todays engines are factors that can accelerate oxidation and shorten coolant life.
A significant amount of test data has been generated on engine coolant performance in 20022004
emission compliant engines. In the case of EGR equipped engines, the used coolant data show slightly
more rapid pH decline, more rapid nitrite reduction, and increased glycolate formation rates compared to
used coolant data obtained from similar non-EGR engines Figs. 3 and 4. The overall test results indicate
that traditional fully formulated, extended service interval and extended life coolants overall are performing satisfactorily with only minimal impacts on oxidation and coolant life. It is anticipated that 20072010
engines will require increased oxidation and thermal stability.
With regards to oxidation stability, there also have been some sporadic incidents in the field involving
black coolant and engine failures. Reports indicate that the incidents have occurred in both older and
newer vehicles/engines with and without emission compliant technologies using a variety of coolants.
Used coolant and failure analyses have often indicated that the failure mechanism includes severe thermal
stressing and oxidation of the coolant. Additional investigation into root causes has indicated a variety of
potential contributing factors may be involved including poor maintenance coolant concentrations/
corrosion inhibitor levels/SCA dosages, mechanical problems, or abnormal operating conditions, or both
high temperatures, hot spots, aeration, etc..
FIG. 4Engine coolant pH results.
13
TABLE 3Metal flow rate limits [10].

Metal
Iron component
General soft metal alloy
Aluminum heat exchange tube
Flow Rate Limit

33 ft/ s
15 ft/ s
7 9 ft/ s
Cavitation
Protection of wet cylinder liners against cavitation corrosion liner pitting continues to be of paramount
importance with diesel engines. Liner pitting is the result of cavitation and erosion processes that occur on
the coolant side of the cylinder liner. Cylinder liners vibrate from the motion of the piston within the
cylinder which can cause low pressure regions of the fluid causing vapor bubbles to form and collapse on
the surface of the liner. The repetitive formation and collapsing of the bubbles generally on the thrust or
anti-thrust side, or both, of the cylinder impinge on the metal surface, removing protective films and
eroding the metal. Previously published work provides an extensive overview of cavitation corrosion of
cylinder liners and its prevention which can be reduced by good coolant maintenance practices, engine and
design materials to minimize vibration, and cooling system design 8. A heavy duty engine cavitation test
based upon an internal John Deere cavitation test is being considered for adoption as a standard ASTM
engine coolant cavitation test. The test has been shown to discriminate between satisfactory and unsatisfactory coolants with regard to cavitation erosion-corrosion protection.
Engine coolants conventional, traditional fully-formulated, extended service interval, and extended
life coolants along with SCAs have commonly used nitrites or a combination of nitrites and molybdate
corrosion inhibitors, or both, for cylinder liner corrosion protection. In view of the more severe operating
conditions which can contribute to more rapid nitrite depletion, it is anticipated that extended life or
extended service nitrite free coolants, or both, will be used to a greater extent in diesel engines. Extended
life OAT coolants that are nitrite free have shown satisfactory performance in the heavy duty engine
cavitation test formerly the John Deere cavitation test and have been used satisfactorily in almost all
engine applications in the field.
Anti-scaling Performance
Scale resulting from the use of hard water, cooling system contaminants, and corrosion inhibiting film
agents can block the ability to transfer heat resulting in overheating and metal fatigue failures. Previous
studies reported that scale layers in the range of 0.01 to 0.05 in. 0.254 to 0.127 cm on the metal surface
can significantly retard heat transfer and increase metal surface temperatures 100 200 F / 38 93 C
around the head or upper part of the cylinder liner depending on conditions of heat flux and coolant flow
9. Scale tends to form in specific areas of the hot side of the engine resulting in localized hot spots, which
also accelerate oxidation degradation of the coolant. The hot scale and deposits 9 test is currently being
considered for establishment as a formal ASTM method for engine coolants. The use of good quality water
and properly inhibited coolants minimizes these deposits.
Erosion-Corrosion
Erosion-corrosion protection is becoming more important in view of the increased use of soft metals
aluminum, copper, and lead in various engine and cooling system components and the more severe
operating conditions of higher coolant flow rates. Erosion-corrosion is typically caused or accelerated by
excessive flow conditions which generate shear forces sufficient to remove corrosion passivating films or
naturally protective oxides, or both. Erosion-corrosion is most prevalent with soft metals which have
critical or limiting flow velocities Table 3 provides several examples which above the critical flow
velocity, corrosion rapidly accelerates. Other factors including turbulence, cavitation, impingement, galvanic effects, and abrasive contaminants casting sand, machining debris can add to the severity of the
attack. Erosion-corrosion problems have been observed in the field with brass fuel injector cups, aluminum
alloy oil coolers, and aluminum heater cores with several different types of coolants. The problems have
been resolved by changes in metallurgy, addition of flow restrictors, or cooling system design changes, or
a combination thereof.
FIG. 5Erosion-corrosion studypH effects.

Engine coolant chemistry can also influence erosion-corrosion protection. A recent erosion-corrosion
study was conducted on two different commercially available coolants containing nitrite and molybdate in
an aluminum alloy oil cooler module at elevated flow conditions 30 gpm. The results Figs. 57 show
that at the elevated flow conditions, the aluminum surface may become unpassivated resulting in conversion of nitrite to ammonia which increases the coolant pH and further accelerates the corrosion of aluminum to form aluminate corrosion metals which are soluble in the coolant.
Future Trends
Diesel engine OEMs are conducting extensive research on various technologies to reduce emissions to
meet more stringent 2007 and 2010 environmental regulations for NOx and particulate matter PM. The
engine manufacturers anticipate meeting these limits through a combination of changes in engine technology and additional emission reduction equipment, particularly heavy EGR to reduce NOx and diesel
particulate filters to reduce PM.
The 2007 emissions regulations will require the use of lower sulfur fuels which may require OEMs to
utilize more sophisticated fuel systems. Some engines will be utilizing dual turbochargers for better
efficiencies. Larger EGR coolers or dual EGR coolers will be required to lower combustion temperatures
to achieve lower NOx. EGR levels are expected to significantly increase from the levels used to meet the
2002 emissions, possibly increasing heat rejection by an additional 25 %. The higher levels of EGR may
FIG. 6Erosion-corrosion studynitrite conversion.
15
FIG. 7Erosion-corrosion studyaluminum corrosion metals.

cause an increase in coolant temperatures, localized boiling, and high skin temperatures. All of these will
increase the stress on the coolant and decrease the life of the coolant. The use of higher EGR is expected
to require improvements in coolant oxidation/thermal stability and nondepleting corrosion inhibitor chemistries.
Diesel particulate filters will be used to lower the PM emissions. The filter itself will not impact the
coolant, but may cause additional stress by modifying the way the engine runs. If the burning of the soot
from the diesel particulate filter is through the cylinder post injection of fuel, cylinder temperatures will
increase and coolant stresses will increase. The use of selective catalytic reduction technology to reduce
NOx emissions may reduce the load on EGR which will lessen the thermal load to the coolant.
The emission reduction technologies will impact coolants and cooling systems. Larger water pumps
will be used to supply higher coolant flow due to higher power requirements. Larger radiators will be used
to reject higher heat loads. Crankcase water jackets may be changed to handle higher pressures. Larger or
double EGR coolers will be needed due to higher EGR rates. Lighter, softer metals are being used in
cooling systems, and specifically, aluminum is being used more widely for cooling systems.
It is also anticipated that advanced modular thermal systems electric water pumps, valves, fans will
be incorporated into vehicles. The use of electric water pumps in place of conventional pumps will provide
benefits in delivering the correct amount of coolant from cold start-up to high operating temperatures. The
electric pump will also eliminate hot soak after shutdown by circulating coolant through the engine.
Electric valves may be used to provide more precise temperature control of coolant and engine temperatures than conventional thermostats. The use of a single electrical fan may not currently be practical due
to the high power consumption required for operation. However, small auxiliary electric fans may be
added to the cooling system to achieve more efficient cooling over a single mechanical fan. The cooling
system will also include computer controls to accurately control the temperatures for the primary engine
cooling, emission equipment, transmission, engine oil, and charge air cooler.
Laboratory and field data indicate that extended life coolants or extended service interval coolants, or
both, provide performance benefits in terms of oxidation-thermal stability which translates to longer
coolant and reduced usage of SCAs. It is anticipated that the usage of extended life and extended service
interval coolants will displace conventional and traditional fully-formulated coolants. In addition, coolant
suppliers will develop truly next generation coolant technology that provides greater high temperature
capabilities, is effective under high flow conditions, and possesses improved compatibility with elastomers. Regarding base fluids, propylene glycol 1,2-Propanediol may be used to a greater extent for the
biodegradability and toxicogical benefits. 1,3-Propanediol PDO is currently receiving significant interest
for its improved oxidation and thermal stability.
Engine coolants in the far future are expected to provide significantly greater heat transfer properties.
Current engine coolants rely primarily on the water concentration/dilution for heat transfer. The use of
nanotechnology particles of 5 nm size dispersed in aqueous medium exhibits significantly greater
thermal conductivities allowing more rapid heat transfer. Ionic fluids are a new class of fluids that are
emerging to replace organic solvents commonly used in chemical processing, cleaning, electrolyte, and
heat transfer fluid applications. Ionic fluids are organic salts with melting points of less than 100 C. Ionic
fluids may be used to reduce or replace glycol, or both, which would also improve heat transfer properties.
The use of nanotechnology or ionic fluids, or both, may require or allow significant changes in cooling
system design, components, and materials.
Acknowledgments
The authors wish to thank Mr. Stede Granger and Mr. James Roberts, with Shell Oil Products U.S., and
Mr. Joseph Hill and Ms. Andrea McCoy, with International Truck and Engine Corporation, for their
assistance and insight on coolant performance in todays heavy duty diesel engines.
References
1
2
3
4
5
6
10
Needham, J. R., Doyle, D. M., and Nicol, A. J., The Low NOx Truck Engine, SAE paper 910731,
1991.
McGeehan, J. A., API: CI-4: The First Oil Category for Diesel Engines Using Cooled Exhaust Gas
Recirculation, SAE paper 2002-01-1673.
Olson, G. D., Vehicle Integration/Thermal Management as Result of 2007 Diesel Emissions Regulations, Society of Automotive Engineers Panel.
Challen, B. and Baranescu, R., Diesel Engine Reference BookSecond Edition; Chapter 15 Auxiliaries, Thermal Loading, Society of Automotive Engineers, Warrendale, PA, 1999, 408pp.
Just the Basics: Diesel Engine, U.S. Department of Energy, Office of Energy Efficiency and
Renewable Energy.
Bussem, H., Farinella, A. C., and Hertz, D. L., Jr., Long-Term Serviceability of Elastomers in
Modern Engine Coolants, Engine Coolant Testing: Fourth Volume, ASTM STP 1335, R. E. Beal,
Ed., ASTM International, West Conshohocken, PA, 1999, pp. 142180.
Greaney, J. P. and Smith, R. A., Engine Coolant Compatibility with the Nonmetals Found in
Automotive Cooling Systems Engine Coolant Testing: Fourth Volume, ASTM STP 1335, R. E.
Beal, Ed., ASTM International, West Conshohocken, PA, 1999, pp. 168181.
Hercamp, R. D., An Overview of Cavitation Corrosion of Diesel Cylinder Liners, Engine Coolant
Testing: Third Volume, ASTM STP 1192, R. E. Beal, Ed., ASTM International, West Conshohocken,
PA, 1993, pp. 107127.
Chen, Y. S., Kershisnik, E. I., Hudgens, R. D., Corbeels, C. L., and Zehr, R. L., Scale and Deposits
in High-Heat Rejection Engines, Engine Coolant Testing: Fourth Volume, ASTM STP 1335, R. E.
Technology Transfer Systems, Inc., Impingement Corrosion, Engine Coolants, ISBN 0-97209270-6, Technology Transfer Systems, Inc., Livonia, MI, 2002, 55 pp.

Paper ID JAI100510
Regis J. Pellet,1 Leonard S. Bartley, Jr.,2 and Paul O. Fritz2
Field Test for Carboxylate Inhibitor Levels in OAT Coolants

ABSTRACT: Wet chemistry test methods have been developed to determine the level of alkyl carboxylate
inhibition remaining in used OAT coolants. The test strategy of these methods depends on the known alkyl
carboxylate ability to protect cooling system metals such as aluminum by forming insoluble metal soaps.
Various test configurations make this test strategy suitable for the rapid analysis of used coolants in the
field. This paper will document the initial test strategies and the development efforts that led to the first field
test for alkyl carboxylate-based coolants. Test kit performance with laboratory and field samples is also
discussed.
KEYWORDS: coolant, field test, organic additive technology, carboxylate, inhibitor
Introduction
In typical operation, a heavy duty diesel engine can generate sufficient heat to warm five single family
homes in winter. Only about 33 % of this heat is converted into crankshaft horsepower. In the past, it was
estimated that 30 % of the heat generated was expelled through exhaust and 7 % was radiated directly into
the atmosphere. This left about 30 % to be carried away by the cooling system. The amount of heat
dissipated by the coolant has risen significantly since exhaust gas recirculation EGR was introduced by
several engine manufacturers in 2002 in order to control emissions. In addition to removing heat generated
by fuel combustion, the cooling system must also remove heat generated by other components such as the
transmission and turbo charger.
Because of the severity of diesel engine operation and the stress that it places on the cooling system,
it is especially important that coolant properties are routinely monitored to assure proper protection of
cooling system components and the engine itself. Moreover, rapid testing in the field is essential if needed
corrections are to be made before damage occurs. At present there is an array of tests available to
determine if coolant freeze and boil protection are adequate and if the coolants corrosion inhibition is
sufficient to protect the engine components from damage. In addition there are tests to detect thermal
degradation and contamination with aggressive agents.
Freeze point is easily measured using a refractometer. Freeze point test strips are also available but can
be somewhat less reliable than the refractometer due to interferences caused by the coolants color.
Another less reliable method for freeze point determination is the hydrometer which is significantly
influenced by coolant temperature and by the possible mixing of ethylene glycol and propylene glycol
based coolants 1.
Coolant degradation can be followed to some extent by monitoring the coolant pH. pH test strips are
available covering the pH range from 612. These strips use multiple acid-base indicators to cover this
broad range of interest 2,3. Coolant degradation and specifically glycol breakdown create acid decomposition products such as formic, glycolic, and oxalic acids which cause the coolants pH to drop. If the
coolant is allowed to become acidic, inhibition becomes ineffective and corrosion damage will occur.
Monitoring coolant pH is a quick way to detect the possibility of thermal degradation in the field.
A rapid pH drop may also be caused by exhaust gas entry into the cooling system. Exhaust gas can
enter the cooling system through leaking head gaskets, for example. In addition to a rapid pH drop,
exhaust gas in the coolant may also be indicated by the presence of elevated levels of sulfate. There are test
Manuscript received February 24, 2006; accepted for publication December 13, 2006; published online February 2007. Presented
at ASTM Symposium on Engine Coolant Technologies: 5th Volume on 17 May 2006 in Toronto, Canada; W. Matulewicz, Guest
Editor.
1
Senior Staff Chemist, Chevron Corporation, New Windsor, NY 12553.
2
Chevron Corporation, New Windsor, NY 12553.
17
strips available to rapidly determine sulfate levels. The test method uses a test pad, impregnated with a
soluble barium salt and colored chelating agent. Sulfates in the coolant solutions will react with barium
irreversibly, removing it from the chelating agent and changing the pad color. Sulfate level is determined
by comparing pad color to a standard set of colors provided for that purpose 3.
Tests for corrosion inhibition focus on coolant nitrite or molybdate levels, or both. These two corrosion
inhibitors are present in most heavy duty coolants to protect the engines cylinder liners against damage
caused by liner cavitation. Nitrite, and to a lesser extent molybdate, are consumed as they provide protection; supplemental coolant additives SCAs are routinely added to the coolant to maintain adequate
liner protection. Routine testing is necessary to assure that effective refortification SCAs is occurring.
Initially, nitrite levels were determined using a wet-chemistry test, where cerous sulfate was added dropwise to a test coolant until a color change from red to blue occurred; the number of drops needed to
produce the color change was related to the coolants nitrite level 4. The presence of organic components
was found to interfere with this test and a test strip method for both nitrite and molybdate was subsequently introduced in 1988 5. With the strip, nitrite levels were estimated colorimetrically by reacting
nitrite with sulfonamide in the test pad to produce a diazo compound which was reacted with an aromatic
amine also present in the pad to produce an azo dye 5. Pad color is related to nitrite level.
With the advent of organic additive technology OAT in the U.S. in 1994, an alternate way to protect
cooling system components, including cylinder liners became available. Organic additive coolants rely on
carboxylate corrosion inhibitors to provide protection; nitrites may also be present for added liner protection but the primary line of defense is provided by carboxylic salts 6.
OAT corrosion inhibition, provided by alkyl carboxylate salts, depletes quite slowly and so does not
require frequent refortification by SCAs to assure on-going corrosion protection. Unlike conventional
coolant technology, frequent testing, performed in the field is not necessary in order to determine compliance with an SCA refortification regimen.
Nonetheless, inadvertent top-off with water or with conventional, silicated coolants will ultimately
result in dilution of the OAT inhibition and reduce the OAT coolants extended life properties. When
over-dilution is suspected, a quick test suitable for use in the field would help the end-user determine the
condition of his engines coolant and take appropriate action if warranted. As discussed above, conventional coolant technologies rely on nitrite and molybdate test strips to determine if the coolant is providing
adequate cylinder liner protection. Nitrite test strips can also be used with OAT coolants. However, options
were limited if rapid field testing for carboxylates were required.
Shortly after the introduction of OAT coolants, a wet chemistry test method was developed to determine the level of carboxylate inhibition remaining in used coolants. The test was highly accurate with field
samples, indicating a pass or fail condition based on carboxylate level. While the test was intended for
rapid analysis in the field, the initial configuration did involve several steps and coolant manipulation. It
has subsequently been replaced with a test strip method that employed the same test strategy but greatly
simplified analysis. The following sections document the initial test strategies and the development effort
for the early field test. Test kit performance with laboratory and field samples is also discussed.
Experimental Details
The organic additive coolants used in this study for the development of a carboxylate field test were based
on the alkyl carboxylate, ethylhexanoate. These coolants were available commercially from Texaco, Inc.,
in a nitrite free version, as Havoline Extended Life Anti-Freeze/Coolant as well as in a heavy duty
version containing nitrite, as Texaco Extended Life Coolant/Antifreeze.
Metal Ion/Carboxylate Ion Solubility Studies
Solubility data were generated by adding 2.0 milli normal mN stock solutions of soluble metal salts of
aluminum, iron, and copper to 2.0 mN stock solutions of carboxylic acids. All components were dissolved
in 50/50 water-glycol; the carboxylate solutions pH values were adjusted to 10 to assure that all acids
were present in the conjugate base form. Also, many commercial coolants have pH values in this region.
After mixing, all solutions were heated in closed containers to 80 C and then held at 80 C overnight and
then cooled, filtered to remove insoluble matter and analyzed for metal ion content by induction coupled
plasma ICP.
PELLET ET AL. ON CARBOXYLATE LEVELS IN OAT COOLANTS 19
Aluminum/Ethylhexanoate Titration
The following experiments were conducted to demonstrate the stoichiometric reaction of aluminum with
ethylhexanoate corrosion inhibitor. Six solutions were prepared by adding Havoline Extended Life AntiFreeze/Coolant in amounts varying from 0 to 10 to 20 mL aliquots of a 0.021 molar aqueous aluminum
stock solution. Havoline Extended Life Anti-Freeze/Coolant is a nitrite free, automotive coolant containing ethylhexanoate anion, EHA, as a key corrosion inhibitor. The mixtures were further diluted to obtain
a constant volume of 50 mL for each resulting solution using deionized water. A precipitate was observed
in all mixtures to which coolant was added. Solutions were filtered to remove the aluminumethylhexanoate reaction product and then analyzed by ICP to determine the amount of aluminum cation
remaining and by ion chromatography to determine the amount of ethylhexanoate remaining after reaction.
Colorimetric EHA Test Development
The following experiments were conducted to demonstrate the feasibility of an EHA test method based on
reactions with aluminum cation and aluminum detection using hematoxylin. Five solutions were prepared
mixing 20 g of aqueous aluminum stock solution 0.021 N with 0 to 24 g Havoline Extended Life
Anti-Freeze/Coolant. The solutions were prepared to yield EHA to Al molar ratios of 0, 1.0, 1.6, 2.0 and
3.0. Total mixture weight was brought to 50 g by adding additional deionized water to keep the total
reaction volume constant. In all but the 0 ratio mixture, an aluminum-EHA soap was formed. The resultant
mixtures were filtered to remove this precipitate and then tested for the presence of aluminum using the
hematoxylin test method 7. Specifically, the pH of each solution was raised to 8 by the addition of
1.0 g of saturated ammonium carbonate buffer; next 1.0 g of hematoxylin indicator 0.1 g in 100 g of
deionized water were added to each mixture; finally each solution was acidified by the addition of 1.0 g
of 30 % acetic acid.
Field Coolant Evaluation
Prototype kit performance was evaluated using coolant samples from an over-the-road, heavy duty diesel
fleet. The fleet employed Texaco Extended Life Coolant/AnitFreeze TELC, an EHA based coolant
containing nitrite. Vehicles in this fleet had been converted to TELC by flush-and-fill procedures, which
involved draining of conventional coolant, flushing with water and then filling with TELC. Additional
vehicles had been converted using Texaco Extended Life Corrosion Inhibitor Concentrate, a superconcentrated inhibitor package based on EHA. The super-concentrate was, on occasion, used to convert a
vehicle to extended life technology by addition to the conventional coolant already in place in the engine
without recourse to the drain, flush, and fill procedure. Because of the high EHA content of the superconcentrate as well as variability of diesel engine cooling system volumes, EHA levels significantly above
those found in fresh TELC were possible. For the purposes of test kit evaluation, 39 samples were obtained
and tested by laboratory methods. Coolant samples were also evaluated using two different prototype
versions of the field test.
Carboxylate Field Test Development
Texaco Extended Life Coolant was the first OAT marketed in the U.S.; it was based on the alkyl carboxylate, ethylhexanoate. At the time of its introduction, there were no rapid and accurate tests for carboxylate
ion concentration in coolants. A clue to potential test methodology came from early field experience that
revealed excellent corrosion protection for cooling system metals, especially for aluminum 8. Primary
evidence came from engine disassembly following extended field testing 300 000 miles which revealed aluminum components in like-new condition. Consistent with these observations was the fact that
aluminum ion was almost never detected in used coolant samples, even applications where significant
aluminum componentry was present throughout the cooling system.
Metal ion/carboxylate ion solubility studies provide insight to help understand the carboxylate protection mechanism. As one might expect, solubility of the metal carboxylate soap depends not only on the
metal ion but also on the chain length of the carboxylate. This can be seen in solubility data presented in
Fig. 1. The figure presents the amount of soluble metal cation in the presence of various alkyl carboxylate
anions. Data are presented for aluminum, copper, and iron ions. The graph shows that as the molecular
FIG. 1Metal carboxylate solubility.
weight or chain length of the carboxylate increases, the amount of soluble metal decreases; the effect is
greatest for aluminum cation which is insoluble in the presence of carboxylates with more than two
carbons. The effect is least pronounced for copper cation which remains partially soluble in the presence
of carboxylates up to ten carbons in length. Thus with Texaco Extended Life Coolant, used in the initial
test development based on C8 and C10 carboxylates, aluminum cation is virtually insoluble.
It is interesting to speculate that the effective corrosion protection, observed with this coolant, may be
provided by this insoluble soap formation at the sight of incipient corrosion; soap formation would
terminate the corrosion process before damage was done while consuming a minimal amount of inhibitor.
For the purpose of field test development, the quantitative reaction of aluminum with C8 and C10
alkyl carboxylates to form an insoluble soap can be related to the amount of carboxylate present in the
starting solution coolant. This is demonstrated in Fig. 2, where the amount of aluminum cation remaining
after reaction with added ethylhexanoate anion EHA is plotted as a function of the amount of ethylhexanoate ion added to the solution. From the graph, it can be seen that there is a linear, inverse relation
between the amount of aluminum remaining in solution and the amount of ethylhexanoate added to the
mixture.
From the graph, all aluminum is removed from the stock solution when sufficient ethylhexanoate is
added to achieve a ratio of EHA to Al of approximately 1.75 to 1. This suggests that the aluminum
ethylhexanoate precipitate formed has an empirical formula approaching Al EHA2. Importantly, the fact
that the graph of aluminum remaining versus ethylhexanoate added is a straight line suggests that this
stoichiometry remains constant over the range of aluminum and EHA concentrations examined.
This may be more apparent from the data in Table 1. Here, the amounts of aluminum and ethylhexanoate ion present in the initial solutions are compared with the amount of ions present after reaction and
filtration. The ratio of EHA and aluminum disappearing from solution remains constant over the concentrations studied.
FIG. 2Al3 titration with ethylhexanoate anion.

TABLE 1Aluminum and ethylhexanoate concentrations (moles/litre) before and after reaction and filtration.
Initial
Al
0.0213
0.0213
0.0213
0.0213
0.0213
Initial
EH
0.0428
0.0341
0.0298
0.0256
0.0213
Final
Al
0
0.00204
0.00407
0.00641
0.00930
Final
EH
0.007
0
0
0
0
Change
in Al
0.0213
0.01926
0.01723
0.01489
0.012
Change
in EH
0.0358
0.0341
0.0298
0.0256
0.0213
Change Ratio
EH/ Al
1.67
1.771
1.73
1.72
1.775
This observation suggests that aluminum can be used to titrate or determine EHA levels in used
coolants. To render this method useful for rapid field analysis, a method of soluble aluminum detection in
required. Conceptually, a field test might be as simple as:
Al+3 + Ethylhexanoate AlEHA2 + excess Al+3
Excess Al+3 + Indicator AlIndicator colored complex
In this conceptual test, a premeasured solution containing a predetermined amount of aluminum is
added to a measured aliquot of coolant sample from the field. The coolant sample contains an unknown
amount of EHA inhibitor. The amount of aluminum in the aliquot can be preselected to be equivalent to the
minimum amount of EHA needed for good corrosion protection this EHA target value can be varied
simply by varying the amount of aluminum cation in the test. The two solutions are mixed; a colorimetric
aluminum indicator is added to the solution portion of the mixture. The presence of aluminum in the
mixture indicates there is insufficient EHA to precipitate all the aluminum and thus there is insufficient
EHA inhibition. The colorimetric detection of aluminum indicates a failing coolant that would need to be
refortified to provide adequate corrosion protection.
There are several colorimetric tests for aluminum reported in the literature; a sampling of possible
techniques is provided in Table 2.
All of these tests permit the visual detection of aluminum at ppm levels by the formation of colored
complexes. Conceptually all could be used in the test described above. However, testing is complicated by
the fact that all heavy duty coolants are dyed to help to distinguish them from other engine fluids. Initially
heavy duty extended life coolants were dyed red to distinguish them from conventional coolants which
were purple or blue. The red color of extended life coolant has since become an industry standard as
proposed by the Technology and Maintenance Councils Recommended Practice 351. Because of coolant
color, aluminum indicators that turn red in the presence of aluminum may be of limited use. From Table
2, it can be seen that tests based on hematoxylin should not suffer from this limitation as it develops a
violet color in the presence of aluminum. Initial efforts to develop a field test for EHA focused on the use
of hematoxylin test which was first reported in 1924.
According to the hematoxylin procedure, a test solution containing aluminum must be buffered to
within a pH range of 6.5 to 8.5 using a saturated solution of ammonium carbonate in order to form the
aluminum indicator complex. The purple colored complex will not form at pH values below 6.5. Above
8.5 the complex forms but decomposes fades rapidly. In addition to being an aluminum indicator,
hematoxylins color is also sensitive to pH. At the pH of solutions made alkaline with ammonium carbonate, uncomplexed hematoxylin is red or purple, masking the violet color produced by the aluminum
complex. However, when pH is lowered by the addition of acetic acid, uncomplexed hematoxylins color
changes to yellow while the aluminum hematoxylin color is unaffected. Thus, lowering the mixture pH
after forming the aluminum complex removes the interference and allows aluminum detection if present.
TABLE 2Colorimetric aluminum indicators.
Aluminum Indicator
Hematoxylin
8-Hydroxyquinoline Oxine
Quinizarin
Aluminon
Aluminum complex
Color
violet
red
red
red
Reference
7
9
10
11
FIG. 3Al3 titration with ethylhexanoate using hematoxylin indicator.

To demonstrate feasibility of this test method, solutions were prepared mixing aqueous aluminum stock
solution with an EHA containing coolant to yield EHA to Al ratios ranging from 0 to 3. The resultant
mixtures were filtered and then tested for the presence of aluminum by raising the pH with saturated
ammonium carbonate buffer, adding hematoxylin indicator and then lowering the pH with acetic acid
solution. The resulting solutions ranged in color from yellow to deep purple or violet; all solutions at
EHA/ Al ratios above 2.0 were yellow; solutions with EHA/ Al ratios below 2.0 were violet. The dramatic
color change can be seen in Fig. 3.
Note that the color change occurs precisely and sharply at the end-point previously determined using
laboratory methods of ion chromatography and ion-coupled plasma. Thus a potential field test should be in
excellent agreement with the more time consuming laboratory analysis requiring ion chromatography.
Again, by selecting the amount of aluminum added to the field coolant, it is possible to determine if
adequate corrosion inhibition is present as indicated by the coolants ability to precipitate all added aluminum. It is also important to note that the dramatic color change is obvious even in black and white
photography and so utility of this colorimetric test would not be limited for a color blind observer.
Obviously, despite its potential accuracy, this multistep test would be too cumbersome for field use
unless carefully designed to minimize coolant and solutions handling and manipulation. With simplification as a goal, a commercial field test kit was designed and ultimately made commercially available. The
contents of the commercial kit are shown in Fig. 4.
The initial commercial kit consisted of three components: a white-capped test tube contains a premeasured amount of aluminum stock solution. A measured amount of coolant was added to this tube and an
aluminum EHA precipitate was formed. The resulting mixture was filtered using the filter syringe provided
and the filtered solution was added to the red-capped plastic test tube. There were three ampoules in this
tube containing ammonium carbonate, hematoxylin indicator, and acetic acid. The ammonium carbonate
ampoule was broken first releasing the buffer and raising the mixture pH to 8; the second ampoule was
FIG. 4Test kit for alkyl carboxylates.

TABLE 3Laboratory analysis of used coolant samples.
%
Carboxylatea
0
12
15
19
30
32
34
37
38
43
45
48
49
52
52
53
54
56
64
69
69
99
99
99
101
101
101
102
106
113
119
120
122
125
127
154
160
185
262
pH
8.3
7.06
7.87
8
8.37
8.75
8.18
8.5
7.83
8.22
7.6
7.66
8.31
8.7
8.3
7.83
8.13
8.1
7.85
8.73
8.76
8.48
8.73
8.11
8.13
8.54
8.51
8.65
8.31
8.78
8.49
8.05
8.12
8.02
8.54
9.03
8.97
8.49
8.8
%
Water
52.2
39.8
54.7
47.4
49.5
45.1
51.5
55.0
50.6
42.4
44.0
54.3
54.7
49.2
41.5
49.4
50.7
51.7
43.5
59.2
55.0
46.5
54.8
52.4
53.0
48.4
47.7
37.5
51.7
58.1
36.9
31.2
58.7
43.8
45.5
47.9
48.6
43.9
33.8
B
ppm
212
246
122
256
527
206
586
140
123
314
460
199
389
542
118
109
71
431
1117
155
514
58
320
7.2
454
10
7.6
349
203
17
291
29
189
427
276
384
200
637
206
Si
ppm
79
81
80
82
86
79
129
72
53
57
87
39
201
55
62
80
52
40
108
21
57
43
33
40
88
4.9
4.7
75
66
56
83
52
56
89
62
29
47
94
60
Mo
ppm
276
37
116
130
154
176
270
2.7
222
156
46
110
151
23
127
22
131
53
66
1
5.6
28
2.1
1
48
12
9.2
140
79
6.2
159
2.8
1
81
38
2.3
18
64
78
NO2
ppm
1160
11.6
660
1140
2300
866
2610
362
761
695
1330
273
1870
250
47.7
490
582
624
1250
242
533
108
580
2110
564
2370
2460
301
71
20.5
381
7
18.9
559
611
995
422
990
276
NO3
ppm
307
2020
955
1500
1800
520
2230
599
538
996
2020
486
1680
875
1160
458
660
1770
2730
305
830
275
680
55.7
1580
70
61
940
620
251
1560
139
243
2450
548
1200
381
1540
515
PO4
ppm
4680
12.2
2600
2580
2300
4280
3080
1520
2800
2970
562
1650
2250
1120
2800
79.7
1410
1930
532
664
1270
677
1250
8
261
118
84
2270
1290
1080
1860
220
205
1500
569
2300
249
2020
772
TTZ
ppm
380
110
280
100
470
1060
300
410
300
740
200
400
600
800
600
460
550
500
210
770
520
1070
770
800
2450
1100
1100
1200
1200
1120
700
1000
1100
720
1000
1380
1460
1700
2300
Percentage of ethylhexanoate, relative to fresh TELC.
then broken releasing the indicator and forming the purple aluminum-hematoxylin complex. The third
ampoule was broken lowering the pH, removing uncomplexed hematoxylin interference. The resulting
color would be yellow if all aluminum had been precipitated by reaction with the coolants EHA in the
white-capped vial. The resultant color would be purple or violet if there was insufficient EHA to completely remove the soluble aluminum that was initially present. Thus, a final yellow or red/orange color
indicated a pass; conversely, a final violet color indicates insufficient carboxylate inhibition, a fail.
As initially configured, the test took less than five minutes to complete and exhibited high accuracy
with laboratory samples. However, a more important indicator was performance with real world, used
coolant samples from the field. To this end, prototype test kits were used to evaluate 39 coolants obtained
from the field. The results of laboratory analysis of these field samples are provided in Table 3. Nominally,
all samples were obtained from a fleet that was using Texaco Extended Life Coolant TELC, an EHA
based heavy duty coolant containing nitrite. However, from the table it can be seen that all coolant samples
had varying degrees of contamination with competitive coolant products indicated by the presence of
FIG. 5Field performance with initial test kit.

phosphate, borate, silicate, molybdate, and nitrate. These conventional corrosion inhibitors were absent in
fresh TELC. Analysis also revealed varying degrees of dilution with water. In the table, coolants are
arranged in order of increasing EHA content which is expressed as a percent EHA relative to fresh coolant.
Thus a fresh coolant would have 100 % EHA. It can be seen that in real world use, coolant contamination
with conventional inhibitors is quite common. Water contents and coolant pH values also vary significantly.
All coolants were tested using the prototype test kit described above. The results of this evaluation are
presented graphically in Fig. 5.
In this figure, results are tabulated as pass or fail depending on whether a yellow or purple color
resulted from the prototype test kit. Results are presented in order of increasing carboxylate content %
EHA. A number of observations can be made. First, in the initial configuration, coolants with less than
fresh 100 % EHA routinely failed the test; there is only one false pass among the 22 coolant samples with
EHA levels less than 100 %. Secondly, for coolants with greater than 100 % EHA, it can be seen that there
are several false fails; specifically of the 17 samples evaluated, seven yield a failing indication. Finally, it
would appear that any coolant with less than 100 % EHA would fail the test as it had been initially
configured. This high end-point and the several false fails observed needed to be corrected. Based on these
results and a close examination of the chemical analysis of the coolant samples, it was discovered that
molybdate interfered with the test by yielding a near black complex with hematoxylin. Its presence in
many of the samples with high EHA, resulted in the false fails observed. In a second test kit which was
ultimately commercially released, the amount of aluminum present in the white tube was lowered so that
failing results would only be obtained when EHA levels fell to below 75 % of fresh. In addition, an
ampoule was added to the white tube containing a lead acetate; lead acetate will precipitate molybdate,
allowing it to be removed upon filtration and prior to hematoxylin addition in the red tube.
The modified prototype was used to evaluate the same 39 coolant samples from the original test.
Results of that evaluation are presented in Fig. 6. Use of the lead acetate ampoule in the white vial has
almost eliminated the occurrence of false fail results and accuracy has risen to nearly 90 %. Furthermore,
FIG. 6Field performance with improved test kit.
by reducing the amount of aluminum cation present in the white vial it was possible to lower the fail point
to about 70 %, i.e., coolants with EHA levels less than 70 % of fresh would now yield the violet fail
indicator.
Conclusions
The first kit for EHA field analysis was commercially introduced in 1998 and exhibited excellent performance in evaluating extended life, alkyl carboxylate coolants even with highly contaminated samples. This
test strategy, relying on aluminum solubility should work with any alkyl-based carboxylate coolant. However, aluminum cation is significantly more soluble in the presence of some aromatic carboxylates and so
this strategy may not be effective for coolants based on these inhibitors. While most of the field data,
presented in this study, were obtained with heavy duty extended life coolant containing nitrite and
molybdate, the strategy is also effective for automotive coolants containing alkyl carboxylates.
Ultimately, the hematoxylin method for detecting soluble aluminum was replaced with a two strip test
kits. The new kit still relies on the reaction of EHA in carboxylate base coolants with a stock aluminum
solution but has been significantly simplified by replacing the hematoxylin wet chemistry test with a test
strip method for aluminum detection. Accuracy for the test strip method has remained high while the test
procedure takes about a minute to execute.
References
1
2
4
5
6
7
8
9
10
11
Hudgens, R. D. and Bugelski, W. G., Analysis of Coolants from Diesel Engines, SAE Technical
Paper 900435, 1990.
Kreiser, T. H., Makowski, E., Martin, H. R., and Hudgens, R. D., Evaluation of Test Strips for
On-Side Monitoring of Coolants in Heavy-Duty Diesel Engines, SAE Technical Paper 960645,
1996.
Kreiser, T. H., Dandashli, E., Makowski, E., and Martin, H. R., Development and Evaluation of a
Test Strip for Estimating the pH, Chloride and Sulfate Levels in Engine Coolants, SAE Technical
Paper 1999-01-0133, 1999.
Kolthoff, I. M., Quantitative Chemical Analysis, The Macmillan Company, London, 4th ed., 1969,
pp. 816839.
Hemmes, P. R., Kreiser, T. H., Valle, S., and Hercamp, R. D., Test Strips for Rapid On-Site
Analysis of Engine Coolants, Engine Coolant Testing, 3rd Volume, ASTM STP 1192, R. Beal, Ed.,
ASTM International, West Conshohocken, PA, 1993, pp. 165179.
Pellet, R. J., Bartley, L. S., and Hunsicker, D. P., The Role of Carboxylate-Based Coolants in Cast
Iron Corrosion Protection, SAE Technical Paper 2001-01-1184, 2001.
Hattfield, W. D., Soluble Aluminum and the Hematoxylin Test in Filtered Waters, Ind. Eng.
Chem., Vol. 16, March 1924, pp. 233234.
Mowlem, J. K. and Van de Ven, P., Comparison of Surface Coating Formed from Carboxylic
Acid-Based and Conventional Coolants in a Field-Test Study, SAE Technical Paper 960640, 1996.
Liang, P., Yand, L., Hu, B., and Jiang, Z., ICP-AES Detection of Ultratrace Aluminum III and
Chromium III Ions with Microcolumn Preconcentration System Using Dynamically Immobilized
8-Hydroguinioline on TiO2 Nanoparticles, Anal. Sci., Vol. 19, 2003, pp. 11671171.
Kdriss, K. A., Hashem, E. Yl, Abdel-Aziz, M. S., and Ahmed, H. M., Direct Spectrophotometric
Determination of Aluminum Oxide in Portland Cement and Cement Clinker, J. Cem., Concr.,
Aggregates (ASTM), Vol. 23, No. 1, June 2001, pp. 5765.
Bertsch, P. M., Allely, M. M., and Ellmore, T. L., Automated Aluminum Analysis with the Aluminon Methods, Soil Sci. Soc. Am. J., Vol. 45, 1981, pp. 666667.

Paper ID JAI100615
R. Hudgens,1 E. Schmidt,2 and M. Williams2
A Comparison of Membrane Technologies for Engine

Coolant Recycling
ABSTRACT: Recycling of used engine coolants containing ethylene glycol and other glycols would appear
to be well established, particularly for reverse osmosis and nanofiltration membrane, electrodialysis, and
distillation-based processes. Both literature and recycling facilities indicate success in employing these
techniques. However, many recyclers, particularly those employing a single treatment technology, are not
capable of producing recycled product meeting original equipment manufacturer OEM requirements for
coolant, and these typically fall far short of approaching virgin nonrecycled coolant quality. In addition,
some recycling facilities have produced and marketed product that led to coolant system damage and
engine failure, either as a result of not sufficiently removing contaminants or inadequately reformulating
with corrosion inhibitors and other additives. The danger of process upsets resulting in inadequate product
is particularly high for those facilities that receive feeds with varying contaminant levels and coolants
containing a range of corrosion inhibitors and additives silicates, organic acids, etc.. However, no study to
date has focused on a fundamental assessment of the separation characteristics and interactions of the
various classes of coolant technologies with the commercially available reverse osmosis, nanofiltration, and
electrodialysis ion exchange membranes typically seen in recycling operations. This study presents results
of a comprehensive evaluation of the separation characteristics of a wide range of these membranes with
a wide range of coolant types. In particular, the study examined production rate characteristics, inhibitor
and other additive separation, and contaminant removal for reverse osmosis, nanofiltration, and electrodialysis. Residual inhibitors remaining in the recycled coolant are examined, with guidance provided on how
these residuals might affect coolant reformulation and performance.
KEYWORDS: used engine coolant, used antifreeze, recycling, electrodialysis, reverse osmosis,
nanofilteration
Introduction
Engine coolants are used to protect internal combustion engines from temperature extremes. The coolants
normally employ ethylene or propylene glycol at concentrations of 30 to 70 % by volume to lower the
freeze point and raise the boiling point of water in internal combustion engines. These coolants also
commonly employ chemical inhibitors at concentrations of approximately 1 to 5 % by weight to counteract corrosion. The useful life of engine coolants is limited by the degradation over time of the glycol and
inhibitor components and introduction of corrosive components such as chlorides 1. Approximately two
billion pounds of concentrated antifreeze is produced in North America each year, with about 80 % of this
sold to refill leaking cooling systems, an estimated 7 % used for factory fill, and 13 % for coolant
change-out. The amount of coolant changed-out in the past has traditionally been discharged to the sanitary
sewer. However, as a result of restrictive legislation on disposal and increasing raw materials cost, recycling engine coolant has and continues to become increasingly desirable. For example, the European
Union has just recently enacted environmental legislation that requires recycling of used engine coolant
Council Directive 2000/53/EC.
While the idea of designing products for recycling is superior to simple disposal, the public perception
of recycling is typically that the recycled product is less in quality. Recently this has been coined downcycling, with the term upcycling meaning that the product quality would be as good or better than its
nonrecycled counterpart 2. Some antifreeze recycling methods do indeed result in downcycled product
compared to virgin coolants; however, other technologies have been successfully employed to yield upManuscript received April 21, 2006; accepted for publication February 12, 2007; published online April 2007. Presented at ASTM
Symposium on Engine Coolant Technolgies: 5th Volume on 17 May 2006 in Toronto, Canada; W. Matulewicz, Guest Editor.
1
Cummins Filtration, Cookeville, TN.
2
EET Corporation, Harriman, TN.
26
HUDGENS ET AL. ON MEMBRANE TECHNOLOGIES 27

TABLE 1Candidate used coolant treatment technologies.
Technology
GRAVITY SEPARATION
Open Tank
Plate or Tube
Centrifuge
Primary Function
Side-Streams
Free Oil and Dirt Removal

Oils, Fuels, Sludge

Oils, Fuels, Sludge
Oils, Fuels, Sludge
CHEMICAL TREATMENT
Precipitation
Demulsification
Coagulation/Flocculation
Alter Solubility of Metals

Demulsify Soluble Oil
Conglomerate Particles
Precipitants
Oil
Sludge
Particle Separation,
Filtration, Absorption
Filters
Media
MEMBRANE
Ultrafiltration
Nanofiltration
Reverse Osmosis
Soluble Oil Removal

Multivalent Ion Removal
Aqueous Salts
Reject, Cleaner
Wastewater and
Membranes
ELECTRO-MEMBRANE
Electrodialysis
Continuous Deionization
Removal of Charged Ions

Removal of Charged Ions
Brine, Membranes
Brine, Membranes
Water Evaporation,
Salt-Out
Wastewater,
Still Bottoms
Dissolved Organics, Color

Removal of Trace Ions
Carbon
Resins
PARTICLE FILTRATION
Cartridge/Bag
Depth/Media
DISTILLATION
POLISHING
Carbon adsorption
Ion Exchange
cycled coolant. Since recycling engine coolant has become commercially available, the different methods
that have been offered include micron filtration, chemically-assisted filtration, centrifugation/filtration,
vacuum distillation, nanofiltration/reverse osmosis, and ion exchange/filtration 312. There are considerable separation efficiency differences between these various processes. The originally developed recycling method, conventional filtration alone 1 m, is not adequate to provide complete purification of
spent coolant, since it cannot remove degradation products and dissolved solids and corrosive species to
provide a consistent finished product with a reduced/known inhibitor balance. Dissolved solids and corrosive species include water impurities, such as chlorides, sulfates, residual inhibitors such as borate,
phosphate, silicate, carboxylic acids, and degradation products of glycol primarily glycolate and formate.
Removing a large portion of these total dissolved solids TDS while achieving high recoveries in a
recycling process is key to recycling economics, since nonrecovered coolant represents lost product and
also must be subsequently disposed. Consequently, the desalting technology unit operations required to
remove TDS and produce on-specification products at high recoveries are the most essential part of any
recycling process. However, antifreeze recycling involves not only the combination of physicochemical
separations to produce a glycol or glycol/water base stock of sufficient purity to reformulate to antifreeze,
but also additive package reformulation to ensure the recycled product performance properties are equivalent to its virgin nonrecycled coolant counterparts. Ingredients in these processes that ensure on- or
off-site success are good quality control and assurance, a well engineered and responsibly operated process, and OEM approved and proven reinhibition glycol additive package technology that should, ideally
at least, integrate with the recycling method selected.
A number of separation techniques have been proposed and are actually in use for recycling used
engine coolant from the vehicular service industry 312. The methods predominately employ, alone or in
combination, one of the following unit operations:
Vacuum Distillation
Membrane Separation
Ion Exchange
These technologies have been under various stages of development for the past 15 to 20 years. The
FIG. 1Pressure-based and ion exchange-based membrane processes.

most predominant candidate treatment technologies, separation function, and side-streams generated are
shown in Table 1. In all these technologies, separating a large portion of TDS from the coolant in the
recycling process is key. The key desalting also called desalination or desalinization technologies that
have been developed over the years are both thermal and membrane-based separation techniques. The
desalting technologies are essential unit operations required to produce an on-specification concentrate or
prediluted recycled product and include any one or a combination of vacuum distillation, membrane
separation, or ion exchange. The thermal and membrane-based desalting devices essentially separate a
saline solution into two streams: one with a low concentration of dissolved salts and the other containing
the remaining dissolved salts often referred to as the concentrate or brine stream. It is important to realize
that desalting processes do not produce more pollutant material or mass; they merely redistribute concentrate that which is present in the feed stream. For used coolant recycling, these technologies are the
same as used in desalting drinking water, with the same inherent advantages and disadvantages, plus
problems caused by the presence of high levels of ethylene glycol EG.
While many early antifreeze studies and recyclers touted each of the recycling technologies as suitable
for producing acceptable product, practical experiences have shown that a commercially successful recycling operation will use multi-stage processes in order to produce recycled coolant meeting OEM requirements. Indeed, for those facilities using only a single unit operation, the danger of process upsets resulting
in inadequate product is particularly great, as waste coolant feeds typically have varying contaminant
levels and contain a range of corrosion inhibitors and additives silicates, organic acids, etc. that can
impact treatment and reinhibition. Some recycling facilities have produced and marketed product that led
to cooling system damage and engine failure, either as a result of not sufficiently removing contaminants
or inadequately reformulating with corrosion inhibitors and other additives 13,14. A primary cause of
these failures and of critical importance in any recycling process, but unfortunately one in which many
recyclers fall short, is removal of corrosive inorganic ions. These include chloride and glycol degradation
products that can cause coolant system failure. Also unfortunately, these failures have also caused many to
skeptically view antifreeze recyclers out of concern that the technologies used cannot consistently produce
a product as good as virgin coolant.
As shown in Fig. 1, the goal of this study was to examine the separation characteristics of two unit
operations commonly used in recycling systems for removing corrosive species, nanofiltration NF, which
is typically misidentified as reverse osmosis RO, and electrodialysis ED, in order to determine if these
technologies could effectively and consistently produce recycled product meeting OEM and virgin nonrecycled coolant specifications for corrosive and other problematic species. Studies were done with a wide
variety of virgin coolants to identify problems that the two unit operations could potentially encounter with
the various coolant additives. The studies also examined the impact of different types of membranes
available for RO/NF and ED on separation of corrosive species and additive components and process
productivity. In addition, the separation characteristics effects on potential corrosion reinhibition strategies
were examined. Finally, studies with actual used coolants were performed to determine if these technologies could produce a product equivalent to virgin coolant, individually or in combination.
RO/NF and ED Terminology
The RO or NF process is relatively simple in design; a schematic is shown in Fig. 2a, and Fig. 2b
identifies the three streams and associated variables that are associated with a pressure-based membrane
FIG. 2(a) Schematic of a pressure-based membrane system and (b) pressure-based membrane streams
and terminology.
process 15. The water or solvent e.g., EG flow through the membrane is reported in terms of water or
solvent flux, Jw, which is volumetric or mass product flow rate through the membrane divided by the
membrane area; typical units are gallons per square foot per day gfd. Water flux can typically be
expressed as a function of pressure as
Jw = AP
where A is termed the water or solvent permeability constant and is particular to a particular membrane,
P is the applied pressure across the membrane, and represents the osmotic pressure difference across
the membrane. As the equation indicates, higher pressures across the membrane serve to increase flux,
while higher osmotic pressure differences across the membrane decrease flux. Degree of separation in
pressure-based membranes is reported in terms of rejection, R, defined as
R=1
CP
CF
where C P is the product permeate concentration and CF is the feed concentration, respectively. Finally,
recovery is defined as the ratio of final product volume to feed volume.
It is important to note the subtle but important difference between RO and NF. Traditional RO
membranes typically have high salt rejection for both monovalent and multivalent ions as well as many
organics and are typically capable of producing high purity water in a single pass. This contrasts with NF,
for which size and ionic charge play major roles in separation characteristics: large organic species such
as dyes and multivalent charged anions such as sulfate and phosphate are much more highly rejected by
NF membranes than monovalent ions such as chloride and nitrate 15. While antifreeze recycling with RO
is many times claimed by commercial recyclers, further investigation reveals their actual use of NF
membranes. It is important to note the distinction to avoid misperceptions concerning the separation
characteristics that can be achieved with NF as opposed to traditional, high rejection RO. While traditional
RO has been used for ethylene glycol concentration, typically these applications have been at very low
glycol concentrations 16.
The ED process is also relatively simple in design 17. A flow diagram identifying the streams of the
ED process is shown in Fig. 3a, and a schematic showing the ED cell is shown in Fig. 3b. Cations and
FIG. 3(a) Schematic of ED process and (b) schematic of ED cell.

anions are transported from the feed diluate stream compartments through the ion exchange membranes
into the concentrate brine stream compartments under the influence of the applied electrical potential
difference.
Antifreeze Terminology and Recycling Specifications
The majority of coolants currently on the market are based on EG. The EG-based coolants use three broad
classes of inhibitors to control coolant system corrosion:
Conventional additives, such as silicates, borates, nitrates, and nitrites.
Organic acid technology OAT based additives, such as 2-ethylhexanoic acid, sebacic acid, and
benzoic acid.
TABLE 2Recycled Coolant Specifications.
Parameter
Total Glycol Degradation
Acids, mg/L
Glycolate/Formate
Chloride, mg/L
Sulfate, mg/L
Nitrite, mg/L as NaNO2
Nitrate, mg/L as NaNO3
% Glycol
New Coolant
Specification
ASTM
D 4656
200
U.S. Military
TACOM
Recycled
Limits
1200 max
Recycled
Coolant
Specification
ASTM D 6471
N/a
25 max
50 max
N/a
N/a
50 min
25 max
N/a
1200 min
N/a
50 min
33
140
N/a
N/a
50 min

TABLE 3RO/NF membrane properties.
Polymer Type
Thin-film
composite,
polyamide
Standard Test Conditions

500 ppm calcium chloride, 70 psi
2000 ppm magnesium sulfate, 70 psi
Standard
Water Flux
gfd
37
31
Nanofiltration
Thin-film
composite,
polyamide
500 ppm calcium chloride, 70 psi

20
17
3550
97
NF-C
Nanofiltration
Thin-film
composite,
polyamide
magnesium sulfate, 100 psi
39
98
NF-D
Nanofiltration
Thin-film
composite,
polyamide
22
98
NF-E
Nanofiltration
Cellulose acetate
2000 ppm, sodium sulfate, 220 psi
28
92
NF-F
Nanofiltration
Thin-film
composite,
polyamide
2000 ppm NaCl, 70 psi

19
24
8595
97
NF-L
Nanofiltration
Thin-film
composite,
polyamide
31
96
RO-G
Reverse
Osmosis
Thin-film
composite,
polyamide
500 ppm sodium chloride, 100 psi
29
9899
RO-H
Reverse
Osmosis
Thin-film
composite,
polyamide
2000 ppm sodium chloride, 225 psi
26
99
RO-I
Reverse
Osmosis
Cellulose acetate
sodium chloride, 420 psi
24
97
RO-J
Reverse
Osmosis
Polyamide
26
99.5
RO-K
Reverse
Osmosis
Thin-film
composite,
polyamide
22
98.9
Membrane
No.
NF-A
Membrane
Class
Nanofiltration
NF-B
Standard
Rejection %
4060
97
Hybrid also called HOAT additives, which include both conventional components as well as OAT
components.
Table 2 lists virgin and recycled coolant ASTM specifications, as well as military recycled coolant
standards.
Experimental
Studies were carried out on lab scale NF/RO and ED systems. The General Electric Sepa Cross Filtration
CF II Med/High Foulant System was used for NF/RO studies. This system had an effective membrane area
of 140 cm2. The system was operated at 300 psi or 600 psi for selected RO membranes with 1.5 L of
feed; temperatures were maintained in the range 20 to 35 C. Feed flow rate was 7 8 L / min, sufficient to

TABLE 4IX membrane properties.
Cation Exchange Membrane
IX Membrane
Set No.
IX_ A
IX_ B
IX_ C
IX_ D
Membrane Type
Homogeneous,
Strong Acid
Homogeneous,
Strong Acid
Homogeneous,
Strong Acid
Heterogeneous,
Strong Acid Heat
Extrusion
Thickness Resistance
mm
ohm-cm2
0.18
3
0.16
0.16
0.34
10
Anion Exchange Membrane

Exchange
Capacity
meq/g
1.7
Exchange
Thickness Resistance
Capacity
2
ohm-cm
Membrane Type
mm
meq/g
Homogeneous,
0.17
3
1.6
Strong Base
2.3
Homogeneous,
0.18
1
2.8
Strong Base
2.3
Homogeneous,
0.17
1.4
2.0
Strong Base
Not Known Heterogeneous,
0.34
7.5
Not Known
Strong Base
Heat Extrusion
minimize polarization effects. Initial screening runs were at least 15 min in duration, with test runs at least
30 min approximately 20 50 % recovery. The NF/RO membranes studied are listed in Table 3 along
with membrane properties. Integrity of the membranes before coolant studies were verified with standard
salt solution. EET Corporations High Efficiency Electrodialysis HEED Laboratory/Bench-Scale System was used for ED studies with 1 L of feed solution. A total of ten cell pairs CPs with an area of
71.1 cm2 per cell was used for each membrane study, with an applied potential of 2 V/CP applied across
the ED cell and a feed rate of 5.7 L / min. Temperatures were maintained in the range 20 to 35 C. Table
4 lists properties of the four ion exchange membrane sets studied. Separation characteristics with each
membrane were verified with standard salt solutions prior to coolant studies. Both the NF/RO and ED
systems were operated in batch mode, with either reject NF/RO or diluate ED recycled to the feed tank
during the course of the run.
Feed solutions consisted of virgin coolants spiked with corrosive water and diluted with deionized
water to 40 % ethylene glycol content and containing 200 ppm chloride and 1500 ppm sulfate. Table 5
lists properties of the coolants. These included conventional coolants, OAT coolants, and hybrid HOAT
coolants with a mixture of conventional and organic acid additives. The used coolant represented a typical
batch collected at EET Corporations antifreeze recycling facility in late 2005. The used coolant was
pretreated using filtration and activated carbon. Concentrations of contaminants and other species were
determined by ion chromatography and high performance liquid chromatography HPLC. Ethylene glycol
content was determined by diffraction.
Results and Discussion
The production rate and separation efficiency of RO, NF, and ED processes were found to be dependent
both on membrane characteristics and coolant chemistry. Table 6 presents NF/RO screening results with
either coolant C1 a conventional coolant, coolant C5 a hybrid or HOAT coolant, or coolant C10 also
TABLE 5Coolant Properties.
Coolant No.
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
Type
Conventional EG
Conventional EG
HOAT EG
HOAT EG
HOAT EG
HOAT EG
OAT EG
OAT EG
HOAT PG
HOAT EG
Major Components
Phosphate, Borate, Nitrate, Silicate
Nitrite, Borate, Nitrate, Silicate
Phosphate, Nitrite, Borate, Molybdate, Sebacic Acid
Nitrite, Nitrate, Molybdate, Sebacic Acid
Benzoic Acid, Borate, Nitrate, Silicate
Sebacic Acid, Nitrate, Tolyltriazole, Phosphate
2-Ethylhexanoic Acid, Tolyltriazole
2-Ethylhexanoic Acid, Tolyltriazole, Molybdate,
Sebacic
Acid, Nitrite
Phosphate, Nitrite, Molybdate, Borate, Sebacic Acid
Sebacic Acid, Benzoic Acid, Molybdate, Nitrate

TABLE 6RO/NF membrane initial screening.
Membrane
NF-A
NF-C
NF-B
NF-D
NF-E
NF-F
NF-L
RO-G
RO-G
RO-H
RO-H
RO-I
RO-J
RO-K
Coolant
50 % EG Solution C10 HOAT
40 % EG Solution C1 conv.
Feed Pressure
psi
300
300
300
300
300
300
300
300
600
300
600
300
300
300
Flux gfd
22
20
6
11
3
1
13
1
1
1
1
2
1
1
Conductivity
Rejection %
78 %
73 %
85 %
74 %
52 %
75 %
44 %
a
87 %
a
a
30 %
a
a
Insufficient product volume to determine rejection.
FIG. 4Membrane flux for various NF and RO membranes with 40 % EG coolant solution.
FIG. 5Conductivity rejection for various NF and RO membranes with 40 % EG coolant solution.
FIG. 6NF membrane fluxes with eight different coolant solutions.

a hybrid. The table confirms that traditional brackish water RO membranes have very low productivities
at the lower pressures 300 psi typically used in brackish water systems, with some having no productivity at all, even for relatively low recovery rates. In fact, all the RO membrane flux rates are too low to
be considered practical. Even at the relatively high pressure 600 psi studied with two RO membranes,
the productivity was very low. Also, coolant chemistry had very little impact on productivity of the
traditional RO membranes: production rates of both conventional and hybrid coolants were similar. In
contrast, the NF membranes exhibited much better productivities. These are compared to those of the RO
membranes in Fig. 4. As would be expected, the more open, lower salt rejecting NF membranes generally
had higher production rates. Conductivity rejection for the eight different spiked coolants covered a wide
range, from 40 % for an NF membrane to almost 90 % for a traditional RO membrane although in several
traditional RO cases, production rate was too low to obtain enough sample to measure conductivity!.
Figure 5 summarizes conductivity rejection with a hybrid coolant. While conductivity alone does not
indicate coolant quality or correlate well with TDS content, it does provide an indication of the membrane
separation efficiency.
While membrane class NF versus RO was critically important, coolant chemistry also impacted
separation characteristics, including for the NF membranes. Figure 6 summarizes average production rate
and production rate ranges encompassing all eight coolants for the four NF membranes determined in the
initial screening to be practical. Conductivity rejections for these are given in Fig. 7. A given coolant type
resulted in as much as 38 % increase or decrease in membrane flux and up to 28 % increase/decrease in
FIG. 7NF membrane conductivity rejections with eight different coolant solutions.

TABLE 7Comparison of EG and PG-based coolant separation properties with NF Membrane A.
Coolant
C5 HOAT
C9 PG HOAT
Initial Feed
Conductivity
S / cm
6160
4520
Recovery %
23.9
15.9
Permeate
Conductivity
S / cm
3399.9
2801.5
Water
Flux gfd
20.1
13.3
Conductivity
Rejection
48.6 %
38.6 %
conductivity removal. Furthermore, the specific membrane also played a key role, as membranes with
similar traditional salt solution production rates and rejections see Table 3 had substantially different
production rates and conductivity rejections with the 40 % EG coolant solutions. For example, looser
NF membrane NF-A had essentially the same or better conductivity removal as tighter membrane NF-C,
with NF-A having much higher production rate; with standard salt solutions, these membranes typically
have more similar separation properties. This indicates the importance of considering not only standard
salt rejection and water flux, but also the differences in interaction of the ethylene glycol and other
constituents of the coolant with the specific membrane used. Key differences between the NF membranes
that have the potential to impact productivity and separation with EG-based coolants include the specific
membrane polymers and membrane charge, membrane structure i.e., thin-film composite versus asymmetric, fouling resistance, and relative porosity. In this study, thin-film composite NF membranes based
on aromatic polyamide with a more open pore structure performed better overall when considering both
flux and removal on all types of coolants compared to both thin-film composite aromatic polyamide
membranes with a tighter pore structure and asymmetric cellulose acetate NF membranes.
In each case, the NF membrane fluxes with the 40 % EG solutions were lower than would be expected
for similar concentration water solutions. This is in part the result of the higher viscosity of EG compared
to water: the higher viscosity EG would be less efficiently transported through the membrane than water
at the same pressure. In addition, it is expected that EG would be less absorbed by the membrane than
water. The combination of these factors would result in a lower flux and a slight decrease of EG concentration 1 to 2 % in the permeate product, which was observed in these studies. This behavior was also
observed with propylene glycol PG based coolants, which had lower flux than those of water solutions
and EG solutions. The PG coolants have even higher viscosities than EG and PG would be less absorbed
by the membrane than EG. Comparison of fluxes for coolant C5 hybrid, EG-based and coolant C9
hybrid, PG-based is given in Table 7.
Figure 8 better illustrates the effect of coolant type on nanofiltration flux. The flux for each membrane
was better with the conventional coolant and less productive with the hybrid or OAT-based coolants.
Rejection, shown in Fig. 9, was generally better for the OAT coolant and worse for the hybrid. These
figures also show the substantial flux and conductivity rejection variability of each membrane with the
different types of coolants. This trend was generally followed for all eight of the coolants studied for each
FIG. 8NF membrane fluxes with three different coolant types.
FIG. 9NF conductivity rejections with three different coolant types.

membrane, as indicated in Figs. 10 and 11 for membranes NF-A and NF-D. These figures also show the
flux and conductivity rejection of a typical pretreated used coolant; flux generally falls below that of the
spiked coolants, while rejection is higher.
Based on ion chromatograph and HPLC analyses, it was determined that the used coolant contained
additives typical of a mix of conventional, hybrid, and OAT-based coolants; Table 8 compares the species
in the virgin coolants to those in used coolant. It is informative to examine the individual species rejection,
as shown in Figs. 12 and 13 for the looser membrane NF-A and tighter membrane NF-D with the used
coolant. As would be expected, multivalent species such as sulfate, phosphate, and molybdate were
rejected well by the membranes, while monovalent species such as chloride, nitrite, and nitrate were
poorly removed. Glycol degradation acids, which would consist of primarily glycolic and formic acids,
were marginally rejected. It is expected the larger, more polar glycolic acid would be better removed than
the smaller formic acid. Silicate and borate, expected to be partially in the nonionized form at the feed pH
8 of the used coolant, was poorly removed. The lower rejection of these would be expected since both are
relatively small molecular weight compounds and so separation would be based primarily on charge; both
nonionized species passed through the membrane. The tighter membrane NF-D performed marginally
better than membrane NF-A; however, it is important to note that neither membrane NF-A nor membrane
NF-D produced a coolant that would meet specifications for reuse without further treatment. In particular,
chloride and glycol degradation acids were too high in the permeate products, even at the low recoveries
studied. Higher recoveries would result in even lower removal rates for these. For the typical coolant
FIG. 10NF membrane fluxes with spiked virgin coolants and pretreated used coolants.
FIG. 11NF conductivity rejections with spiked virgin coolants and pretreated used coolants.
organic additive species, shown in Fig. 13, removals of sebacic acid SA, 2-ethylhexanoic acid 2-EH,
and benzoic acid were excellent. All of these species would be present predominately in the ionic form and
so were rejected well by the charged NF membranes. Conversely, removal of tolytriazole was poor,
possibly because of its expected monovalent charge at the feed pH.
Examination of Figs. 12 and 13 in conjunction with Figs. 8 and 9 provide some insight into the flux
and conductivity rejection behavior for the coolants. In general, the conventional coolants contain substantial amounts of silicate, tetraborate, nitrites and nitrates, and phosphates. While the phosphate is well
removed, removal of the other species is only marginal and so overall conductivity rejection is low.
Species that are not rejected do not contribute to the osmotic pressure difference and so do not reduce the
pressure driving force across the membrane see Eq 1. As a result, flux with the conventional coolants is
high. Hybrid and OAT coolants contain substantial amounts of organic acids that are very well rejected by
the membranes. However, since these are rejected, there is a substantial osmotic pressure drop across the
membrane and corresponding drop in pressure driving force according to Eq 1 and decreases in flux
relative to those of the conventional coolants. As expected, the hybrid coolants, with a mixture of the
conventional components, organic acids, and molybdate, have fluxes that correlate with organic acid
TABLE 8Spiked virgin coolants and pretreated used coolant analyses.
Coolant Type 40 % Solution
Compound
Acids mg/L
Chloride mg/L
Sodium Nitrite mg/L
Sodium Nitrate mg/L
Sodium Phosphate mg/L
Sulfate mg/L
Sodium Molybdate mg/L
Sodium Tetraborate mg/L
Sodium Silicate mg/L
Tolyltriazole mg/L
Sebacic Acid mg/L
2-Ethylhexanoic Acid mg/L
Benzoic Acid mg/L
% EG
pH
C1
C2
C3
C4
C5
C6
Conventional Conventional HOAT HOAT HOAT HOAT
7
10
9
33
11
173
848
2988
1404
1178
782
464
180
1731
469
1430
865
455
243
175
1392
452
3311
1382
684
799
441
480
493
179
1661
767
14
1448
628
479
403
161
580
179
491
2601
1420
C7
OAT
46
C8
OAT
16
170
221
1307
786
1408
234
725
9
1415
1415
829
4710
512
1178
7506
821
11 622
38
9.8
37
9.9
5
37
10.1
37
9.8
9222
39
7.9
39
8.0
39
8.9
17
833
793
12 767
37
8.5
Pretreated
Used
Coolant
994
73
178
1014
1523
411
293
553
120
22
861
1871
1972
37
8.2
FIG. 12Inorganic species rejection by NF membranes for pretreated used coolant.
FIG. 13Organic species rejection by NF membranes for pretreated used coolant.
FIG. 14Electrodialysis system production rates with eight different coolant solutions.
FIG. 15Electrodialysis system conductivity removal with eight different coolant solutions.
content: those containing higher organic acid concentrations as well as molybdate, which is highly
rejected have lower fluxes and higher conductivity rejections while those with higher content of conventional coolant species silicate, borate, nitrite, nitrate have higher flux and lower conductivity rejections.
The lowering of pressure driving force due to high osmotic pressure difference across the membrane also
accounts for the low fluxes of traditional RO membranes: these tight membranes reject most species,
resulting in a relatively high osmotic pressure difference across the membrane and correspondingly low
flux. Similar trends in flux and rejection characteristics for the individual inorganic and organic species for
spiked virgin coolant types traditional, OAT, and hybrid were observed with the NF membranes, confirming the separation characteristics of the individual species in the pretreated used coolant.
As with the NF membranes, both IX membrane types anion and cation exchange membrane pair and
coolant type had substantial effects on productivity of the ED process. Figure 14 summarizes average
production rate and ranges for the four different ion exchange membranes studied with the eight spiked
coolant solutions. Conductivity removal is summarized in Fig. 15. Conductivity removals were substantially higher than those of the NF membranes since batchwise ED operation allows the feed solution to be
processed until either the target conductivity is achieved or no further reductions in conductivity are
possible. In most cases, feed conductivities 100 S / cm were possible with most coolant/membrane
combinations. However, membrane set IX_ D, heterogeneous ion exchange membranes, had a wider range
of final conductivities; in particular, conductivity reduction with some of the hybrid coolants was only
marginal. For the homogeneous membrane sets IX_ A, IX_ B, and IX_ C, removals were more consistent,
FIG. 16Electrodialysis system production rates with three different coolant types.
FIG. 17Electrodialysis system conductivity removal with three different coolant types.
with a minimal 96 % removal rate. In all cases, since the contaminants are transported through the IX
membranes as opposed to the feed solution as in the NF process, recoveries were high at 98 %, with
typically 2 % EG loss into the brine stream.
Figures 16 and 17 provide productivity and conductivity removal for the four different IX membrane
sets for three coolant types conventional, hybrid, and OAT. In general, productivity was higher with the
conventional coolants, followed by the hybrid and the OAT coolants. Conductivity removal was essentially
the same for each coolant type and for each membrane. In general, the higher the exchange capacity and
lower the membrane resistance of the anion exchange membrane as with IX_ B, the higher the productivity with the conventional coolant. However, these had no clear impact on the hybrid and OAT-based
coolants productivity. Figures 18 and 19 compare separation characteristics of the three coolant types with
that of used coolant with membrane set IX_ C, a fouling resistant membrane. Production rate was similar
to that of the OAT coolant, with excellent final conductivity removal.
Figures 20 and 21 provide percent removal of specific inorganic and organic species from the used
coolant with characteristics that were shown in Table 8 with membrane set IX_ C. Glycol degradation
acids, chloride, sulfate, nitrite, nitrate, phosphate, and molybdate were essentially completely removed
over the course of the run. Tetraborate and silicate, which were only partially ionized at the feed pH of the
used coolant 8, were removed to a lesser extent, as would be expected since nonionic species are not
significantly transported through the IX membranes. Tolyltriazole, sebacic acid, and benzoic acid, all
FIG. 18Electrodialysis system production rates with spiked virgin coolants and pretreated used
coolants.
FIG. 19Electrodialysis system conductivity removal with spiked virgin coolants and pretreated used
coolants.
mostly in the ionized form, were also almost completely removed. Removal of 2-ethylhexanoic acid was
less than the other organic acids, possibly due to the side chain branching of the compound, resulting in a
lower transport number in the IX membrane compared to the divalent sebacic acid and the smaller
tolyltriazole and benzoic acid. Comparison of Figs. 18 and 19 with Figs. 12 and 13 shows that the ED
process is capable of reducing both contaminants and the residual inhibitors/additives to a greater extent
than the NF process, even at high recoveries. However, the ED product does have a slight color, usually a
visible yellow tint. While many of the dyes are ionic, these tend not to be completely transported across the
IX membranes. Also, as with the NF studies, ED removals of individual inorganic and organic species in
virgin spiked coolants followed the same trends as the individual species removals in the pretreated used
coolant.
As discussed above, a single process usually falls short of producing an acceptable recycled product,
particularly if the goal is to produce coolant meeting virgin specifications. While the ED process alone can
nearly meet all requirements, the product does contain a slight color. Conversely, the NF process is better
at removing color. Permeate from the NF process is water white, while monovalent species removal is
usually unacceptable. However, an integrated approach combining these two processes utilizes the advantages of each. NF produces a permeate product that is water white with reduced conductivity and contaminants, and the ED process treatment of the permeate product further reduces the conductivity/
contaminants to virgin specifications. Since not all species need to be removed by the NF process, a lower
FIG. 20Inorganic species removal by electrodialysis system for pretreated used coolant.
FIG. 21Organic species removal by electrodialysis system for pretreated used coolant.
rejecting, higher flux membrane may be used to lower system capital and operating cost. In addition, ED
process production rate also increases since part of the species of concern has been removed by NF. Table
9 shows results from a run simulating this process using NF_ A and membrane set IX_ C. The NF
subprocess partially reduced the multivalent species and a fraction of the organic acids, and the ED
subprocess removed the remaining species to near virgin ethylene glycol specifications. Due to the reduced
feed species, ED system productivity increased by 30 %.
Figures 12, 13, 20, and 21 and Table 9 show the individual contaminant and additive species removal
efficiencies of NF, RO, and an integrated process with the used coolant; as indicated above, the used
coolant represents a mix of conventional, OAT, and hybrid coolants. In general, NF removals of chlorides
and conventional additive species were low. However, if the chloride levels met specifications, the presence of the conventional additives would not be a great issue if the recycled coolant reinhibition package
consisted of compatible conventional additives. Similarly, the presence of residual organic inhibitors in the
NF or ED recycled product would not have a great impact on a recycled product reformulated with
compatible OAT-based additives. However, some incompatibilities might exist between some conventional
and OAT-based additives. For example, high silicate levels may not be desirable in certain formulations of
TABLE 9Integrated process separation characteristics with pretreated used coolant.
Integrated Process Test Samples
Compound
Acids mg/L
Chloride mg/L
Sodium Nitrite mg/L
Sodium Nitrate mg/L
Sodium Phosphate mg/L
Sulfate mg/L
Sodium Molybdate mg/L
Sodium Tetraborate mg/L
Sodium Silicate mg/L
Tolyltriazole mg/L
Sebacic Acid mg/L
2-Ethylhexanoic Acid mg/L
Benzoic Acid mg/L
% EG by Brix
pH
ED
Used Coolant Pretreated NF Permeate
ED Diluate Concentrate
Overall
Feed
Used Coolant
Product
NF Concentrate Product
Brine
Removal %
100.0 %
1088
994
1018
1030
1
190
50
190
1171
1678
197
315
631
121
207
2356
2132
2621
37
8.1
73
178
1014
1523
411
293
553
120
22
861
1871
1972
37
8.2
73
184
1088
393
109
61
514
84
17
0
957
1891
37
8.1
12
47
365
10328
2384
1649
699
184
0
7075
6178
2209
41
8.4
1
1
1
1
1
1
142
67
0
0
0
0
36
5.8
56
10
0
134
112
33
96
20
0
0
184
504
1
8.4
99.0
99.7
100.0
99.9
99.7
99.8
77.5
44.5
100.0
100.0
100.0
100.0
%
%
%
%
%
%
%
%
%
%
%
%
OAT-based coolants, in which case the silicate levels must be reduced substantially more, with corresponding drop in process productivity. Ideally, each coolant could be characterized and processed to remove
corrosive species and degradation acids to meet corrosive species specifications, with further processing
limited only to the extent necessary to reduce species incompatible with the planned reformulation additives. However, due to the expense and lag time of the analytical methods, a more practical alternative is
to use operating experience with NF, ED, or NF/ED hybrid processes, knowledge of the robustness of the
planned reformulation package, and gross measures such as conductivity to guide extent of processing.
Establishment of levels such as conductivity at which corrosive species meet specifications and inhibitor
additives are acceptable for reformulation could greatly improve process productivity and overall recycling
economics.
Conclusions
Both coolant chemistry and membrane type have been found to tremendously impact productivity and
extent of separation for both pressure-based membrane RO/NF and ion exchange-based membrane
systems ED. Fluxes of traditional, high salt rejection RO membranes have been verified to be impractical, despite claims by many recyclers that they use RO. NF membrane productivities are acceptable, but
conductivity and contaminant removal range from only marginal to good, with none of the studied NF
membranes capable alone of producing recycled coolant meeting virgin coolant specifications. While the
removals of most organic acids and divalent species were excellent, removal of monovalent species such
as chlorides and nonionized species such as silicates were poor. The ED process was capable of reducing
conductivity to very low levels and well as removing individual contaminants and other ionic components,
although some slight color remained. The productivity of the ED was greatly improved and the product
solution was water white when it was combined with an NF process, with ED treating the NF permeate.
Ideally, the degree of removal of the residual inhibitors could be customized for each individual batch of
used coolant based on the planned reinhibition additive and laboratory analyses for each species present in
the coolant. Practically, the robustness of the type of reinhibition additive to be used and conductivity can
serve to guide the extent of deionization required.
References
1
2
3
4
5
6
7
8
9
Coburn, C. B., Hudgens, R. D., and Mullen, M. D., Environmental Effects of Engine Coolant
Additives, SAE Technical Papers, Engine Coolants and Cooling Systems, SP-1456, p. 87, International Congress and Exposition, Detroit Michigan, 14 March, 1999.
Leadership and InnovationDesigning the FutureNewsweek, 16 May, 2005.
Frye, D. K., Chan, K., and Pourhassanian, C., Overview of Used Antifreeze and Industrial Glycol
Recycling by Vacuum Distillation, Engine Coolant Testing: Fourth Volume, ASTM STP 1335, R.
E. Beal, Ed., ASTM International, West Conshohocken, PA, 1999, p. 236.
Haddock, M. E. and Eaton, E. R., Recycling Used Engine Coolant Using High-Volume Stationary
Equipment, Engine Cooling Testing, Fourth Volume, ASTM STP 1335, R. E. Beal, Ed., ASTM
International, West Conshohocken, PA, 1999, pp. 251260.
Kugn, W. and Eaton, E. R., Development of Mobile, On-Site Engine Coolant Recycling Utilizing
Reverse-Osmosis Technology, Engine Coolant Testing, Fourth Volume, ASTM STP 1335, R. E.
Kurio, N., Shirahase, T., and Oda, H., Development of Coolant Recycling Technology, JSAE Rev.,
Vol. 16, 1995, p. 61.
Jehle, W., Staneff, T., Steinwandel, J., and Wagner, B., Work-up of Spent Coolant Ethylene
Glycol by a Membrane Hybrid Process, Chem.-Ing.-Tech., Vol. 66, 1994, p. 671.
Richardson, R. C., A Multi-Stage Process for Used Antifreeze/Coolant Purification, Engine Coolant Testing: Third Volume, ASTM STP 1192, R. E. Beal, Ed., ASTM International, West Conshohocken, PA, 1993, pp. 258275.
Hercamp, R. D. and Remiasz, R. A., Coolant Maintenance and Extension of Coolant Life for Light
Duty Vehicles, ASTM Special Technical Publication 1192, ASTM International, West Conshohocken, PA, 1993, p. 248.
10
11
12
13
14
15
16
17
Huff, J. R., Using Reverse Osmosis to Recycle Engine Coolant, SAE Technical Paper Series,
921635, SAE, Warrendale, PA, 1992.
McCosh, D., All the Ways to Recycle Antifreeze, Popular Science, Vol. 241, 36, 1992.
Gavaskar, A. R., Olfenbuttel, R. F., Jones, J. A., and Webb, P. R., Automotive and Heavy-Duty
Engine Coolant Recycling by Filtration, EPA Report, EPA/600/2-91/066 PB92-126804, Oct.
1991.
Penray Technical Bulletin 99.001, The Penray Companies, Elk Grove Village, IL, www.penray.com,
1999.
Antifreeze Recycling Users GuideU.S. Army Tank-automotive and Armaments Command Research, Development, and Engineering Center, Warren, MI 48397-5000, March 2005.
Ho, W. S., and Sirkar, K. K., Eds., Reverse Osmosis, Membrane Handbook, Van Nostrand
Reinhold, NY, 1992.
Preliminary Data Summary, Airport Deicing Operations, U.S. EPA, EPA-821-R-00-016 August
2000.
Strathmann, H., Ion-Exchange Membrane Separation Processes, Elsevier Science, 2004.

Paper ID JAI100502
Bo Yang,1 Filipe J. Marinho,1 and Aleksei V. Gershun1
New Electrochemical Methods for the Evaluation

of Localized Corrosion in Engine Coolants
ABSTRACT: Due to the need of increasing energy efficiency, reducing pollution and lessening dependency
on petroleum, vehicles using more advanced propulsion technologies such as fuel cell and hybrid electric
e.g., gasoline-electric or diesel-electric hybrid power are being developed constantly. At the same time,
extensive development efforts are being devoted to research aiming to increase the use of lighter metals
such as magnesium alloys in todays engines. New engine coolants are often required to meet many of
these new developments and the associated changes in cooling system requirements. Since corrosion
protection is one of the key performance parameters for engine coolants, new and more effective corrosion
measurement methods are useful for evaluating old and developing new coolants to meet the needs of new
cooling systems or having improved corrosion protection performance, or both. Particularly, new electrochemical methods capable of more reliable, quantitative, and fast ideally, real-time measurements of
localized corrosion such as pitting, crevice, and under-deposit corrosion, and corrosion under heat rejecting
conditions are highly desired. Existing ASTM test methods for engine coolants either rely on inspection of
the sample after a relatively long exposure period to determine the extent of localized attack or do not yield
results directly related to localized corrosion. In this paper, coupled multi-electrode sensors test and simulated localized corrosion cell technique are compared and discussed to gain new insight for facilitating the
development of more effective inhibited coolants.
KEYWORDS: antifreeze/coolant, localized, pitting, crevice, galvanic corrosion, aluminum
Introduction
To satisfy the customers desire for more power, comfort, and safety, and to meet the need of lower fuel
consumption and reduced exhaust emission, new vehicle technologies are being developed constantly.
Extensive efforts are being devoted to research to develop new and more environmentally friendly propulsion technologies, such as fuel cell and petroleum-hybrid electric power, and new material technologies, and to explore methods to increase the use of lighter metals or materials, or both. Since corrosion
protection is one of the key performance parameters for engine coolants, new and more effective corrosion
measurement methods are useful for developing new coolants to satisfy the needs of the new cooling
systems or to improve corrosion protection performance, or both.
It is recognized that the majority of corrosion phenomena that occurs in engineering systems is
nonuniform or localized 14. In vehicle engine cooling systems pitting, crevice, under-deposit corrosion,
galvanic corrosion, and erosion-corrosion or cavitation are some of the most commonly observed forms
of localized corrosion. Existing industry test methods usually rely on inspection of the sample after a
relatively long exposure period to determine the extent of localized attack or used tests which do not yield
results directly related to localized corrosion 59. One electrochemical method is used by many to
determine the repassivation potential of metal as a measure of relative susceptibility to pitting corrosion in
engine coolants 10. However, this method is conducted at room temperature and does not provide a
quantitative localized corrosion rate. Thus, methods capable of more reliable, quantitative, and fast ideally, real-time measurements of localized corrosion such as pitting, crevice, and under-deposit corrosion,
and corrosion under heat rejecting conditions are highly desirable for developing new coolants with
improved corrosion protection performance.
Since the 1990s, significant advancements have been made in developing more effective, reliable and
Manuscript received February 22, 2006; accepted for publication October 4, 2006; published online November 2006. Presented at
1
Honeywell, Danbury, CT 06810
45
quantitative measurement techniques for localized corrosion. In the last 10 to 15 years, a number of newly
developed techniques such as electrochemical noise, scanning vibrating or reference electrode, zeroresistance ammeter ZRA-based occluded cell techniques, differential flow cells, and coupled multielectrode sensors are being used increasingly to measure the rates of localized corrosion 1120. Particularly, two of the methods, namely the differential flow cell or more appropriately the simulated localized
corrosion cell and coupled multi-electrode sensors, appear to be most promising for use as real-time,
reliable, and quantitative measurements of rates of localized corrosion such as pitting, crevice, underdeposit corrosion, and galvanic corrosion.
The coupled multi-electrode sensor, also called the wire-beam electrode method, was developed for
measuring localized corrosion and other heterogeneous electrochemical processes by Tan 12,13. The
multi-electrode sensor probes are usually fabricated from an array of nominally identical metal wire
electrodes typically 1 mm in diameter embedded in insulating material e.g., an epoxy resin. The surface
of one end of the wire electrodes is exposed to the test solution. The other end of the wire electrodes are
coupled electrically via zero-resistance ammeters or an equivalent sensing instrument. Localized corrosion
can be estimated by measuring the coupling current flowing into or out of the selected wire electrode. A
further refinement was introduced by Yang and coworkers by incorporating the use of statistical parameters
i.e., standard deviation and mean values of the measured coupling current distribution of the multielectrode probe to calculate the maximum penetration current as a representation of localized corrosion
rate 14,15. The coupled multi-electrode sensors have been used as a real-time localized corrosion monitor for carbon steel, stainless steels, aluminum, copper, and several nickel-based alloys in various environments, including cooling water, simulated sea water, under salt deposits in air, concentrated chloride
solutions, and process streams of chemical plants at elevated temperatures 14. However, the localized
corrosion rates determined by the coupled multi-electrode sensor probes have not been verified by independent reliable measurements on the same electrodes. In addition, similar to scanning vibrating electrode
and ZRA-based occluded cell techniques, the accuracy of the localized corrosion rate obtained depends on
the reliability of the assumption that there is only metal dissolution current associated with the anodic
reaction on the wire electrode having the highest coupled anodic current 14.
The differential flow cell or more appropriately simulated localized corrosion cell technique was
developed recently for the real-time, on-line, and reliable measurement of localized corrosion rates of
metals in industrial water systems 2,16,18. In this technique, a unique combination of linear polarization
resistance LPR and zero resistance ammeter measurements ZRA is used to obtain the rate of localized
corrosion such as pitting, crevice/under-deposit, microbiologically influenced corrosion for metals including carbon steel and admiralty brass in aqueous solutions 19. The measurements are carried out in an
electrolytic cell simulating the essential features of the propagating localized corrosion conditions for a
given systems conditions e.g., a differential flow cell is used to simulate the localized corrosion conditions in cooling water systems. The simulated localized corrosion cell contains one or more anodes or
preferential attack areas with a small exposed surface area and one cathode or nonpreferential attack
area with a much larger exposed surface area. The anodes and the cathode of the cell are normally coupled
electrically via the ZRA to simulate the localized corrosion conditions. The ZRA measurements are used
to provide the component of the localized corrosion current that results from the galvanic cell interaction
between the large cathode and the small anodes. The LPR measurements on the anodes provide the
component of the localized corrosion current that results from the contributions of cathodic reactions e.g.,
oxygen reduction, hydrogen evolution inside the pits, etc. occurring on the anodes toward their own
corrosion. The cell used in this method simulates faithfully the localized corrosion conditions under the
studied conditions. Based on this technique, a new localized corrosion monitor LCM capable of monitoring both localized and general corrosion rate in real-time was developed. It has been used extensively
in laboratory studies and field applications. Good agreement was obtained between the corrosion rates
determined by using a calibrated microscope to measure the penetration depth, and the time average
corrosion rates determined electrochemically from the LCM on the same electrode samples under various
laboratory test conditions 16. Under properly chosen simulation conditions, the corrosion rate results
both localized and general rates obtained from the LCM in the field applications were also in agreement
with independent physical measurement i.e., coupons and heat exchanger inspection e.g., ultrasonic
inspection or operation results e.g., service life or leakage frequency obtained under comparable conditions 14. The LCM has been used successfully in many industrial cooling water systems, including
YANG ET AL. ON CORROSION IN ENGINE COOLANTS 47
open-recirculating and closed-loop cooling water systems in petroleum refineries, nuclear and fossil fuel
power plants, pulp and paper mills, food processing plants, and chemical processing industry plants. The
LCM was demonstrated to be very useful for localized corrosion monitoring and for the performancebased optimization and control of chemical treatments i.e., corrosion inhibitors, scale inhibitors, and
biocides in these systems.
In this paper, the coupled multi-electrode sensors and the simulated localized corrosion cell methods,
as well as conventional electrochemical and mass loss methods, are used to study corrosion of aluminum
and other alloys in engine coolants. Particularly, localized corrosion results related to pitting and galvanic
corrosion obtained from the two methods, i.e., coupled multi-electrode sensors and simulated localized
corrosion cell techniques, are compared and discussed to gain new insight for facilitating the development
of more effective inhibited engine coolants.
Experimental
Solutions
The base test solutions were prepared by mixing commercially available coolants with deionized water to
yield a coolant concentration of either 25 vol. % or 50 vol. %. Aqueous solution of 40 % w/v KF from
Spectrum Chemical Mfg. Corp. was used as the source of fluoride. Other components of the test solution
were sodium chloride ACS grade and commercial products supplied by the producers.
NanoCorr Coupled Multi-electrode Sensor (CMS) Tests
A Corr Instrumnets NanoCorr Coupled Multi-electrode Sensor Analyzer with CorrVisual Software, Version 1.0.3 was used to determine the localized corrosion rates of cast aluminum in the test solution. In this
study, a 25-electrode sensor array probe made of either 25 cast aluminum SAE 329, UNS A23190 square
wire having an exposed surface area of 1 mm2 was used. The 25 wire electrodes sealed in epoxy and
spaced uniformly in a 1.2 by 1.2 cm matrix array were connected electrically via the NanoCorr Coupled
Multi-electrode instrument. The coupled multi-electrode probe simulates the corrosion conditions of a
conventional one-piece electrode surface having an exposed surface area of about 1.4 cm2. One can obtain
a localized corrosion rate as a function of time from the probe by measuring the coupling current from
each individual electrode in the probe and performing statistical analysis of the measured data. The
localized corrosion rate or maximum penetration rate, hmax is calculated by the data acquisition software
according to the following equation:
hmax = 2.5 + ImeanWe/FA
where and Imean are the standard deviation and the mean of one set of coupled currents from the
multi-electrode probe; We is the equivalent weight of the material of the wire electrodes; F is the Faraday
constant; is the density of the electrode; and A is the surface area of a wire electrode. In this study, a
sampling rate of 30 s per set of data was used.
A Pyrex glass beaker holding 500 mL test solution was used as the test cell. The coupled multielectrode array sensor probe, a Ag/ AgCl 3M KCl reference electrode placed in a Lugin probe with the
opening close to the multi-electrode sensor probe, and two temperature sensor probes i.e., a thermal
couple and a resistance temperature detector with stainless steel sheath are mounted on a Teflon cell cover
and immersed in the solution in the beaker. The Teflon cover was used to minimize solution loss during the
experiment and used to fix the position of the test probes in the cell. A microprocessor control hot plate
was used to heat the solution to the desired temperature during the test. A Teflon coated magnetic stirring
bar was also used to agitate the solution during the test. The solution was exposed to the air during the test.
In the test designed to study galvanic corrosion, the cathode i.e., a nickel plated copper, 1.1 cm2 surface
area sealed in an EG&G flat electrode Teflon holder by a silicone O-ring was also inserted into the cell via
a Teflon cell cover. The cathode was connected to the coupling point of the NanoCorr CMS analyzer to
complete the galvanic coupling connection to the electrodes of the multi-electrode sensor probe. The
distance between the CMS probe and the cathode surface was about 1 cm.
Simulated Localized Corrosion Cell (SLCC) Tests

The aluminum alloy anode and cathode used in the simulated localized corrosion cell tests were sealed in
epoxy. The aluminum electrodes were cast aluminum cut from coolant channels of an engine block or a
power electronic device case of a gasoline-electric hybrid powered vehicle 0.45 cm2. In some tests, a
cathode i.e., a nickel plated copper, 1.1 cm2 surface area cut from the heat sink of the power electronic
device of the hybrid vehicle sealed in an EG&G flat electrode Teflon holder by a silicone O-ring was
used. A Pyrex glass beaker holding 500 mL test solution as the test cell and a platinum wire as the counter
electrode were also used in the test. The distance between the anode and cathode surface is about 1 cm.
Other test equipment is the same as those used in the CMS test.
Electrochemical measurements were conducted using a commercial potentiostat manufactured by
Gamry Instrument. The localized corrosion current density Ilocalized corrosion of the anode is calculated
according to the following equation 2,16.
Ilocalized
corrosion = IZRA + ILPR
where IZRA presents the galvanic coupling current density measured between the anode and the cathode
from the simulated localized corrosion cell SLCC; ILPR represents the LPR or linear polarization resistance corrosion current density measured from the anode alone when the anode is temporarily disconnected from the cathode. A Stern-Geary constant for aluminum alloys used to convert the polarization
resistance to LPR corrosion current density was either calculated based on anodic and cathodic Tafel
slopes measured at the end of the tests on the anodes or assumed to be 49.9 mV according to Ref. 21.
The localized corrosion rate of the anode is calculated from the localized corrosion current density,
Faraday constant, equivalent weight, and density of the anode.
ASTM D 1384 and D 4340 Corrosion Tests
Tests were conducted in accordance with ASTM Test Method for Corrosion Test for Engine Coolants in
Glassware D 1384 and Standard Test Method for Corrosion of Cast Aluminum Alloys in Engine Coolants
Under Heat-Rejecting Conditions D 4340, respectively. A high lead solder alloy L50113 sample containing 97 % lead, 2.5 % tin, and 0.3 % silver was also used in the ASTM D 1384 test.
Conventional Electrochemical Tests
Tests were conducted either using a modified GM 9066-P Method 21 or in the CMS test cell, using a
commercial potentiostat. The working electrodes were aluminum alloy samples cut from an engine block
coolant channel. The counter electrode was a platinum wire. An Ag-AgCl 3M KCl reference electrode
placed in a Lugin probe with the opening close to the working electrode was also used in the test. No
mechanical stirring of the solution was used in the test.
ASTM D 1384 and D 4340 Test Results
Test results obtained according to ASTM Standard Test Methods D 1384 and D 4340 specifications for two
organic acid technology OAT coolants with and without corrosive ion contamination fluoride and a
corrosion inhibition additive are shown in Tables 1 and 2. As shown in the tables, the corrosion protection
performance of the two OAT coolants were both very good, yielding corrosion mass loss values well
below the acceptable limits specified in ASTM Standard D 3306 for the various metal test samples.
In the presence of fluoride ions a corrosive species that can be introduced into the engine coolant by
the dissolution from the excessive amounts of the flux residue accumulated inside the heat exchangers
manufactured by the controlled atmosphere brazing process, corrosion of cast aluminum specimen was
increased substantially in both OAT coolant formulations, yielding average mass loss values obtained
under D 1384 conditions approaching the limits specified by ASTM D 3306. The corrosion of Sn30A
solder was also increased in OAT coolant B by the presence of 400 mg/ L fluoride, yielding an average
mass loss value approaching the limit specified by ASTM D 3306. The corrosion of other metals under D

TABLE 1ASTM Standard Method D 1384 test results for OAT coolantsaverage mass loss, mg/specimen.
Organic Acid Technology OAT Coolant Concentrate
OAT Coolant A
OAT Coolant B
OAT Coolant A with 400 mg/ L fluoride
OAT Coolant B with 400 mg/ L fluoride
OAT Coolant A with 400 mg/ L fluoride and
inhibitive additive
ASTM D 3306 Limits
Time Averaged Uniform Corrosion Rates
Corresponding to D 3306 Limitsa
High Lead
Solder
108
196
91.6
150
13.4
Copper
0.6
1.4
2.0
1.1
1.8
Sn30A
Solder
1.3
1.6
1.8
28.5
6.4
Brass
1.2
1.3
0.9
1.5
1.9
Carbon
Steel
0.4
0.0
0.5
1.6
1.8
Cast
Iron
1.2
0.5
0.3
2.0
1.0
Cast
Aluminum
3.3
2.8
26.6
27.2
6.0
Report
NA
10 max
10
30 max
29
10 max
11
10 max
12
10 max
12
30 max
95
Note: Negative value indicates the test specimen had weight mass gain after the test. NA= Not available.
a
The unit for corrosion rate is m / year. High lead solder is Alloy L50113, 97 % lead, 2.5 % tin, 0.5 % silver.
1384 test conditions was not affected by the presence of fluoride contamination. Visual inspection of the
metal samples after the tests indicated that pitting and crevice corrosion under the washer connections
occurred, especially for the cast aluminum samples exposed to the coolants containing fluoride ions.
The addition of the coolant inhibitive additive was very effective for the improvement of the corrosion
protection performance of OAT coolant formulation in the presence of fluoride contamination, as shown in
Table 1, and as a result, the corrosive effect of the fluoride ions towards cast aluminum was eliminated by
the addition of very small amounts of the additive to OAT-type coolant formulations. No degradation of
corrosion protection performance of other metals used in the D 1384 tests was observed due to the addition
of the coolant corrosion inhibition additive.
It should be noted that while the ASTM D 1384 and D 4340 standard tests are very useful as a tool for
evaluation of corrosion protection performance of coolants, and they are required corrosion tests for
qualifying antifreeze for use in vehicles by vehicle manufacturers, the corrosion results are the averaged
values for the exposed sample surface area and the test time periods. Thus, the mass loss results do not
provide direct information about the extent of localized corrosion attack under the test conditions. One
may use visual observation or tools such as a calibrated microscope to obtain information related to the
extent of localized corrosion on the test samples. However, obtaining quantitative localized corrosion rate
data using these methods is tedious and labor intensive. It should also be noted that the 30 mg mass loss
limit for cast aluminum in the D 1384 test corresponds to a calculated time average uniform corrosion rate
of only 95 m / year. The cast aluminum corrosion rate limit of 1.0 mg/ cm2 / week in the D 4340 test
corresponds to a calculated time average uniform corrosion rate of 193 m / year.
Conventional Electrochemical Test ResultsAluminum Engine Block Sections
Corrosion test results obtained using conventional electrochemical methods such as polarization resistance
measurements and Tafel extrapolation of the anodic polarization curves are shown in Tables 3 and 4. The
tests were conducted using aluminum alloy samples cut from sections of an automotive engine block
coolant channel surface as electrodes in OAT coolants A and B, without the addition of any corrosive ion.
The electrodes used in obtaining the results given in Table 3 were sealed in a high-temperature epoxy
except for a small section of the original coolant channel surface were exposed to the test coolants. The
engine block coolant channel surface has both rough and smooth areas. To determine if the two different
TABLE 2ASTM Standard Test Method D 4340 results for OAT coolants.
Organic Acid Technology OAT Coolant Concen- Cast Aluminum UNS A03190 Average Corrosion
trate
Mass Loss Rate, mg/ cm2 / week
OAT Coolant A
0.18
OAT Coolant B
0.40
ASTM D 3306 Limit
1.0 max
Time Averaged Uniform Corrosion Rate
193
Corresponding to D 3306 Limita
Note: The negative value indicated that the specimens had mass gain after the tests.
a
The unit for corrosion rate is m / year.

TABLE 3Aluminum engine block surface area average corrosion rates in OAT coolants.
50 vol. % OAT Coolant A, Solution Temperature= Electrode Surface Temperature= 88 1 C

Smooth Surface
Polarization Resistance
E-corr
Time at 88 C
LPR CorrRate
CorrRateTafelanodic
hours
V / AgAgCl
Ohm*cm2
m / y
m / y
1
0.610
6272
86.9
2
0.574
7064
77.2
2.2
0.573
73.9
Rough Surface
Time at 88 C
E-corr
LPR CorrRate
CorrRateTafelanodic
hours
V / AgAgCl
m / y
m / y
Ohm*cm2
1
0.811
4390
124
2
0.679
5624
97.0
2.2
0.651
88.4
50 vol. % OAT Coolant B, Solution Temperature= Electrode Surface Temperature= 88 1 C
Smooth Surface
Time at 88 C
E-corr
LPR CorrRate
CorrRateTafelanodic
hours
V / AgAgCl
m / y
m / y
Ohm*cm2
1
0.477
12379
44.2
2
0.454
9389
58.2
2.2
0.461
48
Rough Surface
Time at 88 C
E-corr
LPR CorrRate
CorrRateTafelanodic
hours
V / AgAgCl
m / y
m / y
Ohm*cm2
1
0.636
5996
91.2
2
0.652
6598
82.8
2.2
0.658
70.4
Note: Stern-Geary Coefficient of 49.90 mV used to convert polarization resistance to LPR corrosion rate.
surface sections would exhibit different corrosion behavior in the test coolants, electrodes cut from both
surface sections were used. The electrode used in obtaining the results listed in Table 4 was an aluminum
alloy plate section cut from the same engine block. It was polished to 600 grit sand paper and degreased
in acetone before installation into a test cell.
The results show that good corrosion protection performance for the aluminum samples was obtained
in both coolants. The surface area average corrosion rates obtained decrease as immersion time increases.
As expected, the corrosion rates also increase when temperature increases. The results in Table 3 also
suggest that the corrosion rates obtained from the rough surface sections tend to be slightly higher than
those obtained from the smooth surface sections. In general, the corrosion rates obtained from both coolant
formulations were largely the same, especially in view of the fact that different sections of the engine
block surface were used to make the electrodes. The differences observed are most likely within the
experimental errors of the test methods used. Figure 1 shows the anodic polarization curve measurement
of the sample of polished aluminum engine block in 50 vol. % OAT coolant B under conditions similar to
heat rejecting engine block operating conditions e.g., similar to those specified in GM 9066-P. The
general features of the polarization curve are similar to those obtained on cast aluminum UNS A03190
TABLE 4Aluminum engine block surface area average corrosion rates in OAT coolant B.
50 vol. % OAT Coolant B, Electrode Surface Temperature= 137 4 C

600 grit Sand Paper Polished Surface
Polarization Resistance LPR CorrRate CorrRateTafelanodic Surface T
Immersion Time
E-corr
V / AgAgCl
Ohm*cm2
m / y
m / y
hours
C
6.0
0.810
2015
270.5
136.8
22.0
0.075
17104
3.18
21.0
28.0
0.762
3160
172.5
133.6
28.2
0.768
154
133.8
Note: Test conditions similar to those specified in GM 9066-P. Stern-Geary Coefficient of 49.90 mV used to
convert polarization resistance to LPR corrosion rate.
FIG. 1Anodic polarization curve of polished sample of aluminum engine block sample in 50 vol. % OAT
coolant B under conditions simulating heat-rejecting surface.
under comparable conditions. The anodic current shows a rapid increase with increasing anodic potential
around 0.5V / AgAgCl 3M KCl. This potential may be considered as the pitting potential of the aluminum
sample under the test conditions. It should be noted that although the conventional electrochemical tests
such as polarization resistance and polarization curve measurements may be used to obtain corrosion
protection performance of a test coolant much quicker than various mass loss based corrosion evaluation
methods, the corrosion rates obtained were averaged over the whole exposed surface area. Information
related to localized corrosion, such as pitting potential, obtained from the conventional electrochemical
methods, is largely qualitative, and cannot be used to obtain a reliable localized corrosion rate under the
test conditions.
Galvanic Interaction of Different Aluminum Engine Block SectionsSLCC Results
Since the rough surface sections and the smooth surface sections are physically connected in the same
engine block, galvanic interactions among these surface sections affecting the corrosion processes are
expected. The simulated localized corrosion cell SLCC is well suited to quantify the galvanic interactions
and their effects on corrosion. Figures 2 and 3 show the results of using the SLCC method to study the
galvanic corrosion of the rough surface area section coupled to a smooth surface area section of the
aluminum engine block in an OAT coolant formulation at 88 C. The surface area ratio of the electrodes
used in the test was roughly the same as observed on the real engine block.
The results in Figs. 2 and 3 suggest that the galvanic coupling between the rough surface and smooth
surface sections led to an increase of about four to five times the corrosion rates of the rough surface
section in comparison to the values observed without the presence of the galvanic interactions see Table
FIG. 2SLCC test resultsRough surface in OAT coolant A.
FIG. 3Comparison of measured couple current versus calculated galvanic corrosion current.
3. The galvanic corrosion rate of the rough surface was observed to decrease rapidly with time. The
contribution of cathodic reduction on the smooth surface area electrode towards the corrosion of the rough
surface electrode was time-dependent and it generally decreased with time. As shown in Fig. 3, the
measured galvanic coupling current i.e., Icouple in Fig. 3 accounted for 80 % of the total rough
surface corrosion current denoted as Roughgal.corrslc in Fig. 3 at the initial 1 2 hours of the test. It
decreased to about 15 % after 20 hours of immersion. The results indicate that the OAT coolant A is very
effective in controlling corrosion of the different engine block sections under the test conditions. Post-test
visual examination of the electrode surfaces indicated that the corrosion attack on the surface was uniform.
In addition, the corrosion rate of the rough surface electrode or anode determined at the end of the test
using Tafel extrapolation of the anodic polarization curve to the couple corrosion potential was
76 m / year. This value was in good agreement with the value 88 m / year shown in Fig. 3, determined
by using the combined ZRA and LPR measurements. These results suggest that the simulated localized
corrosion cell method appears to be applicable for the determination of localized corrosion rates of
aluminum alloys in coolants.
Galvanic Corrosion of Aluminum and Ni-plated CuSLCC Method
The simulated localized corrosion cell method is also well suited for the quantitative measurement of
galvanic corrosion of aluminum alloy and the nickel plated copper material. Figure 4 shows that the
aluminum alloy galvanic corrosion rate increases with increasing temperature. Increasing solution temperature from 75 to 88 C led to an increase of the galvanic corrosion rate by 100 %. Furthermore, the
FIG. 4SLCC resultsAluminum alloy 0.45 cm2 and Ni-plated Cu 1.1 cm2 galvanic corrosion in
50 vol. % OAT coolant A.
FIG. 5Comparison of measured couple current and galvanic corrosion currentsame conditions as in
Fig. 4.
aluminum galvanic corrosion rate decreases rapidly with time. After 150 test hours of cycling between
room temperature and 75 C 7 h per day, the aluminum galvanic corrosion rate was reduced to
roughly 40 % of the value observed during the first day of immersion.
Post-test visual examination of the aluminum electrode surfaces indicated that the corrosion attack on
the surface was uniform. In addition, the corrosion rate of the aluminum determined at the end of the test
using Tafel extrapolation of the anodic polarization curve to the couple corrosion potential was
209 m / year. This value was in good agreement with the value 197 m / year shown in Fig. 4, determined by using the combined ZRA and LPR measurements. These results suggest that the simulated
localized corrosion cell method can provide an accurate and reliable measurement of galvanic corrosion of
aluminum alloy under the chosen test conditions.
Figure 5 shows the comparison of measured galvanic coupling current Icouple flowing between the
aluminum anode and the Ni-plated Cu cathode and the galvanic corrosion current Igal.corr of the
aluminum anode determined according to the simulated localized cell method. The results indicate that the
contribution of cathodic reaction current on the aluminum anode towards aluminum galvanic corrosion
was quite substantial under the test conditions. Conventional approach of measuring the coupling current
alone to calculate the galvanic corrosion rate would underestimate the true galvanic corrosion rate significantly. The galvanic couple corrosion potential as a function of time is also shown in Fig. 5, and indicates
that the corrosion potential tended to move to a more anodic value as the galvanic corrosion rate of the
aluminum alloy decreased.
Galvanic Corrosion of Aluminum and Ni-plated CuNanoCorr CMS Results
Figure 6 shows the maximum galvanic localized corrosion of cast aluminum UNS A23190 and temperature as a function of time obtained from NanoCorr Couple Multi-electrode Sensor CMS exposed to
50 vol. % OAT coolant A. The general trend of the CMS localized corrosion rate is similar to those
obtained from the simulated localized corrosion cell method, except the corresponding corrosion rate
values are about five to six times higher. Similar to the results obtained from the simulated localized
corrosion cell method, the CMS localized corrosion rate for the cast aluminum decreased rapidly with
time. After four days of cyclic temperature exposure in the solution, the maximum galvanic localized
corrosion rate decreased to about 1 / 2 of the values observed during the first day of exposure. Increasing
temperature from 75 to 88 C led to a 100 % increase in CMS maximum galvanic localized corrosion rate.
Results shown in Fig. 6 also suggest that the addition of small amounts of corrosion inhibition additive
into the 50 vol. % OAT coolant solution reduced the maximum galvanic localized corrosion rate of the cast
aluminum to about 400 from greater than 1000 m / year. Doubling the amount of the corrosion inhibition
additive did not lead to further reduction of the localized corrosion rate of the cast aluminum. Use of a
lower level of the inhibition additive also had little detectable effect on the localized corrosion rate of cast
aluminum. The time of adding the inhibitive additive and the corresponding cast aluminum maximum
localized corrosion rate measured by the CMS instrument were as follows: 1 At 10:54 a.m., slugged low
FIG. 6CMS resultsgalvanic corrosion of cast Al and Ni-plated Cu in 50 vol. % OAT coolant A.
dose of an inhibitive additive. The CMS cast aluminum localized corrosion rate was 944 956 m / y just
before the additive addition. 2 At 11:29 a.m., slugged regular dose of the inhibitive additive. The CMS
cast aluminum localized corrosion rate was 1124 1135 m / y just before the additive addition. 3 At
14:34, slugged dose two times of regular dose of the inhibitive additive. The CMS cast aluminum localized
corrosion rate was 419 430 m / y. 4 One hour after the addition of two times of regular dose of the
additive, the CMS cast aluminum localized corrosion rate was 419 433 m / y.
Figure 7 shows the maximum galvanic localized corrosion current I corr cal= 2.5 + absImean, the
maximum anodic current from the coupling current from the 25 cast aluminum wires Imaxano, and the
coupling current of the most corroded wire at the end of the test i.e., at the end of the test, the wire had
the highest value of time averaged anodic current as a function of time. One can see that the three current
values are quite close to each other in most cases. Among them, the coupling current of the most corroded
wire tended to yield the smallest time average value. Thus, the results indicate that the NanoCorr CMS
FIG. 7CMS resultscomparison of various localized corrosion current values.
FIG. 8CMS resultsmean galvanic coupling current, maximum anodic current, and couple corrosion
potential versus time.
Analyzer may tend to yield a localized corrosion rate higher than the actual maximum average corrosion
rate measurable on the probe using an independent physical measurement technique.
Figure 8 shows the mean coupling current of the 25 wires on the sensor probe Imean, the maximum
anodic current from the coupling current from the 25 wires Imaxano, and couple corrosion potential as
a function of time. One can see that the couple corrosion potential generally increases as corrosion rates
decrease, in agreement with the results obtained from the simulated localized corrosion cell method. The
mean coupling current is smaller than the corresponding maximum anodic current value. The mean
coupling current values were much higher than the corresponding galvanic coupling current shown in Fig.
5, probably due to the fact that the anode/cathode surface area ratio in the NanoCorr CMS test was only
about 55.6 % of the one used in the simulated localized corrosion cell test. In addition, the likely difference
in aluminum alloy composition used as the anode in the two tests may also contribute to the observed
differences. It should be noted that in calculating the maximum localized corrosion rate, NanoCorr CMS
Analyzer assumes that cathodic reaction on the anode sites or wire of the probe is negligible. Thus, since
cathodic reaction on the anode site tends to reduce the observable true anodic current, the true localized
corrosion rate may be even much higher than those yielded by the NanoCorr CMS instrument. Based on
the results obtained from the simulated localized corrosion cell method, the true maximum localized
corrosion rate may be typically 40 to 80 % higher than the values reported by the NanoCorr CMS
instrument.
Localized Corrosion of Cast Aluminum in OAT CoolantsNanoCorr CMS Test Results
Localized corrosion results of cast aluminum UNS A23190 in 25 or 50 vol. % OAT coolant formulations
measured by the NanoCorr CMS probe are shown in Figs. 912. The effects of changing temperature,
addition of corrosive species such as chloride and fluoride, and addition of corrosion inhibitor additives
were studied. One can see from Figs. 912 that the NanoCorr CMS probe yielded a localized corrosion
rate higher than the surface area average corrosion rates obtained from conventional electrochemical
methods and mass loss methods. The localized corrosion rate obtained correlates very well with corrosivity
changes in the test solution. For example, the CMS localized corrosion rate increases with increasing
temperature and the addition of corrosive ions and it decreases with the addition of known effective
aluminum corrosion inhibitors. In addition, the CMS probe also shows that fluoride may be a more
corrosive species with regard to cast aluminum localized corrosion than chloride ions and corrosion
inhibition additives are very effective localized corrosion inhibitors for cast aluminum in OAT coolants,
even in the presence of high concentrations of fluoride and chloride ions. It should be noted that results in
FIG. 9CMS resultslocalized corrosion of cast aluminum in 50 vol. % OAT coolant A. (see text for a
full explanation)
Fig. 11 show that the CMS calculated localized corrosion current Icorrcal values were generally significantly higher than the comparable maximum anodic current or the anodic current from the most
corroded wire measured by the CMS probe.
In Fig. 9, the time of solution heating and additive addition is as follows. At 11:10 a.m., the heater was
FIG. 10CMS resultslocalized corrosion of cast aluminum in 25 vol. % OAT coolant B. (see text for a
full explanation)
FIG. 11CMS resultscomparison of various localized corrosion current. (see text for a full explanation)
FIG. 12CMS resultslocalized corrosion of cast aluminum in 50 vol. % OAT Coolant B. (see text for a
full explanation)
turned on. At 13:27 and 15:23, inhibitive additive was added. At 16:13, the heater was turned off. The
relevant cast aluminum localized corrosion rates determined by CMS instrument as were follows:
2701 m / y at 13:26; 19.9 m / y at 15:20.
In Figs. 1012, the time of addition of corrosive ions and inhibitive additive, and heating of the
solution is as follows. At 11:10 a.m., the heater was turned on. At 13:51 and 15:00, 100 mg/ L fluoride was
added. At 15:45, inhibitive additive was added. The relevant cast aluminum localized corrosion rates
determined by CMS instrument were as follows: 318 m / y at 13:48; 1556 m / y at 14:58; 2199 m / y at
15:44; 28.8 m / y at 17:09.
In Fig. 12, the time of addition of corrosive ions and inhibitive additive, and other changes of
corrosivity in the solution is as follows. At 9:39 a.m., the heater was turned on. At 10:47 a.m. and 12:12,
100 mg/ L fluoride ions were added. At 10:17 a.m., solution temperature reached 88 C. At 11:21 a.m.,
stirring of the solution was started. At 13:08, 100 mg/ L chloride ions were added. At 13:39 and 14:36, an
inhibitive additive was slugged dose into the solution. The relevant cast aluminum localized corrosion
rates determined by CMS instrument were as follows: 22 m / y at 9:40 a.m.; 277 m / y at 10:20 a.m.;
255 m / y at 10:46 a.m.; 624 m / y at 11:19 a.m.; 1321 m / y at 12:11; 2217 m / y at 13:04;
2290 m / y at 15:08; and 1818 m / y at 14:35.
It should be noted that the trends obtained from the CMS tests with regard to the addition of corrosive
ions e.g., fluoride, and inhibitive additive are in agreement with those observed in ASTM D 1384 tests
provided in Table 1. The trends were also consistent with those obtained from conventional electrochemical tests described in separate publication 22.
Conclusions
Recent development in localized corrosion monitoring technology has made the task of development of new and more effective engine coolants for controlling localized corrosion of metal easier
to accomplish.
The simulated localized corrosion cell method was shown to be well suited for studying aluminum
galvanic corrosion in engine coolants and yielded results in good agreement with those determined
by an independent reliable method.
The coupled multi-electrode sensor probe method has the advantage of incorporate statistical analysis in obtaining localized corrosion information and yielded a maximum localized corrosion rate
that is correlating well with the corrosivity change in test coolant solutions.
The two methods should be very useful for measuring localized corrosion in engine coolant
conditions.
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Yang, B., Minimizing Localized Corrosion via New Chemical Treatments and Performance Based
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Corrosion Monitoring Using Coupled Multielectrode Array Sensors, NACE Corrosion/2005, 2005,
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J. ASTM International.

Paper ID JAI100521
Anthony P. Skrobul,1 Steven L. Balfe,1 and Fred C. Alverson1
Compatibility Testing of Multi-Vehicle Coolant Chemistries

ABSTRACT: Multi-vehicle or universal coolants, or both, have been introduced into the marketplace to
satisfy the wishes of mass merchandisers, automotive garage and repair shops, quick oil change establishments, and the general public for a convenient single coolant for use in the myriad makes and models
of vehicles. Universal coolants are recommended for top off, as well as complete drain and fill of the
customers cooling system, regardless of the color or inhibitor chemistry of coolant already in use. Coolant
mixing, and potential compatibility issues, will result for the top-off scenario, but may also be of concern
following coolant system flush-and-fill. However, there are currently no standard compatibility tests to define
satisfactory compatibility when coolants of different chemistry are mixed. Previous work to establish compatibility of coolant mixtures documents that potential coolant deterioration of the corrosion protection may
occur in the ASTM D 4340 1 Aluminum Heat-Rejection Test when mixing coolants with different additive
chemistries. Compatibility testing has been conducted on various universal coolants with traditional high
silicate, traditional low silicate, hybrid phosphate free, hybrid phosphated, and OAT-only technologies.
This paper provides results of the coolant compatibility tests and correlation of coolant chemistry with
coolant performance in these tests.
KEYWORDS: multi-vehicle coolants, universal coolants, compatibility, antifreeze, OAT, hybrid
coolant
Introduction
It would be an understatement to say that a lot has happened since the introduction of the first formulated
ethylene glycol-based antifreeze in the United States in 1927 2. In the early 1960s, all three U.S. car
companiesGeneral Motors, Ford Motor Company, and Chryslerbegan installing a 50/50 mix of ethylene glycol antifreeze/water in their new cars 3. Engineering accomplishments have led to the introduction of more efficient engines with more rigorous performance requirements, and placed greater demands on the engine coolant. The use of lightweight metals and plastics in engine cooling systems, as well
as new elastomer and hose materials has hastened the evolution of traditional antifreeze. Armstrong and
Pellet have also pointed out the contribution of a global marketplace with import and export of vehicles
and parts, and how changing attitudes toward the protection of human health and the environment, have
impacted antifreeze development 4. There is now a plethora of antifreeze/coolants in the marketplace,
and this abundance of antifreeze/coolant choices has resulted in some consumer confusion 5. Many
antifreeze/coolant products, while based on glycol either ethylene glycol or propylene glycol, differ in
formulation and color. The vehicle manufacturers unique antifreeze/coolant specifications, defining
physical/chemical requirements, corrosion protection requirements, and service life, have resulted in a
proliferation of antifreeze/coolant formulations.
Fortunately the confusion can be attenuated somewhat by classifying antifreeze/coolants into three
broad categories. The three basic types of coolants are 6:
IAT or conventional North American green antifreeze. IAT stands for Inorganic Additive Technology. The corrosion inhibitors used are sodium or potassium salts of inorganic anions. Phosphate,
borate, silicate, nitrite, and nitrate are most commonly used. A given formulation contains varying
amounts of two or more of these chemicals. The formulation would usually contain an azole
compound tolyltriazole, benzotriazole, or mercaptobenzothiazole as a copper corrosion inhibitor.
According to Carley 6, The fast-acting silicate and phosphate corrosion inhibitors provide quick
Manuscript received March 3, 2006; accepted for publication September 19, 2006; published online April 2007. Presented at
1
Coolant Advisor, Technology Manager, and Coolant Advisor, respectively, Shell Global Solutions US Inc., 3333 Highway 6
South, Houston, Texas 77082.
59
protection for bare iron and aluminum surfaces, and have a proven track record for providing
trouble-free service in virtually any vehicle application domestic, Asian, or European, assuming
the chemistry is correct. Because the corrosion inhibitors in traditional coolants deplete in service,
this type of coolant should be changed every two to three years or at 30 000 miles 48 280 km.
OAT-based coolants. OAT stands for Organic Acid Technology, and includes organic acids such as
2-ethylhexanoic acid, sebacic acid, azelaic acid, and benzoic acid, among others, providing broadspectrum corrosion protection. Sometimes two or more organic acids are used in the same formulation. At typical pH values of about 7.59.0, the organic acids in OAT coolants are in the form of
their sodium or potassium salts depending upon whether the pH is adjusted with sodium hydroxide
or potassium hydroxide. OAT coolants also contain an azole additive as a copper corrosion inhibitor. OAT coolants generally provide longer service life than inorganic types. The recommended
service life is typically five years or 150 000 miles 241 402 km. OAT-based coolants are usually
dyed a different color to distinguish them from traditional North American green antifreeze 6.
GMs DEX-COOL dyed orange is an example of an OAT extended-life coolant.
Hybrid OAT coolants, also known as HOAT. Hybrid OAT coolants use an organic anion as the
primary corrosion inhibitor. Selected inorganic salts are added to enhance certain properties. HOAT
coolants also contain an azole additive as a copper corrosion inhibitor. North American and European hybrid formulations usually contain silicate as a major inorganic anion. Japanese hybrid
formulations usually contain phosphate as a major inorganic anion.
While it may be desirable to follow the vehicle manufacturers recommendations for coolant type
when topping-off or changing coolant, practically speaking, mass merchandisers and shops dont have the
shelf space to stock different coolants for each make and model of vehicle. U.S. aftermarket service fill
outlets are embracing multi-vehicle coolants in cases where reduced shelf space and stock keeping units
are desired. This has given rise to the popularity of coolants described as universal, global, or multivehicle. The successful use of such coolants in all makes and models of automobiles requires at least two
considerations, product color and product compatibility.
1. Product color of universal products is neutral, and as such will mix with other engine coolant
colors without making coolant color an issue. Product color is easy to deal with, but begs the
question of compatibility.
2. For the most part, universal coolants are sold as aftermarket products. As such, most of the time
the coolant will be added to a cooling system as top-up to the coolant already in the vehicle. If the
initial coolant is working properly, then the cooling system is already passivated prior to the
addition of the universal coolant for top-up. If there is no chemical instability, and therefore no
inhibitor dropout, the consumer would expect little risk of damage associated with the mixing of
two different coolants. It remains for the marketer of the coolant to adequately verify compatibility
between their universal coolant and the variety of OEM and service-fill coolants in the
marketplace.
This paper provides test results for a multi-vehicle coolant that provides excellent corrosion protection
by itself, and in mixtures with current OEM and service-fill coolants.
Experimental Method
Test Procedure
Tests were conducted on 50/ 50 volume % mixtures of the multi-vehicle coolant candidate with various
OEM and service fill coolants, in accordance with ASTM Standard Specification for Glycol Base Engine
Coolant for Automobile and Light-Duty Service ASTM D 3306-05 7. We also conducted ASTM
Standard Test Method for Corrosion Test for Engine Coolants in Glassware ASTM D 1384-05 8, and
ASTM Standard Test Method for Corrosion of Cast Aluminum Alloys in Engine Coolants Under HeatRejecting Conditions ASTM D 4340-96 Reapproved 2001 1 on the following volume ratios of the
multi-vehicle coolant with OEM and service fill coolants: 90/10, 75/25, 50/50, 25/75, and 10/90. However,
we didnt necessarily test each of the above ratios for all coolant mixtures. In many cases we focused only
on the 50/50 mixture of coolants, since this ratio would intensify possible additive interactions, and
historically was most prone to display incompatibility issues. Given the large number of ASTM D 1384 8
and ASTM D 4340 1 tests required with the above coolant ratios, we deviated from the standards in some
SKROBUL ET AL. ON COMPATIBILITY TESTING OF MULTI-VEHICLE COOLANT CHEMISTRIES 61

TABLE 1Engine coolant inhibitor formulation.
Inhibitor
Coolant
A
B
C
D
E
F
G
H
I
J
K
L
M
N
O
P
B4O2
7
NO2
X
X
X
X
X
X
X
X
X
X
X
NO3
X
X
X
X
X
X
X
X
X
X
X
X
X
HPO2
4
MoO2
4
X
X
X
X
SiO2
3
X
X
X
X
X
X
X
Azole
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Benzoatea
X
Mono
Acid
Dibasic
Acid
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Benzoate includes the salts of benzoic acid and substituted benzoic acid.
cases with regard to the number of runs. For the ASTM D 1384 8 we made duplicate runs with one
exception in which we made a single determination at a 50/50 ratio and reported both runs, rather than
reporting the average of triplicate runs per the standard. For the ASTM D 4340 1 we typically made two
runs per the standard but in some cases we made three determinations, and in other cases single determinations.
With the exception of the number of test runs discussed above for the ASTM D 1384 8 and ASTM
D 4340 1 tests, we followed the standard conditions for these tests. ASTM D 1384 8 requires
1
33 3 volume % coolant diluted with corrosive water 100 ppm of chloride Cl, sulfate SO=4 , and bicarbonate HCO3 introduced as sodium salts at 88 C 190 F for 336 h 2 weeks. The metals exposed to
the aerated engine coolant aeration rate of 100 mL/ min solution were copper, Alloy Grade 30A SAE
3A solder, brass, steel, cast iron, and cast aluminum. Corrosion was measured by weight changes incurred
by the specimens. ASTM D 4340 1 requires 25 volume % coolant diluted with corrosive water 100 ppm
chloride Cl introduced as the sodium salt under a pressure of 193 kPa 28 psi. The cast aluminum test
specimen heated from underneath while engine coolant sits on its top surface is maintained at 135 C
275 F throughout the 168-h 1 week test. Heat-transfer corrosion is evaluated on the basis of the weight
change of the test specimen.
Test Fluids
The multi-vehicle coolant was mixed with various OEM and service coolants conforming to the above
definitions for OAT, conventional and hybrid coolants. Table 1 provides an overview of the inhibitor
compositions of the tested coolants. Coolant A is the multi-vehicle coolant under investigation.
Commercial OAT Coolants
Table 2 provides ASTM D 4340 1 performance compatibility results for two commercially available
OAT coolants Coolants B and C, in combination with either an OAT coolant Coolant C or hybrid-type
coolants Coolants F, L, and G. The three hybrid coolants all contain silicate. As expected, the two OAT
coolants were completely compatible at all coolant ratios. However, OAT Coolant B was incompatible
with Coolants F and L, and Coolant C was incompatible with Coolants L and G when tested at a 50/50
ratio. Coolant mixtures B&F and C&L were also incompatible at a 75/25 ratio. The relatively high
corrosion rates of certain coolant mixtures in the ASTM D 4340 1 test are well documented in the
literature 9,10. According to Van de Ven and Maes 9, the ASTM D 4340 1 test discriminates silicate

TABLE 2ASTM D 4340 compatibility testing.
Corrosion Rate mg/ cm2 / week
Coolant Mix
B/C
B/F
B/L
C/L
C/G
10/90
0.02, 0.03
...
...
...
...
25/75
0.04, 0.03
0.06
...
0.03
...
50/50
0.14
9.6, 4.9
2.0, 4.3
4.9, 4.4
3.86, 3.69, 3.77
75/25
0.03
3.1
...
1.76
...
90/10
0.08, 0.01
...
...
...
...
Note: The limit by ASTM D 3306 is 1.0 mg/ cm2 / week, max.
containing coolants on the basis of their silicate content: below a threshold level corrosion will occur;
above this level the coolants are no longer differentiated. The test results shown in Table 2 are consistent
with this conclusion.
The authors quoted above also tested mixtures of an OAT coolant with a silicate-containing coolant in
the ASTM D 1384 8 test. Their data showed no incompatibility problem occurs under heat receiving
conditions 9. We did not test the coolant mixtures in Table 2 in the ASTM D 1384 8 test.
Multi-Vehicle Coolant Candidate
ASTM D 1384 Glassware Corrosion TestThis product was designed to be performance compatible
with traditional, hybrid, and OAT engine coolant technology, when tested under the static heat-rejecting
conditions of the ASTM D 4340 1 test. We also needed to confirm there are no compatibility issues with
mixtures of Coolant A and other coolant technologies in the ASTM D 1384 8 test Tables 35, or in any
of the performance tests required by ASTM D 3306 7. In this case we see no incompatibility problem
under the heat receiving conditions of the ASTM D 1384 8 test. The weight gain for aluminum with the
mixture of 75 % Coolant A / 25 % Coolant I Table 4 was surprising, since no weight gain was observed
for 100 % Coolant A. Van de Ven and Maes observed a trend on the aluminum specimen when they tested
mixtures of an OAT coolant and a traditional silicate-containing coolant 9. Adding more of the silicatecontaining coolant resulted in a higher weight gain. The authors concluded that the silicates presented in
TABLE 3ASTM D 1384 compatibility testing: Coolants B and A.
Max.
Allowed
Test Results on the Various Product Mixes

Metal
Copper
Solder
Brass
Cast Iron
Steel
Aluminum
90 % B
10 % A
2, 1
2, 1
2, 1
3, 3
1, 0
0, 1
75 % B
25 % A
2, 2
2, 1
2, 2
3, 2
1, 1
7, 2
50 % B
50 % A
2
1
2
3
0
1
25 % B
75 % A
0, 2
1, 1
1, 0
0, 0
1, 0
1, 1
10 % B
90 % A
1, 1
2, 1
0, 1
0, 1
0, 1
19, 29
Wt. loss,
mg/coupon
10
30
10
10
10
30
TABLE 4ASTM D 1384 compatibility testing: Coolants I and A.

Max.
Allowed
Test Results on the Various Product Mixes

Metal
Copper
Solder
Brass
Cast Iron
Steel
Aluminum
90 % I
10 % A
0, 0
0, 1
0, 1
0, 1
2, 1
1, 0
75 % I
25 % A
2, 0
1, 0
0, 0
1, 1
3, 2
6, 3
50 % I
50 % A
0, 1
1, 1
1, 1
1, 2
1, 1
6, 9
25 % I
75 % A
1, 0
1, 1
0, 1
0, 0
2, 4
30, 35
10 % I
90 % A
...
...
...
...
...
...
Wt. loss,
mg/coupon
10
30
10
10
10
30

TABLE 5ASTM D 1384 compatibility testing of 50/50 mixtures.
Max.
Allowed
Test Results on 50/50 Mixtures

Metal
Copper
Solder
Brass
Cast Iron
Steel
Aluminum
50 % D
50 % A
1, 2
1, 1
1, 2
1, 0
1, 0
0, 0
50 % E
50 % A
1, 0
2, 3
1, 1
2, 0
2, 19
0, 1
50 % K
50 % A
1, 0
0, 2
0, 1
2, 2
0, 0
1, 0
50 % M
50 % A
0, 0
4, 2
1, 2
2, 1
1, 1
1, 0
50 % N
50 % A
1, 0
1, 1
0, 0
2, 2
0, 1
1, 1
50 % O
50 % A
0, 1
1, 2
0, 1
1, 2
0, 0
0, 1
Wt. loss,
mg/coupon
10
30
10
10
10
30
the silicate-containing coolant deposited into the pores of the cast aluminum coupon, and were not removed during the chemical cleaning process. Insufficient cleaning may explain some of the weight gain
we observed.
Table 5 includes ASTM D 1384 8 data for 50/ 50 volume % mixtures of Coolant A with six commercial coolant technologies. Coolant D is an OAT coolant, Coolant E is a traditional North American
automotive coolant, Coolants K, M, and N are Japanese OEM coolants, and Coolant O is a fully formulated heavy-duty coolant. No compatibility issues were observed with these coolant mixtures. Our data
show that ASTM D 1384 8 does not discriminate between neat coolants and mixtures.
ASTM D 4340 Heat Rejecting Aluminum Corrosion TestThe test results show no deterioration of
corrosion protection in the ASTM D 4340 1 test for the mixed coolants in Table 6. The commercial
coolants in the table cover the gamut of coolant categories discussed in the Introduction. Coolant B is an
OAT coolant, Coolant J is a nonsilicate hybrid coolant, Coolant L is a silicate-containing hybrid, Coolant
M is a nonsilicate hybrid coolant with phosphate, and Coolant P is a traditional fully formulated phosphate
free coolant. Reference 10 contains a review of previous studies examining the effect of low levels of
silicate and other inorganic inhibitors on hot aluminum corrosion protection. Much discussion is devoted
to the observation that mixtures of traditional coolants, at low levels, with carboxylate coolants yield high
ASTM D 4340 1 corrosion rates. The authors reject the widely held interpretation that the high corrosion
rates are due to incompatibility between these technologies, since an abundance of field data with slightly
contaminated vehicles does not show aluminum corrosion 10. The authors go on to show that the
Dynamic Heat Transfer Test is a better predictor of the performance of mixed coolants under aluminum
heat-rejecting conditions 10. The data of Table 6 show it is possible to formulate a coolant that, when
contaminated with other coolant technologies, does not cause the usual high ASTM D 4340 1 corrosion
rates.
TABLE 6ASTM D 4340 compatibility testing of commercial coolants and coolant A.
Product Mix Test Results mg/ cm2 / week
Commercial
Coolant
B
J
L
M
P
90/10
0.11, 0.39
0.29
0.44, 0.28
0.05, 0.02
0.20, 0.29
75/25
0.02, 0.09
0.03, 0.05
0.28, 0.15
...
0.03, 0.05
50/50
0.05, 0.2
0.06
0.26
0.03
0.06
25/75
0.09, 0.11
0.11, 0.20
0.10, 0.39
0.02
0.11, 0.20
10/90
0.06, 0.12
0.12, 0.18
0.30
0.0, 0.05
0.12, 0.18
1. The test limit by ASTM D 3306 7 is 1.0 mg/ cm2 / week, max.
2. For each coolant listed, the first number in each mix ratio is that for the commercial coolant. For
example, in the case of Coolant B in column two, the mixture is 90-volume % Coolant B and 10volume % Coolant A.
3. Most test results showed a slight weight gain as indicated by the negative sign.

TABLE 7ASTM D 3306 physical, chemical and performance testing of Coolant A.
Requirements
Physical/Chemical
Requirements
Relative density
15.5/ 15.5 C
Freezing point, C F
50 vol % in DI water
Boiling point, C F
50 vol % in DI water
Undiluted
Ash content, mass %
pH: 50 vol % in DI water
Chloride, ppm
Water, mass %
Reserve alkalinity, mL
Effect on automotive finish
General Requirements
Color
Performance Requirements
Corrosion in glassware
Wt. loss, mg/specimena
copper
solder
brass
steel
cast iron
aluminum
Simulated service test
Wt. Loss, mg/specimena
copper
solder
brass
steel
cast iron
aluminum
Corrosion of Cast Al
Alloys at Heat-Rejecting
Surfaces, mg/ cm2 / week
Foaming
Volume, mL
Break time, s
Cavitation-Erosion,
ratingd
ASTM Test
Method
D 1122
Specifications
Results
1.110 to 1.145
1.122
D 1177
37 34 max
37 34
D 1119
D 1287
D 3634
D 1123
D 1121
D 1882
108 226 min

163 325 min
5 max
7.5 to 11
25 max
5 max
report
no effect
108.4 227.1
173.9 345.0
0.80
8.3
6
2.53
3.0
no effect
...
Distinctive
Light yellow
D 1120
D 1384
10
30
10
10
10
30
max
max
max
max
max
max
2, 1
1, 1
1, 1
0, 0
0, 1
1, 2
20
60
20
20
20
60
max
max
max
max
max
max
2, 4, 2
5,12, 2
2, 0, 1
2, 0, 1
1, 0, 2
3, 17, 0
D 2570
D 4340
1.0 max
0.1b, 0.1c
150 max
5 max
8 min
30
0.46
10, 9, 9, 9, 9e, 8e, 8e
D 1881
D 2809
Each result is an average of three determinations.

Average of two determinations.
c
Average of three determinations.
d
Each result is a single determination.
e
Result at 300 hours.
b
ASTM D 3306 Tests of Neat Coolant A and MixturesTable 7 contains all test results for universal
Coolant A required by the ASTM D 3306 7 protocol. All of the Performance Requirements of ASTM D
3306 7 with the exception of Foam were performed at least in duplicate. ASTM Standard Test Method
for Simulated Service Corrosion Testing of Engine Coolants D 2570 11 was run in triplicate. We also
evaluated 50/50 mixtures of Coolant A with various commercial coolant technologies against the Performance Requirements of ASTM D 3306 7. The commercial coolants tested in mixture with Coolant A are:
TABLE 850/50 mix of Coolant B and Coolant A: ASTM D 3306 performance data.
Requirements
Wt. loss, mg/specimen
copper
solder
brass
steel
cast iron
aluminum
Wt. Loss, mg/specimen
copper
solder
brass
steel
cast iron
aluminum
Surfaces, mg/ cm2/week
Foaming
Volume, mL
Break time, s
Cavitation-Erosion, rating
ASTM Test
Method
Specifications
Results
D 1384
10
30
10
10
10
30
max
max
max
max
max
max
2
0
2
1
2
2
20
60
20
20
20
60
max
max
max
max
max
max
13
10
0
2
2
4
D 2570
D 4340
1.0 max
0.52
150 max
5 max
8 min
60
1.2
9
D 1881
D 2809
TABLE 950/50 mix of Coolant D and Coolant A: ASTM D 3306 performance data.
Requirements
copper
solder
brass
steel
cast iron
aluminum
copper
solder
brass
steel
cast iron
aluminum
Foaming
Volume, mL
Break time, s
ASTM Test
Method
Specifications
Results
D 1384
10
30
10
10
10
30
max
max
max
max
max
max
1
1
1
0
1
3
20
60
20
20
20
60
max
max
max
max
max
max
8
0
7
1
1
3
D 2570
D 4340
1.0 max
0.35
150 max
5 max
8 min
43
0.48
10
D 1881
D 2809
TABLE 1050/50 mix of Coolant E and Coolant A: ASTM D 3306 performance data.
Requirements
Wt. loss, mg/specimen copper
solder
brass
steel
cast iron
aluminum
copper
solder
brass
steel
cast iron
aluminum
Foaming
Volume, mL
Break time, s
ASTM Test
Method
Specifications
Results
D 1384
10
30
10
10
10
30
max
max
max
max
max
max
2
4
2
1
0
3
20
60
20
20
20
60
max
max
max
max
max
max
0
1
2
3
4
11
1.0 max
0.1
150 max
5 max
8 min
27
0.46
10
D 2570
D 4340
D 1881
D 2809
TABLE 1150/50 mix of Coolant H and Coolant A: ASTM D 3306 performance data.
Requirements
copper
solder
brass
steel
cast iron
aluminum
copper
solder
brass
steel
cast iron
aluminum
Foaming
Volume, mL
Break time, s
ASTM Test
Method
Specifications
Results
D 1384
10
30
10
10
10
30
max
max
max
max
max
max
2
1
1
1
1
2
20
60
20
20
20
60
max
max
max
max
max
max
1
3
2
1
1
5
D 2570
D4340
1.0 max
0.17
150 max
5 max
8 min
110
4.2
8
D 1881
D 2809
TABLE 1250/50 mix of Coolant I and Coolant A: ASTM D 3306 performance data.
Requirements
copper
solder
brass
steel
cast iron
aluminum
copper
solder
brass
steel
cast iron
aluminum
Foaming
Volume, mL
Break time, s
ASTM Test
Method
Specifications
Results
D 1384
10
30
10
10
10
30
max
max
max
max
max
max
2
0
1
1
1
17
20
60
20
20
20
60
max
max
max
max
max
max
0
3
1
2
1
2
D 2570
D 4340
1.0 max
0.87
150 max
5 max
8 min
50
1.4
8
D 1881
D 2809
TABLE 1350/50 mix of Coolant K and Coolant A: ASTM D 3306 performance data.
Requirements
copper
solder
brass
steel
cast iron
aluminum
copper
solder
brass
steel
cast iron
aluminum
Corrosion of Cast Al Alloys at Heat-Rejecting
Foaming
Volume, mL
Break time, s
ASTM Test
Method
Specifications
Results
D 1384
10
30
10
10
10
30
max
max
max
max
max
max
2
0
1
1
1
1
20
60
20
20
20
60
max
max
max
max
max
max
2
3
1
2
2
3
D 2570
D4340
1.0 max
0.10
150 max
5 max
8 min
40
2.8
8
D 1881
D 2809
Coolants, B, D, E, H, I, and K. The test results are given in Tables 813, respectively.
To date, all mixtures we have tested meet the performance requirements of ASTM D 3306 7.
Fleet Testing
Fleet testing in New York City taxicabs was initiated in July 2005 to confirm the real world performance
of multi-vehicle Coolant A when used as a top-off antifreeze/coolant, or for complete drain-and-fill. We are
monitoring three sets of cabs during this field test: 1 a control group with factory-fill coolant, 2 a set of
cabs that has been drained and filled with Coolant A, and 3 a set of cabs for which the coolant is
50 volume % original fill and 50 volume % Coolant A. This 150 000 mile test 241 402 km will take
about 1.5 2 years to complete.
Conclusions
A multi-vehicle hybrid coolant has been developed that provides excellent corrosion protection by itself,
and in mixtures with current OEM and service-fill coolants. Mixtures of the multi-vehicle hybrid coolant
with OAT, hybrid, and traditional coolants show no deterioration of corrosion protection in the ASTM D
4340 1 test or in the ASTM D 1384 8 test.
Acknowledgments
The authors wish to thank Mr. Terry Charles for his blending and testing support. The authors also thank
Southwest Research Institute and Amalgatech for coolant evaluations. Finally, the authors acknowledge
the help of Mr. Charlie Doiron of Recochem, Inc., for product development and product validation
support.
References
1
2
3
4
5
6
7
8
9
10
11
ASTM D 4340, Standard Test Method for Corrosion of Cast Aluminum Alloys in Engine Coolants
Under Heat-Rejecting Conditions, ASTM Standards on Disc, Vol. 15.0506, ASTM International,
West Conshohocken, PA, pp. 14.
Antifreezes and Deicing Fluids, Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 3, 4th
ed., John Wiley & Sons, Inc., 1992, pp. 347367.
Prestone Company Timeline, URL: http://www.prestone.com/company/timeline.php, December 8,
2005.
Armstrong, R. and Pellet, R., Extended Life Coolants, Lubrication, Vol. 87, No. 2, 2001, p. 1.
Weissler, P., Coolant Confusion: Its Not Easy Being Greenor Yellow or Orange or, http://
www.motor.com/MAGAZINE/Pdf/082004_04.pdf.
Carley, L., Universal Coolants: The Ultimate Answer?, URL: http://www.aa1car.com/library/
2004/us120426.htm, December 7, 2005.
ASTM D 3306, Standard Specification for Glycol Base Engine Coolant for Automobile and LightDuty Service, ASTM Standards on Disc, Vol. 15.0506, ASTM International, West Conshohocken,
PA, pp. 15.
ASTM D 1384, Standard Test Method for Corrosion Test for Engine Coolants in Glassware,
ASTM Standards on Disc, Vol. 15.0506, ASTM International, West Conshohocken, PA, pp. 18.
Van de Ven, P. and Maes, J.-P., A Compatibility Study of Mixtures of a Monoacid/Dibasic Acid
Coolant and a Traditional Nitrite-Free Coolant, SAE 940769, Society of Automotive Engineers,
Warrendale, PA, 1994.
Fritz, P. O., Bartley, L., Maes, J.-P., and Van de Ven, P., Extended Life Carboxylate Coolant
Compatibility with Other Coolant TechnologiesExamining the Data, SAE 2000-01-1977, Society of Automotive Engineers, Warrendale, PA, 2000.
ASTM D 2570, Standard Test Method for Simulated Service Corrosion Testing of Engine Coolants, ASTM Standards on Disc, Vol. 15.0506, ASTM International, West Conshohocken, PA,
pp. 17.

Paper ID JAI100421
Carol Jeffcoate,1 Mary Ranger,2 Jerry Grajzl,3 Bo Yang,1 Peter Woyciesjes,1 and
Aleksei Gershun1
Investigation of Interaction Between Coolant Formulations

and Flux Loading/Compositions in Controlled
Atmosphere Brazed CAB Aluminum Surfaces in Heat
Exchanger Applications
ABSTRACT: An investigation was made into the effects of flux formulation and after brazing residue on the
pitting potential of the aluminum surface in various types of coolants during laboratory evaluations.
Samples of CAB brazed radiator header alloy aluminum, with various flux loadings, were supplied by Behr
and the Ford Motor Company. The flux is generally in the form of potassium fluoroaluminate, general
formula K13AlF46.xH2O. The samples in the flux loading study were all passed through the brazing ovens
with the following flux loadings: No flux, Half the regular amount of flux, The regular amount of flux,
Double the regular amount of flux, Regular amount of flux over half of the surface area. The individual
coolants used in the flux loading study were 25 % volumes of the following, each with 100 ppm of chloride:
Conventional, Hybrid HOAT, Organic Acid OAT, Modified Organic Acid MOAT. In the flux composition study, different compositions of potassium fluoroaluminate from three different suppliers were
evaluated with hybrid type coolant. All the aluminum samples were run according to a Ford Laboratory Test
Method FLTM BL105-01 A Rapid Method to Predict the Effectiveness of Inhibited Coolants in Aluminum
Heat Exchangers 1. The samples were heated and boiled in coolant for 1 h. The temperature was
lowered to 70C and the samples were electrochemically tested by either potentiodynamic polarization or
modified Ford FLTM BL105-01. Each coolant at the end of the test was submitted for chemical analysis of
fluoride content. The electrochemical results of the flux loading study showed that the higher the flux
loading on the aluminum header material, the easier it is to initiate corrosion. Chemical analysis showed the
presence of significant quantities of fluoride in the end of test fluids. As the only fluoride-containing component of the system is the flux residue, it was concluded that fluoride leached from the flux residue. The
second study showed that not all potassium fluoroaluminate brazing flux is alike. Samples of three fluxes
from three different suppliers of the same loading on aluminum were tested with hybrid coolant. When
subjected to heating and potentiodynamic polarization, significantly different results were obtained from the
three different fluxes.
KEYWORDS: antifreeze/coolant, aluminum surface, CAB braze process, heat exchangers, potassium fluoroaluminate flux
Introduction
The method for producing radiators has changed over the years. The material of choice for light vehicle
applications is now predominantly aluminum. As well as the material, construction methods have also
changed. Instead of vacuum brazing or mechanically assembling the components, a process known as
controlled atmosphere brazing is being used increasingly. Controlled atmosphere brazing CAB is brazing
in a controlled nitrogen gas atmosphere using a potassium fluoroaluminate flux. Flux is applied to the
surfaces to be joined, the assembled unit is heated in a nitrogen atmosphere controlled oven at high
temperatures, and joining occurs.
The flux used in this process has been developed by several manufacturers, but was originally developed by Alcan as Nocolok flux and is a mixture of K3AlF6 KAlF4. The flux is inactive at temperatures
below 560 C but at brazing temperature, it turns active and removes the aluminum oxide layer to enable
Manuscript received February 7, 2006; accepted for publication October 4, 2006; published online November 2006. Presented at
W. Matulewiez, Guest Editor.
1
2
Ford Motor Company, Dearborn, MI 48121
3
BEHR Heat Transfer Systems, Inc., Charleston, SC 29405
69
joining. The residue of the flux left on the surface after brazing has been thought to be insoluble and
nonaggressive, hence no removal was necessary, and allowed the elimination of the costly residue removal
operations.
In the production process prior to fluxing a heat exchanger, it typically goes through a cleaning step to
remove residual lubricants and forming oils. The flux is applied after cleaning to individual parts or
assembled units as aqueous slurry by flooding, spraying, or dipping. Agitation is required to prevent the
flux from settling. The slurry concentration, typically in the range from 5 to 25 %, regulates the flux
loading. An air blow-off step is typically used to remove excess slurry accumulated at the downside of
the fluxed part. The goal is to achieve a uniform coating of the flux without significant accumulation in any
one place, especially inside the radiator or heater tubes.
After fluxing, the part is dried, usually at about 200 C. Care is taken not to overheat the heat
exchanger as excess heat 250 C may cause high temperature oxides to form on the aluminum surfaces.
The aim of the dry off is simply to remove water from the fluxing stage so that the component is
completely free of adsorbed water prior to entering the brazing furnace.
CAB flux brazing is carried out in an inert atmosphere such as nitrogen in either batch type furnaces
or more commonly in continuous tunnel furnaces 2,3. Nitrogen is introduced in the critical brazing
section of the furnace and flows towards the entrance and exit. At the critical brazing zone, the furnace
atmosphere has a dew point of 40 C and an O2 concentration less than 100 ppm. These conditions are
necessary for optimum brazing results. In the brazing temperature range of 530 to 560 C, traces of flux
KAlF4 evaporate and, in the presence of moisture, can react to form traces of HF.
To the authors knowledge, there are no previously reported studies of the interaction between flux
loading or types and different coolant types. It has always been assumed that the flux was inert.
Experimental
Two studies were conducted; in the first study, samples of aluminum radiator header material with differing amounts of Nocolok flux loadings were tested in various coolant formulas. The second study looked
at three different flux chemistries from three different suppliers. The main differences between the flux
chemistries were the amount of crystalline water and the mole ratio between the major components KAlF4
and K2AlF5. There were other differences that were thought to be significant. One was particle size and
particle distribution and the other was the trace metals in the flux.
First Study
Sheets of AA 3003 aluminum header alloy with one side AA4045 clad 4 were prepared with flux on the
braze clad side. Various amounts of flux were applied to the sheets: regular amount, twice the regular
amount, half the regular amount, and regular amount of flux on one-half of the sheet. The amount of flux
applied was determined by weighing a virgin plate with no flux. Then the sheet was sprayed with flux in
the production process and the sheet was weighed again. The weight of flux for that surface area was taken
as a regular flux loading. The weight of the other flux loadings required was weighed and the flux applied
by hand. The sheets were then brazed and cut into 2 by 2 in. sections. The sample quality was variable in
coverage and thickness of flux. Samples used in the experiments were chosen to be as representative as
possible. The samples with only half of the surface fluxed had a thin layer of flux residue over the entire
surface after the brazing process i.e., the flux wetted out.
JEFFCOATE ET AL. ON CAB ALUMINUM SURFACES 71

TABLE 1Approximate composition of flux from three different suppliers
Supplier/
Composition
A
B
C
KAlF4
% wt.
90
80
84
K2AlF5 . xH2O
% wt.
2.4 no water
15 water present
15 water present
K3AlF6
% wt.
5
1
Second Study
For the second study the various flux suppliers provided samples with the specifications outlined in Table
1.
The plates were 4 by 4-in. pieces of aluminum AA3003 with one side 4045 clad alloy 4. Twenty
percent by weight flux the typical regular flux loading was sprayed on the clad side. The flux-coated
plates were put on a tray and dried at 150 C. The plates were then put into an inert nitrogen controlled
atmosphere furnace. The braze ovens have a 45 C dew point to prevent any moisture in the furnace that
would liberate HF or KF, or both. The O2 was approximately 50 ppm.
Fluids Tested
For the first study with various amounts of flux loading, the following coolant fluids were tested at 25 %
coolant concentrate with deionized water and 100 ppm of chloride in the form of sodium chloride:
Conventional Silicate Coolant
Hybrid Coolant i.e., coolant containing both silicate and an organic acid
Organic Acid Coolant
Modified Organic Acid Coolant
For the study of the fluxed and brazed samples from various suppliers, only hybrid coolant was used.
The solution was 25 % by volume of coolant with 100 ppm of chloride.
Electrochemical Testing
The samples were placed into an electrochemical cell specified in FLTM BL-105-01 1,57, yielding an
exposed aluminum surface area of 8.04 cm2. Test coolant fluid was added to the cell and the aluminum
heated until the fluid boiled. The fluid was boiled for 1 h, while maintaining the fluid volume by additions
of deionized water if required, and then the temperature of the fluid was reduced to 70 C. Upon reaching
this temperature either the modified FLTM BL-105-01 1 or potentiodynamic polarization tests were
conducted. At the end of the test, samples of before and after test fluid were submitted for analysis of
fluoride ions.
Modified Ford FLTM BL 105-01Galvanostatic TestThe general procedure for the test method
FLTM BL 105-01 1,57 was followed with the exception that the cell was at elevated temperature.
Testing of varying flux loadings in conventional and hybrid coolants was performed. The temperature of
the solution in the cell after boiling for 1 h was lowered to 70 5 C. The sample was connected to a
Solartron SI 1287 potentiostat as the working electrode. A graphite rod counter electrode and a silver/silver
chloride 3 M KCl reference electrode in a Luggin probe, both connected to the potentiostat, were added
to the cell.
The open circuit potential Eoc was measured for 5 min then an anodic current of 100 A cm2 was
applied to the aluminum. The potential applied to the cell was monitored with time, for 1 h. The lowest
potential measured, after the initial spike, was recorded. This value was used as an approximation of the
repassivation potential for aluminum. This test will be referred to as the galvanostatic test for the rest of
this paper.
Potentiodynamic PolarizationThe same experimental setup was used as described for galvanostatic
testing above except for testing with increasing potential and recording the resulting current.
The open circuit potential Eoc was measured for 5 min and a potentiodynamic polarization scan was
started at 20 mV versus Eoc i.e., the open circuit potential. The potential was scanned at a rate of
2 mV s1 in the anodic positive direction until pitting i.e., a substantial and rapid increase of current

TABLE 2Lowest potential measured, after the initial spike, during a galvanostatic test.
Solution
Conventional
Hybrid
No
Flux, V
0.21
0.01
1
2
Flux,
V
0.28
0.07
Regular
Flux, V
0.40
0.24
Double
Flux, V
0.24
0.15
2 Area
Fluxed, V
0.14
0.21
was observed or the potential reached +2 V, whichever happened first. The current was recorded as a
function of potential. The pitting potential and the passive current were tabulated.
Corrosion Properties
Galvanostatic Test-Flux Loading StudyThe lowest potential measured, after the initial spike, for the
solutions and flux loading are listed in Table 2. All values are reported as volts versus Ag/ AgCl 3 M KCl
reference electrode SCE-35 mV.
As the current is first applied, the potential rapidly climbs from the open circuit value. For conventional coolants the rapid climb is followed by a rapid fall in the potential as corrosion has been initiated,
Fig. 1. The potential generally becomes approximately constant. The lowest potential, after the initial spike
is recorded, is an indication of how the system repassivates after corrosion has been initiated. The tests are
designated by Ford as pass or fail with a pass defined as a potential above the arbitrarily chosen value of
0.4 V versus SCE.
For the conventional coolant, lower potentials are measured with increasing flux loading, up to a
regular flux amount. The regular amount of flux caused the sample to have a marginal test result. Interestingly, the double flux loading on the sample had a higher potential measurement. The double fluxed
sample was crusty in appearance due to a hard crystalline deposit covering the surface. The lower
potential is probably associated with the limited surface area of exposed aluminum on the sample, due to
the heavy deposits.
The hybrid coolant behaved similarly to the conventional coolant in this test. The lowest potential
measured decreased with increased flux loading up to the regular amount of flux. In this case, however, the
test was a pass. For the double fluxed sample, the potential was slightly higher than in the regular flux
sample. This increase was probably due to the heavy deposit on the surface that limited the amount of
aluminum surface area exposed to the solution.
For both coolants, any amount of the flux on the surface lowers the pitting potential as compared to
the sample without flux. The lowest potential in both types of coolant was the sample with the regular flux
loading.
The sample appearances after the test for different coolants were different. The hybrid coolant samples
exhibited dark staining small pits around the gasket area. The conventional coolant samples exhibited
small pits evenly distributed over the surface.
FIG. 1Schematic of polarization curve from the galvanostatic test, (a) conventional coolant, (b) organic
acid coolant.

TABLE 3Pitting potential, V versus Ag/ AgCl (3M KCl), passive current, A cm2, measured during
a potentiodynamic polarization curve, and surface-area average corrosion rate, m / year, determined
by the Tafel extrapolation method.
Solution and Test

Conventional
Hybrid
Organic Acid
Mod. Organic Acid
Pitting
Passive Current
Average Corrosion Rate
Pitting
Passive Current
Pitting
Passive Current
Pitting
Passive Current
No Flux
0.27
1.75
0.23
None
NA
0.23
1.02
7.4
13.1
1
3.89
1.79
1
2
Flux
0.1
5.09
3.00
0.053
3.37
2.26
1
11.79
25.4
1
7.16
1.96
Regular
Flux
0.16
1.03
0.65
0.25
3.05
1.98
1
15.6
14.5
0.53
1.1
0.91
Double
Flux
0.32
2.66
2.30
0.18
1.35
2.21
0.37
2.05
6.2
0.27
0.35
0.59
2 Area
Fluxed
0.005
1.96
1.46
0.05
5.59
3.40
1
16.62
18.0
0.65
4.11
1.45
NA= Not applicable.
Potentiodynamic Polarization-Flux Loading StudyFrom the polarization curves, three values were
reported: the pitting potential, the onset of stable pitting corrosion; the passive current, the current required
to maintain the passive film on the aluminum surface; and surface-area average corrosion rate, determined
by Tafel extrapolation of the polarization curve to the corrosion potential. Results are shown in Table 3.
The onset of stable pitting is indicated by a change of slope where a large increase in current is
coupled with a relatively small increase in potential. The potential at which this rapid increase in current
occurs is known as the pitting potential, see Fig. 2. The lower the potential, the easier it is to initiate
pitting.
For the conventional coolant, the pitting potential decreased with increasing flux loading, Fig. 2. The
reduction in pitting potential from no flux to double the regular flux load amounted to 590 mV. This
indicates a lowering of the pitting potential with increased flux loading. In other words, it indicates that the
flux is not passive inert, as has been previously thought, but is active and is affecting the corrosion
potential of the aluminum.
In hybrid coolant, no pitting potential could be discerned in the sample with no flux residue because
there was no rapid change in slope during polarization, see Fig. 3. The potential increased as the current
increased, however, in a nonlogarithmic way, and reached a high potential similar to that measured during
active pitting in other samples. The sample with no flux in hybrid solution also had pitting potential
approximately 400 mV above the fluxed samples. This is similar to the conventional coolant and indicates
FIG. 2Potentiodynamic polarization curve of aluminum 3003 with various flux loading in heated 25 %
conventional coolant with 100 ppm chloride.
FIG. 3Potentiodynamic polarization curve of aluminum 3003 with various flux loading in heated 25 %
hybrid coolant with 100 ppm chloride.
that flux loading affects the corrosion potential of the aluminum.
Potentiodynamic polarization curves in organic acid coolants generally behave in the following manner: as the potential of the aluminum is increased a broad region of passivity is measured, with no pitting
occurring before the scan is stopped. This was the case for the organic acid coolant samples with no flux
loading and half the regular amount of flux loading, where the pitting potential measured over 1 V. In the
sample with double the regular amount of flux loading the pitting potential was measured at 0.37 V.
The passive current in Table 3 is the amount of current required to maintain the passive film at the
metal solution interface. In the passive region no active pitting is taking place, even though a measurable
current is recorded. The region is characterized by only a small change in current over a wide change in
potential. The passive currents reported in Table 3 were all within a small range of values from
1.03 to 7.16 A cm2, with the exceptions of the samples tested in organic acid coolant, with passive
currents up to 16.62 A cm2. The lowest passive current was for a double fluxed sample in modified
organic acid coolant at 0.35 A cm2. The hybrid solution with aluminum with no flux residue had no
clear region where the current changed little with increasing potential, and is recorded in the table as NA.
As shown in Table 3, for both conventional and hybrid coolants, the presence of flux generally leads
to an increase in the corrosion rate. The increase in corrosion rate may be as much as more than an order
of magnitude, depending on the amount of flux present on the surface. The corrosion rates in the organic
acid coolant were generally higher than the rates in other coolants. But organic acid coolant was less
affected by the presence of flux on the surface. Modified organic acid coolant yielded substantially lower
corrosion rates under the test conditions. The corrosion rates in modified organic acid coolant were similar
and in some cases, even lower than the corresponding values obtained in conventional or hybrid coolants,
or both, Table 3. It should be noted that the average corrosion rate in all four coolants was very low for the
short immersion period of the tests.
Potentiodynamic PolarizationFlux Commercial Compound StudyWhen samples of the three commercially available flux compounds, brazed into aluminum, were tested by potentiodynamic polarization,
very different curves were recorded than in the flux loading study, Fig. 4. The pitting potentials, passive
currents, and surface-area average corrosion rates are shown in Table 4.
The flux sample A had the highest pitting potential of the three samples tested. Flux sample C
evidenced the lowest pitting potential but the highest passive current and the highest average corrosion
rate. Sample B appears to be the best formulation of those tested, due to having the lowest passive
current and lowest average corrosion rate, as long as it could be maintained below its pitting potential.
Fluoride Ion ContentFlux Loading StudyThe majority of coolants after galvanostatic and potentiodynamic testing were analyzed for fluoride ion content. The results for the fluoride analysis are shown
in Table 5.
When no flux residue is present on the aluminum surface, no fluoride is measured in the end of the test
fluid. However, when flux residue is present on the aluminum surface, fluoride is measurable by ion
chromatography in the coolant sample after test. In addition, the more flux residue present, the higher the
FIG. 4Potentiodynamic polarizations of three different flux compounds on aluminum sheet, 25 % hybrid
coolant with 100 ppm chloride. The potential value versus an Ag/ AgCl (3 M KCl) reference electrode.
levels of fluoride measured. The galvanostatic test maintains the sample at high temperature longer than
the potentiodynamic test, approximately 2 h 20 min versus 1 h 45 min, respectively. This most likely
explains the higher levels of fluoride in the galvanostatic test fluids than the potentiodynamic test fluids.
Of the fluids tested, the organic acid coolant had the highest levels of fluoride at the end of the test
50 g / mL for the regular flux sample in the potentiodynamic test. The next highest levels were found in
the hybrid 25 g / mL and the conventional coolant 14 g / mL. The lowest levels occurred in the
modified organic acid 5 g / mL.
To confirm that the electrochemical testing was not causing the presence of fluoride in the end of test
fluids, testing was conducted with double fluxed aluminum samples. The samples were immersed in
conventional and hybrid coolants and heated in a similar way as the samples prepared for electrochemical
testing boil for 1 h, reduce temperature to 70 C, maintain at 70 C for 15 min but were not electroTABLE 4Pitting potential and passive currents for three different fluxes on aluminum in 25 % hybrid
coolant solution with 100 ppm chloride.
Test/ Flux Supplier
Pitting Potential, V
Passive Current, A / cm2
Average Corrosion Rate,
m / year
A
0.164
7.66
20.4
B
0.203
4.62
12.8
C
0.27
32.5
49.8
TABLE 5Fluoride content in after test fluid in g / mL. Measured by ion chromatography.
Solution and Test
Conventional
Galvanostatic
Potentiodynamic
Hybrid
Galvanostatic
Potentiodynamic
Organic Acid
Potentiodynamic
Mod. Org. Acid
Potentiodynamic
Conventional
No E-Chem
Hybrid
No E-Chem
Note: ND= None detected.
No
Flux
1
2
Flux
Regular
Flux
Double
Flux
2 Area
Fluxed
1
1
9
8
19
14
9
7
8
9
1
1
26
24
33
25
81
16
28
20
25
50
100
55
ND
11
69

TABLE 6Fluoride content in end of test fluid, measured by ion chromatography.
Concentration of
Fluoride/Flux Supplier
Fluoride, g / mL
A
71
B
31
C
168
chemically tested. Significant amounts of fluoride were present in the end of test fluids, as shown in Table
5. This indicates that fluoride freely leaches into the test fluids from the flux residue during the test. The
variation in the amount of fluoride measured in the nonelectrochemistry samples versus the electrochemically tested samples could be due to sample to sample variation.
Fluoride Ion ContentFlux Commercial Compound StudyOf the three different flux types tested in
hybrid solution with 100 ppm chloride, type B flux had the lowest amount of fluoride in the end of the
test fluid, as shown in Table 6. The flux type C has poor corrosion resistance, as well as the highest
fluoride content.
Conclusions
Test results indicate the flux from the CAB brazing process is not inert on aluminum surfaces in the
presence of various types of coolants, from conventional to hybrid to organic acid. The greater the
amount of reacted flux on an aluminum surface, the more active the flux.
The electrochemical results showed that the higher the flux loading on the aluminum header material, the lower the pitting potential and the easier it was to initiate corrosion. This was consistent
with all fluids tested.
Chemical analysis shows the presence of significant quantities of fluoride in the end of test the fluid
for samples with flux. The modified organic acid coolant evidenced negligible fluoride in the end of
the test solution. In the case of no flux loading, no fluoride was detected in all coolants.
Since the only fluoride containing component of the system is the flux, it appears fluoride leaches
from the flux.
Results indicate brazing flux composition also affects corrosion potential. Samples of three different
flux compositions with the same flux loading and tested with hybrid coolant evidenced significantly
different electrochemical results and fluoride ion concentrations. In this round of testing for leaching of fluoride, flux type B was considered a better formulation for engine coolant applications.
References
1
2
3
4
5
6
7
Ford Test Method BL 105-01, A Rapid Method to Predict the Effectiveness of Inhibited Coolants
in Aluminum Heat Exchanger, Ford Motor Company, 2001, pp. 15.
Claydon, D. and Sugihara, A., Brazing Aluminum Automotive Heat Exchange Assemblies Using a
Non-Corrosive Flux Process, SAE 830021, February-March 1983.
Ando, Y., Nita, I., Uramoto, M., Ochiai, H., and Fujiyoshi, T., Development of Aluminum Radiators Using the Nocolok Brazing ProcessCorrosion Resistance of New Aluminum Radiators by
Applying a Nocolok Brazing Process, SAE 870180, February 1983.
CASTI Metals Red BookNonferrous Metals, 4th ed. on CD-ROM, Casti Publication, Inc., Edmonton, Alberta, Canada, 2003.
Wiggle, R. R., Hospadaruk, V., and Tibaudo, F. M., Corrosion of Aluminum Alloys Under Heat
Transfer Conditions, SAE 810038, Society of Automotive Engineers, Warrendale, PA, 1981.
Wiggle, R. R., Hospadaruk, V., and Styloglou, E. A., The Effectiveness of Automotive Engine
Coolant Inhibitors for Aluminum, J. Mater. Eng. Perform., National Association of Corrosion
Engineers, Houston, 1981, pp. 1318.
A Rapid Method to Predict the Effectiveness of Inhibited Engine Coolants in Aluminum Heat
Exchangers, SAE 800800, Society of Automotive Engineers, Warrendale, PA, 1980.

Paper ID JAI100505
Bo Yang,1 Aleksei V. Gershun,1 Filipe J. Marinho,1 and Peter M. Woyciesjes1
Effect of Fluoride on Corrosion of Cooling System Metals

in Ethylene Glycol-Based Antifreeze/Coolants
ABSTRACT: Automotive and light-duty vehicle heat exchangers such as radiators are now predominantly
made of aluminum alloys. For over 20 years, a brazing technique known as controlled atmosphere brazing
CAB with noncorrosive fluxes has become the preferred process for producing aluminum automotive
heat exchangers for original equipment manufacturers and aftermarket suppliers. Fluoride-based fluxes are
typically used in the CAB processes to dissolve the aluminum oxide layer on the surface and inhibit
reoxidation during the brazing cycle to allow the clad alloy to flow properly. The flux is generally a mixture
of potassium fluoroaluminate, K3AlF6, K2AlF5, and KAlF4. The flux residue left on the internal surface of
heat exchangers after brazing is thought to be insoluble and noncorrosive, hence no removal is necessary.
Although external corrosion of brazed aluminum heat exchangers has been studied using salt spray tests,
a study addressing the effect of interaction between different antifreeze and flux residues on internal
corrosion has not been reported. To the authors knowledge, few studies on the effect of fluoride in engine
coolants on metal corrosion are available. In this paper, laboratory test data are provided to show that flux
residue is soluble in commercially available coolants and can generate fluoride ions that enhance cooling
system corrosion. Systematic study on the effect of fluoride on metal corrosion in cooling systems and its
remedies are also presented and discussed.
KEYWORDS: antifreeze/coolant, aluminum corrosion, fluoride, brazed aluminum, heat exchangers,
potassium fluoroaluminate flux
Introduction
Aluminum alloys are predominantly used as the material of choice for various components in modern
light-duty automotive cooling systems to reduce the weight of the vehicles. Specifically, in addition to the
engine block, a variety of heat exchangers in the cooling systems, such as radiator, condenser, evaporator,
and heater core, are made of aluminum alloys. In the past, mechanical expansion techniques have been
used for mass-production of automotive heat exchangers 1. Because of having inferior thermal performance and relatively high weight, heat exchangers assembled mechanically are not widely used. Heat
exchangers are now predominantly formed by a brazing operation, wherein the individual components are
permanently joined together with a brazing alloy.
Recently, one brazing technique known as controlled atmosphere brazing CAB has become accepted by the automotive industry for making brazed aluminum heat exchangers, including radiators,
condensers, evaporators, heater cores, air charged coolers and inter-coolers 24. CAB brazing has been
preferred over a previous brazing method, i.e., vacuum furnace brazing 2, due to improved production
yields, lower furnace maintenance requirements, greater braze process robustness, and lower capital cost
of the equipment employed.
In the CAB process, a fluxing agent is applied to the preassembled component surfaces to be jointed.
During brazing at approximately 560 575 C, the fluxing agent starts to melt and the melted flux reacts,
dissolves, and displaces the aluminum oxide layer that naturally formed on aluminum alloy surface and
frees up the filler metal clad aluminum. The filler metal starts to melt at about 575 590 C and begins to
flow toward the joints to be brazed. During the cooling process, the filler metal solidifies and forms braze
joints. The flux present on the surface also solidifies and remains on the surface as residue. Additional
functions of the fluxing agent are to prevent reformation of an aluminum oxide layer during brazing, and
Manuscript received February 22, 2006; accepted for publication September 22, 2006; published online October 2006. Presented
at ASTM Symposium on Engine Coolant Technologies: 5th Volume on 17 May 2006 in Toronto, Canada;
1
77
enhance the flow of the brazing alloy. The fluxing agent is typically a mixture of alkaline metal fluoroaluminates with the general formula K1-3AlF4-6 xH2O. One widely used flux for brazing aluminum is sold
under the trademark Nocolok, which is essentially a mixture of K3AlF6, K2AlF5, and KAlF4 5,6.
Fluoride-based fluxes are preferred over chloride-based fluxes for brazing aluminum or aluminum alloys
because they are considered to be inert or noncorrosive to aluminum and its alloys, and substantially water
insoluble after brazing. Hence, no removal is necessary after the brazing operation. Due to the noncorrosive nature of the flux together with its tolerance to brazing assembly fit-up and flexible control, Nocolok
flux brazing is one of the lowest cost methods for the joining of aluminum heat exchangers. It is now
commonly used by the automotive industry for manufacturing of heat exchangers 3,7.
Corrosion of brazed aluminum heat exchangers has been studied using salt spray tests 7. The presence of flux residues on a heat exchanger surfaces is shown to enhance the corrosion resistance. A study
by Davies and Prigmore 8 suggested that the presence of 100 ppm sodium fluoride in distilled water
containing 100 ppm KC1 at 25 1 C could delay the onset of pitting of a commercially pure aluminum at
0.85 V versus a Hg/ HgSO4 reference electrode due to a probable formation of a surface film made of
some form of aluminum oxyfluoride or hydroxyfluoride. However, replacing the distilled water with 50 %
ethylene glycol solution showed that no delay of the onset of pitting of the aluminum under similar test
conditions was observed 8. It was determined that a much thinner surface film containing fluoride was
formed in the 50 % ethylene glycol solution. To the authors knowledge, studies conducted under conditions more relevant to engine cooling system operating conditions have not been reported.
Research conducted by Prestone R&D Laboratory shows that the flux residue on an aluminum alloy
surface will leach out fluoride ions which can lead to localized corrosion on the metal substrate when it is
immersed in a number of commercial coolants under engine cooling system operating conditions. Systematic study on the effect of fluoride on metal corrosion in cooling systems and its remedies are also
presented and discussed.
Experimental
Solutions
The base test solutions were prepared by mixing commercially available coolants with deionized water to
yield a coolant concentration of either 25 vol. % or 50 vol. %. Aqueous solution of 40 % w/v KF from
Spectrum Chemical Mfg. Corp. was used as the source of fluoride. Other components of the test solution
were sodium chloride ACS grade and commercial products supplied by the producers.
Metal Plate Samples and Test Procedures
Brazed Aluminum with Flux ResiduesSheets of aluminum header alloy AA 3003 were prepared
with flux. The sheets were applied with various load concentrations of flux. The flux types were designated
as B1 and B2, respectively. The concentrations of the applied flux were either a regular flux load amount
B1 or a double amount of flux B2 on the surface. The amount of flux applied was determined by
weighing a virgin plate with no flux. Then the sheet was sprayed with flux in the production process and
the sheet was weighed again. The amount of the flux for that surface area was taken as a regular flux
loading. The sheets were then brazed and cut into 2 by 2 in. sections. The sample quality was variable in
coverage and thickness of flux. Samples used in the experiments were chosen to be as representative as
possible. The samples were used as received.
Wrought Aluminum AA 3003 (UNS A93003)Sheet of AA 3003 1 / 16-in. thick obtained from
McMaster-Carr were cut into 2 by 2 in. sections. The samples without any visible scratches were chosen
for use as the electrode. In some tests, 600 grit silicon carbide sand paper polished plates of Al 3003
1 / 4-in. thick, 2 by 2 in. were also used as the test electrode. The electrode sample was cleaned with
acetone and air dried just before immersion in the test solution for electrochemical tests.
Cast Aluminum AA 319 (UNS A03190)Round plate of AA 319 2-in. diameter by 3 / 8-in. thick
obtained from The Metaspec Co. were used as the electrode. The samples were polished by 600 grit silicon
carbide sand paper, cleaned with acetone, and air dried before immersion into the test solution.
YANG ET AL. ON EFFECT OF FLUORIDE 79
Test CellsA Ford Laboratory Test Method FLTM BL-105-1 A Rapid Method to Predict the
Effectiveness of Inhibited Coolants in Aluminum Heat Exchangers test cell was used to conduct the tests
for the metal plate sample. The FLTM BL-105-01 test cell would give an exposed aluminum surface area
of 8.04 cm2. The volume of solution used in a test was about 45 mL. A graphite rod was used as counter
electrode. A silver/silver chloride 3 M KCl reference electrode placed in a Luggin probe was used as the
reference electrode.
Test ProceduresThree test conditions were used for the plate metal samples. In one test, the test
coolant fluid was added to the cell and the aluminum heated until the fluid boiled. The fluid was boiled for
1 h, while maintaining the fluid volume by additions of deionized water if required, and then the
temperature of the fluid reduced to 70 C. Once the solution in the cell had reached the temperature of
70 C, the sample was connected to a potentiostat as the working electrode. The open circuit potential was
measured for 5 min and a potentiodynamic polarization scan started at 20 mV versus the open circuit
potential. The potential was scanned at a rate of 2 mVs1 in the anodic positive direction until pitting was
observed or the potential reached 2 V more anodic than the open circuit potential, whichever happened
first. The current was recorded as a function of potential. At the end of the test, samples of before and after
test fluid were submitted for analysis of fluoride ions.
In the second test, the test fluid was added to the cell and the flux residues covered brazed aluminum
sample was heated until the solution reaching 80 C and maintained at this temperature for 6 h. At the end
of the test, the mass loss of the brazed aluminum sample was determined after drying in a 60 C oven
overnight. Samples of the test fluid before and after the test were analyzed for fluoride ions. In this test, no
electrochemical measurement was conducted on the sample.
In the third test, test coolants containing various concentrations of fluoride ions were used. The test
solution was added to the cell and the aluminum AA 319 or AA 3003 electrode sample was heated until the
solution reaching 85 C and maintained at this temperature for the duration of the test, typically ranging
from 4 h to 7 h. Once the solution in the cell had reached the temperature of 85 C, the sample was
connected to a potentiostat as the working electrode. The open circuit potential was then measured for at
least 30 min. Immediately after the open circuit potential measurement, a polarization resistance measurement of the sample was conducted using a scan rate of 0.1667 mVs1. Afterwards, a potentiodynamic
polarization scan using a scan rate of 2 mVs1 in the anodic positive direction until reaching about 5 V
versus Ag/ AgCl 3 M KCl was conducted.
NanoCorr Coupled Multi-electrode Sensors for Measuring Localized Corrosion
A Corr Instruments NanoCorr Coupled Multi-electrode Sensor CMS Analyzer with Corr Visual Software, Version 1.0.3, was used to determine the localized corrosion rate of cast aluminum in the test
solution. The CMS method is a new electrochemical method capable of real-time monitoring of localized
corrosion rates of metal in corrosive media 9. A more detailed description of the use of this method for
use in coolant research is described in a separate paper 10. In this study, a 25-electrode sensor array
probe supplied by Corr Instruments was used. Each electrode of the probe is made of the same cast
aluminum SAE 329, UNS A23190 square wire having an exposed surface area of 1 mm2. The 25 wire
electrodes sealed in Epoxy and spaced uniformly in a 1.2 by 1.2 cm matrix array were connected electrically. The coupled multi-electrode probe simulates the corrosion conditions of a conventional one-piece
electrode surface having an exposed surface area of about 1.4 cm2. One can obtain a localized corrosion
rate as a function of time from the probe by measuring the coupling current from each individual electrode
in the probe and performing statistical analysis of the measured data 9. In this study, a sampling rate of
30 s per set of data was used.
A Pyrex glass beaker holding 500 mL of test solution was used as the test cell. The coupled multielectrode array sensor probe, a Ag/ AgCl 3 M KCl reference electrode placed in a Lugin probe with the
opening close to the multi-electrode sensor probe, and two temperature sensor probes i.e., a thermal
couple and a resistance temperature detector with stainless steel sheath are mounted on a Teflon cell cover
and immersed in the solution in the beaker. The Teflon cover was used to minimize solution loss during the
experiment and also used to fix the position of the test probes in the cell. A microprocessor control

TABLE 1Fluoride concentration after electrochemical tests on brazed aluminum in various coolants. Solution boiled for 1 hr. Test
Solution Volume 45 mL. Potentiodynamic scan test done after solution temperature cooled to 70 C. Surface area average corrosion
rate determined by Tafel extrapolation of the anodic polarization curve.
Coolant ID
Fluoride, mg/L
25 % OAT coolant A + 100 ppm Cl
56
25 % OAT coolant A + 100 ppm Cl, No flux or
0
brazed
25 % HOAT coolant+ 100 ppm Cl
113
25 % SIT coolant+ 100 ppm Cl
26
25 % OAT coolant A + Additive 1 + 100 ppm Cl
7
25 % OAT coolant A + Additive 2 + 100 ppm Cl
5
Observation
Corrosion Rate, m / y
90 % surface area were attacked
9.02
Surface AA3003 showed minimal attack
13.1
Surface
Surface
Surface
Surface
attacked intensively
showed isolated localized attack
showed very minor attack
showed no noticeable attack
140
0.85
1.56
3.81
Note: % coolant is by volume.
hot-plate was used to heat the solution to the desired temperature during the test. A Teflon coated magnetic
stirring bar was also used to agitate the solution during the test. The solution was exposed to the air during
the test.
Brazed AluminumEffects of Different Coolant Chemistry and Organic Additives
Table 1 shows the results of solution analysis of fluoride concentrations in various coolant formulations
after exposing to a potassium fluoroaluminate flux-brazed aluminum sample and after conducting anodic
polarization curve measurements on the sample while immersing in the coolants. The results show that
while coolants at 25 vol. % dilution containing organic acids OAT, low silicate organic acid hybrid
HOAT and conventional SIT high silicate-based corrosion inhibitor formulations can provide excellent
corrosion protection for aluminum alloys without any flux residue in vehicle operation conditions, their
corrosion protection for brazed aluminum containing fluoride-based flux residue on the surface have room
for improvement. Concentrations of fluoride in the post-test fluids were 26, 56, and 113 mg/ L for SIT,
OAT and HOAT, respectively. Addition of a small amount of corrosion inhibition additives to an organic
acid-based coolant resulted in substantial improvement in corrosion protection of the brazed aluminum
containing flux residue. The amount of fluoride ions being released into the test fluid was also reduced
drastically by the addition of the corrosion inhibition additives. Different additives appeared to yield
different results under the same dosage conditions. The anodic polarization curve results see Fig. 1 show
similar results as previously described in Table 1. It should be noted that the results shown in Fig. 1
indicate that additive 1 appeared to yield better corrosion protection for the brazed aluminum than additive
2 under comparable conditions.
Table 2 shows the results on solution analysis of fluoride concentrations and brazed aluminum sample
mass loss under a different set of test conditions using 50 vol. % coolants. No electrochemical measurement was conducted on the samples in this set of tests. The samples were immersed in the test solutions
longer than the ones used in Table 1. The results suggest that electrochemical measurements are not the
sole cause of fluoride ions being release from the flux residue covered surface. The addition of 100 ppm
chloride seemed to result in an increase in the amount of fluoride ions being release into the test solution.
The brazed aluminum corrosion protection performance was increased substantially when a small amount
of organic corrosion inhibiting additives was added into an organic acid based coolant. The improvement
in corrosion protection performance was demonstrated by the reduction in both the mass loss of the test
sample and the amount of fluoride being release to the test solution detected at the end of test by ion
chromatography. The results in Table 2 show that the corrosion behavior of the brazed aluminum in
50 vol. % coolant solution is similar to the ones observed in 25 vol. % coolant solutions.
Effect of Flux Loadings on Corrosion Protection Performance
Table 3 show the corrosion test results i.e., surface area average corrosion rates and corrosion potentials
and fluoride concentrations contained in the 25 vol. % OAT coolant A OAT and a modified OAT coolant
FIG. 1Effect of coolants on corrosion of brazed aluminum covered with flux residue.
A MOAT end of test solutions for the various brazed aluminum samples having normal flux loading e.g.,
designated as B1 and at a double flux loading e.g., designated as B2. The results indicate the following:
1. The average corrosion rates determined from Tafel extrapolation of the anodic polarization curves
on the brazed aluminum surface with double amount of the flux loadings were higher than the
corresponding values with regular amount of flux loading.
2. Addition of organic additive 1 contained in the MOAT solution, substantially reduce the average
corrosion rates by about 77 to 93 % in comparison with the corresponding values for the coolant
TABLE 2Mass loss and fluoride concentration results for brazed aluminum in various coolants. Solution heated to 80 C for 6 h.
Sample exposed surface area 8.04c sq cm. Solution V 45 mL.
50
50
50
50
50
50
%
%
%
%
%
%
OAT
OAT
OAT
OAT
OAT
OAT
Coolant ID
Coolant A
Coolant A + 100 ppm Cl
Coolant B + 100 ppm Cl
Coolant C + 100 ppm Cl
Coolant A + Additive 2 + 100 ppm Cl
Coolant A + Additive 3 + 100 ppm Cl
Fluoride, mg/L
37
71
47
30
3
5
Mass Loss, mg
5.9
6.4
4.9
5.4
0.8
0.6
Note: % coolant is by volume.
TABLE 3Fluoride concentration in end of test solution and surface area average corrosion rate determined by Tafel extrapolation of
the anodic polarization curve, and corrosion potential of various brazed aluminum in OAT coolants.
Brazed Aluminum ID
B1
B2
25 vol. % OAT Coolant A

Fluoride, mg/L
Corrosion Potential, V/AgAgCl
Average Corrosion Rate, m / y
Fluoride, mg/L
Corrosion Potential, V/AgAgCl
Average Corrosion Rate, m / y
90
65
0.61
0.584
13.8
40.5
25 vol. % Modified OAT Coolant A
5
5
0.682
0.765
3.11
2.94
FIG. 2Effect of coolant chemistry on brazed aluminum corrosion.

without the additive. The corrosion rates in the modified OAT coolant A show little variation with
regard to the flux loading.
3. Significant amounts of fluoride ions were detected in the end of test solutions by ion chromatography. The amount of fluoride released to the solution may vary to some degree due to a number
of variables involved in the brazing operation.
4. In the modified MOAT A, the amount of fluoride ions being released to the solution were substantially reduced. The very low concentrations of fluoride ions being detected at the end of the
test showed little variation with regard to the flux loading.
The anodic polarization curves determined by potentiodynamic scan measurements corresponding to
the conditions given in Table 3 are shown in Fig. 2. The anodic polarization curve of sample B1 in OAT
coolant, showed no obvious pitting potential; however, the current density did increase steadily and
exceeded 10 A cm2 when the potential exceeded 0 V versus Ag/ AgCl reference electrode. The same
test with a MOAT coolant gave a more positive corrosion potential and lower overall passive currents, Fig.
2. Similar results were obtained on samples with double the flux loading, i.e., B2 sample. The MOAT
coolant maintained the current densities at levels seen within the test with the B1 sample, while the
corrosion current in OAT coolant was considerably higher with the B2 sample.
Effect of Fluoride on Cast Aluminum Corrosion
The effect of fluoride ions on corrosion of cast aluminum UNS A03190 in OAT coolant A is shown in
Fig. 3. The corresponding surface area average corrosion rates are given in Table 4. One can see that
increasing fluoride concentration in coolants generally lead to an increase in corrosion in aluminum parts
not covered with brazed residue, e.g., engine block. The higher the concentration of fluoride, the more
aggressive the coolant could become. An increase in the cast aluminum corrosion rate in the 25 vol. %
OAT coolant A can be observed at a fluoride concentration as low as 28 mg/ L. As shown in Table 4,
fluoride ions appear to be more corrosive than chloride ions under the test conditions.
Effect of Fluoride on Corrosion of Wrought Aluminum AA 3003 in OAT Coolant B
The effects of fluoride ions on corrosion of wrought aluminum AA 3003 in 25 vol. % of OAT coolant B
is shown in Fig. 4. The corresponding surface area average corrosion rates are shown in Table 4. Similar
FIG. 3Effect of fluoride on corrosion AA 319 in 25 vol. % OAT coolant A.

to the results obtained on cast aluminum in 25 vol. % OAT coolants A, one can see that increasing fluoride
concentration in coolant B generally led to an increase in corrosion of wrought aluminum parts not
TABLE 4Effect of fluoride on corrosion of aluminum alloys in OAT coolants.
Cast Aluminum UNS A03190 in 25 vol. % OAT Coolant A
Polarization Resistance LPR CorrRate CorrRateTafelanodic
Fluoride Concentration
Ecorr
Ohm* cm2
m / y
m / y
mg/L
V/AgAgCl
None
0.833
4300
127
192
None
0.858
5430
100
152
28
0.871
1660
328
425
55
0.922
897
608
797
112
0.998
675
807
1376
100 mg/ L Chloride
Time at 85 C
h
1
1
1
1
1
0.863
1
1610
339
209
Wrought Aluminum AA 3003 in 25 vol. % OAT Coolant B
Time at 85 C
Ecorr
m / y
m / y
h
mg/L
V/AgAgCl
Ohm* cm2
1
None
0.919
7618
71.5
73.8
1
117
1.037
275
1985
1224
1
228
1.081
173.6
3139
1945
1
561
1.125
64.2
8491
2199
Wrought Aluminum AA 3003 in 25 vol. % OAT Coolant A + Org. Additive
Time at 85 C
Ecorr
mg/L
V/AgAgCl
m / y
m / y
h
Ohm* cm2
1
563
0.9405
8576
63.6
48.9
Wrought Aluminum AA 3003 in 50 vol. % OAT Coolant B
Ecorr
Immersion Time
m / y
m / y
mg/L
V/AgAgCl
h
Ohm* cm2
0.9035
15650
34.8
20.2
54 h of cycling between
None
565
1.0266
1708
319
217
85 C 6.5 h and Room T17.5 h
Note: Corrosion rates were surface area averaged values. Polarization resistance measurements were conducted 10 min before anodic scan.
Stern-Geary coefficient of 49.9 mV was used to convert the polarization resistance value to the LPR corrosion rate value.
FIG. 4Effects of fluoride and organic additive on corrosion AA 3003 in 25 vol. % OAT coolants.
covered with brazed residuals. The effect increases with increasing fluoride concentration. In the presence
of 560 mg/ L fluoride, the surface area average corrosion rate of the AA 3003 sample was increased
approximately 30 times in comparison with the values observed in the absence of fluoride in 25 vol. % of
coolant B. Addition of a small amount of organic additive is very effective in reducing corrosion rate of
AA 3003 even in the presence of approximately 560 mg/ L fluoride. The effect of fluoride on increasing
corrosion rate of AA 3003 persisted after 54 h of cyclic immersion between high temperature
6.5 h per day and room temperature rest of the day, as shown in Fig. 5. Again, the average corrosion
FIG. 5Effect of fluoride on corrosion AA 3003 in 50 vol. % OAT coolant B.
FIG. 6Localized corrosion rate of cast aluminum in 25 vol. % OAT coolant B.

rate of AA 3003 in 50 vol. % OAT coolant B in the presence of approximately 560 mg/ L fluoride after
54 h of the cyclic temperature exposure conditions was increased by about ten times in comparison with
the values obtained in the absence of the fluoride ions.
Effect of Fluoride and Organic Additives on the Localized Corrosion of Cast Aluminum
Figure 6 shows the test results obtained from the NanoCorr Coupled Multielectrode Analyzer instrument
using a 25-electrode probe immersed in 25 vol. % OAT coolant B. Each electrode of the probe is made of
the same cast aluminum UNS A23190 square wire having an exposed surface area of 1 mm2. As shown
in Fig. 6, localized corrosion rate of the cast aluminum was generally much higher than the comparable
general or surface area average corrosion rate determined from conventional electrochemical methods
e.g., the ones determined from Tafel extrapolation of the anodic polarization curve given in Table 4.
There was also substantial fluctuation in the localized corrosion rate measured by the instrument, probably
reflecting the nonsteady state nature of the pitting corrosion processes. As solution temperature increases,
the cast aluminum localized corrosion rate also increases. As immersion time increases, the localized
corrosion rate appears to be decreased slightly. The cast aluminum localized corrosion rate increased by
more than 300 % after the addition of approximately 100 mg/ L fluoride into the solution from
300 40 m / y to 1600 350 m / y. The addition of another 100 mg/ L fluoride total approximately
200 mg/ L into the solution increased the cast aluminum localized corrosion rate further, e.g., to about
2300 500 m / y, and simultaneously increasing the fluctuations of the localized corrosion rate. Addition
of a small dose of organic additive led to a very rapid reduction of the cast aluminum localized corrosion
rate. About 1.5 h after the corrosion inhibition additive was introduced, the cast aluminum localized
corrosion rate was reduced to about 29 m / y. After the solution temperature decreased the localized
corrosion rate decreased further, reaching to a value of about 1.3 m / y after 3 h of additional testing.
Conclusions
Flux residue remaining on the aluminum alloy heat exchanger surface is soluble in commercial
coolants and will leach out fluoride ions that enhance the corrosion of metals in the engine cooling
system.
The amount of fluoride ions that releases into the coolant depends on the chemical compositions of
the coolant and other variables e.g., flux loading, compositions of the flux used, etc. involved in
the brazing process.
The corrosive effect of fluoride for aluminum alloys increases with increasing concentration of
fluoride ions.
Addition of the small amount of organic additives into the OAT coolants are shown to be very
effective in eliminating the damaging corrosive effect of the fluoride ions on aluminum components
of engine cooling system.
References
1
2
3
4
5
6
7
8
9
10
Conn, P. J., and Schrameck, W. J., US Patent No. 5,360,158.

Van Evans, T., Zaluzec, M. J., Mehraban, H., Burt, R. P., Uyeda, S. Y., and Eye, J. B., US Patent
No. 6,120,848.
Liu, J., NOCOLOK Flux and Aluminum Brazing, SAE Paper No. 960244, 1996.
Field, D. J. and Steward, N. I., Mechanistic Aspects of the NOCOLOK Flux Brazing Process,
SAE Paper No. 870186, 1987.
Wallace, E. R., and Dewing, E. W., US Patent No. 3,951,328.
Cooke, W. E., US Patent No. 3,971,501.
Rajagopalan, R., Pierre, E., and Ramez, A., Effect of Post Brazed Flux Residues of CAB Evaporators on the Consistency of Conversion Coating, SAE Paper No. 2005011773, 2005.
Davies, D. E. and Prigmore, R. M., The Effect of Sodium Fluoride on the Localized Corrosion of
Aluminum in Distilled Water and 50 % Ethandiol Solution, Proceedings of International Congress
on Metallic Corrosion, Vol. 4, June 37, 1984, Toronto, Canada, pp. 356351.
Yang, L., Sridhar, N., Pensado, O., and Dunn, D. S., Corrosion, NACE, Vol. 58, 2002, p. 1004.
Yang, B., Marinho, F., and Gershun, A. V., Proceedings of ASTM 5th International Symposium on
Engine Coolant Technologies, May 1718, 2006, Toronto, Canada.

Paper ID JAI100686
Glen Davis and Mark Sarlo
Heavy-Duty Diesel Engine Cavitation Test

ABSTRACT: The objective of this study was to develop a test procedure to evaluate the ability of a
heavy-duty diesel engine coolant to provide protection against damage resulting from a phenomenon
known as cylinder liner cavitation corrosion. The engine cavitation test procedure was developed by modifying a production OEM diesel engine to consistently produce the operating conditions that accelerate
damage from cylinder liner cavitation. The resulting, 250-h test procedure was able to quantify a coolants
ability to protect wet-sleeve cylinder liners from cavitation corrosion. Dozens of coolants were evaluated
using this test procedure. The ranking of cylinder liner pit area counts from this procedures discrimination
matrix was in agreement with the ranking of pit area results seen in high-mileage field tests. Conversely,
upon investigation, an acceptable correlation could not be established between field test pit area counts
and the results from a known bench test. Obtaining results in a few weeks from a short duration procedure
such as this can offer a coolant formulator advantages compared to waiting for the completion of a properly
conducted field test. This test procedure creates an accelerated, yet realistic level of liner cavitation that
ranks protection levels of coolants being evaluated. This ranking or discrimination is often not possible in
field testing because the field test is run under mild service conditions or the engine components have little
tendency to promote liner pitting. In addition, the difficulty in controlling field tests often yields unusable,
inaccurate results. The test procedure was shown to be repeatable within labs and reproducible between
labs thus confirming the viability of this test procedure as a useful tool to assess a coolants ability to protect
against cylinder liner cavitation damage. It is recommended that the presently developed test procedure be
considered for adoption as an ASTM test method.
KEYWORDS: cavitation, pitting, pitted area, heavy duty engine coolant, cylinder liner, engine coolant
Introduction
Heavy-duty HD diesel engines with wet sleeve liners are likely to experience cylinder liner cavitation
and resulting damage unless a properly formulated, heavy-duty diesel engine coolant is used in the engine
cooling system. Heretofore, companies manufacturing engine coolant had no way of testing their coolant
as to its performance for suppressing cylinder liner cavitation other than running extensive dynamometer
tests or long term fleet tests. John Deere has modified a production engine to be used as a test engine, and
developed a 250-h engine test procedure, that will consistently produce cavitation in order to evaluate
coolants as to their tendency to suppress cylinder liner cavitation and resulting damage. One of these
modified engines and the test procedure have been given to Southwest Research Institute SwRI to run
on a commercial basis.
The purpose of this paper is to provide a description of the test engine, the test method, and the
supporting data to ASTM for determining the viability of this test becoming a standard for testing the
capability of a candidate coolant to suppress cylinder liner cavitation and resulting damage in heavy-duty
diesel engines.
An engineering test report from Cummins/Fleetguard is included in the Appendix as supporting data
and ongoing research. This report is important since it is an application of this test method by an engine
coolant manufacture with the test being run by an independent lab SwRI.
Historical Background
This engine test was originally developed at John Deere Product Engineering Center 1994 in order to test
the capability of propylene glycol PG base coolant to suppress cylinder liner cavitation and resulting
damage as compared to ethylene glycol base coolant. 1 After completing that program, the need was
Manuscript received June 7, 2006; accepted for publication October 11, 2006; published online September 2007. Presented at
87
evident for a fired engine/dyno test that would discriminate between coolants as to cavitation control and
protection from cavitation damage. Contributing factors for developing an in-cell, engine/dynamometer
test were 1 the high costs of fleet testing; 2 the difficulty of controlling a fleet test, which sometimes
can result in bad data or no usable data; 3 the inability of bench tests to distinguish closely the difference
in protecting the cylinder liners from cavitation damage.
A test program was started using the same modified engine configuration to compare different coolants
as to their ability to suppress cylinder liner cavitation damage. In 1997 a separate test engine was built,
tested, and sent to SwRI to test for reproducibility between labs, repeatability, and ultimately to be used
for commercial running of this test procedure. The Appendix is a Cummins/Fleetguard engineering report
on the results of a coolant test program using this test engine and test method. In excess of 40 tests have
been run using the two test engines.
Test Engine Description
The test engine is a John Deere, inline six-cylinder, 10.1-l 6101H, intercooled, turbo-charged, heavyduty, direct injected diesel engine. The coolant thermostats were removed in order to control coolant out at
the correct temperature. The direct cooling to the top annulus of each cylinder liner was removed. Each set
of test liners was machined to give more annular clearance between the piston outside diameter OD and
liner inside diameter and between the liner OD and the engine block in order to enhance liner vibration
cavitation in a controlled manner.
Summary of Test Method for Diesel Engine Coolant Cavitation Test
Scope
This test procedure was designed to evaluate an engine coolants ability to prevent, inhibit, or suppress
cavitation damage to engine cylinder liners exposed to coolant within the cooling system.
Background
During the power stroke in a diesel, compression ignition engine, the forces exerted on the internal surface
of a diesel engines cylinder liners can cause the liner wall surface to vibrate. This vibration can result in
the exterior surface of the liner, in contact with the coolant, to rapidly vibrate the coolant, resulting in a
potentially damaging mechanism known as cavitation. Without proper protection for this exterior liner
surface, damage can occur which will result in pitting of the metal surface. This pitting can propagate
through the entire thickness of the liner allowing engine coolant to enter the cylinder chamber ultimately
resulting in engine failure. It was found that if certain dimensions of an engines geometry were configured
in a certain way and certain operating conditions were controlled, damage from cavitation could be
enhanced. The John Deere, six-cylinder, 10.1-l, 6101H, turbo-charged, intercooled, heavy-duty diesel
engine, with several modifications and operational conditions to optimize an environment for cavitation,
was found to be a good test tool to discriminate between the coolants ability to protect from cavitation
damage.
Test Engine
The test engine is a John Deere, six-cylinder, 10.1-l, 6101H, turbo-charged, intercooled, heavy-duty
diesel engine. Rated speed is 2100 RPM; peak torque is at 1500 RPM. Before each test, the engine is
rebuilt with specially machined, pre-measured, cylinder liners. Except for gaskets and expendables, the
remaining engine components are reused and replaced according to an as-needed basis.
Test Cell
Fully instrumented test cell equipped with a dynamometer or equivalent capable of absorbing up to
300 kW at 2100 RPM and/or 1425 Nm at 1500 RPM. Maximum speed capability for dynamometer should
be 2700 RPM. Entire cooling system should be configured for a total volume of about 50 10 liters and is
DAVIS AND SARLO ON HEAVY-DUTY DIESEL ENGINE CAVITATION TEST 89
run without a pressure cap. Coolant inlet plumbing to the engines coolant pump is configured with
smooth, large-diameter piping to reduce flow restriction so that the coolant pump does not cavitate.
Test Sequence
Break-In After Installing Test Liners
Step Number
1
2
3
4
5
Step Time, min

1
2
10
5
1
RPM
950
2100
2100
2100
2600
Torque, Nm
Min Loada
780
780
1186
Min Loada
Power, kW
Record
172
172
261
Record
Coolant Out, C
Record
Record
70
70
70
Ramp Time, RPM
30 s
1 min
1 min
Ramp Time, Torque
30 s
1 min
1 min
Min Load indicates no excitation to dynamometer and the magnitude would be the resulting load from drag
The engine oil and filter are changed to remove wear metals resulting from break-in. This is not an oil
evaluation test procedure.
20-h, Steady-State, Extended Break-In
Step Time, h
20
RPM
2100
Torque, Nm
762
Power, kW
168
Coolant Out, C
70
On Test, Cyclic, 230 h

Step
Step Time,
Throttle
Number
min
Step Name Position, %
1
1.5
Low idle
0
2
1.0
Peak torque
100
3
4.0
Full load
100
4
1.0
FLoad O-spd
100
5
0.5
Fast idle
0
Torque, Power, Coolant

RPM
Nm
kW
Out, C Fuel kg/hr Intake Air, C Fuel, C Ambient, C
800
Minb Record 70 5
29 10
40
1045
1500 1425 225 70 5
29 10
40
1045
2100 1200 260 70 5
61
29 10
40
1045
2310 795 195 70 5
29 10
40
1045
2625 Minb Record 70 5
29 10
40
1045
Min indicates no excitation to dynamometer and the magnitude would be the resulting load from drag
Oil additions are allowed as this is not an oil evaluation test.

After the test engine is rebuilt with the modified test liners, new gaskets, and expendables, the engine
is charged with 29.3 kg of John Deere Plus 50 15W-40 heavy-duty engine oil or equivalent. A new oil
filter is installed. The engines cooling system should be vacuum filled with approximately 50 l of the
coolant to be evaluated. The engine is run through the 19-min break-in sequence and allowed to cool
down. The engine oil is drained and the oil filter removed. Again, the engine is charged with 29.3 kg of
John Deere Plus 50 15W-40 heavy-duty engine oil or equivalent. A new oil filter is installed. The test
time clock is reset to zero hours and the engine is run through the steady-state, 20-h extended break-in
sequence followed by 230 h approximately 1725 8-min cycles of On Test conditions to accumulate a
total test duration of 250 h.
Oil and Coolant Sampling and Analysis
Collecting oil and coolant samples is required for this test procedure. As good practice, to monitor the
overall condition of the engine, 120-ml oil samples may be collected at each 50-h interval. The lab
conducting this test procedure may choose to have the oil sample tested for wear metals, total base
number, kinematic viscosity, fuel dilution and possibly soot level. Additionally, as good practice, 250-ml
coolant samples may be collected and analyzed at 125- and 250-h intervals.
Analysis of Results (Pit Area Counting Procedure)
Original MethodAfter completion of each 250-h test, the engine was disassembled and the cylinder
liners cleaned for pit counting. A transparent grid 2.16-mm squares was used to count the pits in the
following manner.
1. Visually inspect each liner. With a fine point permanent marker, outline the outside boundary of
pitted areas. This could range from a single pit to many pits concentrated in a given area. Histori-
FIG. 1Accelerated heavy duty engine cavitation coolant testing. The original method of counting pits
was used for these data. A1, John Deere Cool-Gard; A1, John Deere Cool-Gard; A2, John Deere CoolGard (slight modification); A2, John Deere Cool-Gard (slight modification); Z1, Universal Low Silicate
ASTM D 4985 (no SCA); Z1, Universal Low Silicate ASTM D 4985 (no SCA); Z1, Universal Low Silicate
ASTM D 4985 (no SCA); Z2, Traditional Automotive; B1, European Hybrid; B2, European Hybrid (different version); C, European Organic Acid Technology (OAT); D1, Asian OAT; D2, Asian OAT (10 %
reduction in additive package); E1, Asian Hybrid; E2, Asian Hybrid; F1, Water John Deere Coolant
Conditioner @ 6 %; F2, Water John Deere Coolant Conditioner @ 3 %.
cally, most of the pits were on the major thrust side of the liner, although pits or pitted areas could
occur anywhere on a liners exterior surface. The major thrust side is the right side looking from
the flywheel end to front as the liner is installed in the engine. Determination of pits and the
boundary of pit areas followed by counting were done using a lamp with a lighted magnifying
glass.
2. Place the transparent grid over the cavitated area. Assign a count of one pit area to each grid
square containing a pit or pits. The pit or pits does not have to cover the entire square. If any
portion of a pit or group of pits is contained in a square, it gets a count of 1.
3. Total all the pit areas on a given liner and then total the pit areas on all six liners. This is the total
pit area count for the coolant being tested.
However, there were problems with this procedure. 1 It was difficult to determine what a pit was, what
was not, and determining where the pits actually stop when looking at large area of pits. 2 Consistency
from person to person when counting pits. 3 Counting pit areas only gives an area pit count. It does not
take into account the depth of the pits.
These problems have been minimized to a certain extent by the following. 1 One person performing
the counting and/or training others and verifying counts. 2 Measuring and recording the depth of the
deepest pit on each liner.
This original method was used in counting the pits in all the data shown in Fig. 1.
Second MethodRecognizing the problems of the original method of counting the pit areas on a liner,
there has been a constant effort to improve this technique. About the time a test engine was sent to SwRI
for commercial running of the cavitation test, both labs started using a low-magnification, binocular
microscope to look at the liner when marking the pitted areas and counting of pits. As in the original
method, the transparent grid was placed over the pitted area on the liner. This has now become the standard
FIG. 2Fleetguard Bench test versus John Deere dyno test. Test temperature: 71C; test duration: 22 h;
test frequency: 20 000 Hz; test amplitude: 0.8 mils; test material: Cast iron.
method of counting pit areas. Obviously, the inherent accuracy of this method results in a higher pit area
count due to being able to see pits in areas that previously were not as obvious. Particularly, pitted areas
concentrated at the top and bottom O-ring sealing edges of the liner area exposed to coolant. This total
count difference is evident in Fig. 2. Coolants E and F were counted using this second method, whereas the
remainder of the table were counted use the original method. A correlation factor will be developed to
relate the two methods.
Efforts are continuing to improve this process and assure reproducibility and calibration among those
who count pit areas.
Participating Laboratories
The Diesel Engine Cavitation Test was originally used as an in-house test at John Deeres Product
Engineering Center. Repeatability at John Deeres facility is shown in the table below. The 250-h test
showed discrimination between coolants in their ability to prevent, inhibit or suppress cavitation damage
to engine cylinder liners exposed to coolant within the cooling system. After development at the John
Deere facility, another, specially-configured engine was installed at Southwest Research Institute.
Test Repeatability at John Deere Product Engineering Center
Test Number
1
2
3
Average
Standard Deviation
John Deere Cool-Gard

78
77
77.5
0.5
John Deere Cool-Gardslight modification

71
71
71
0
Universal Low Silicate No SCA

956
699
757
804
110
Precision Matrix
To verify the reproducibility of this test method between laboratories, Southwest Research Institute installed an engine according to direction from John Deere personnel and conducted 250-h tests using known
coolant formulations.

Test Reproducibility Between John Deere Product Engineering Center and Southwest Research Institute
Coolant
John Deere Cool-Gard
Universal Low Silicate No SCA
Average Pit Count

77.7
812
Standard Deviation
0.47
96
Number of Tests
3
4
Fuel
Fuel meeting ASTM D 975, Grade Low Sulfur No. 2-D, is specified. This broad fuel specification is
specified since this is not a wear or deposit test, but a mechanical distress test for cavitation damage on the
exterior surface of cylinder liners.
Results of Tests
Figure 1 illustrates the types of coolants tested. All coolants, except F1 and F2, are 50/50 mix.
Conclusions
1. The diesel engine coolant cavitation test adequately provides a method of discriminating between
testing heavy-duty diesel engine coolants as to their capability of suppressing cylinder liner cavitation and resulting damage.
2. Resulting data from field tests appears to correlate well with this test when run according to the
test procedure described in this paper.
3. If done consistently, the cavitation pit counting procedure gives reproducible and repeatable results
of cavitation that occurs on cylinder liners in a heavy-duty diesel engine.
4. Southwest Research Institute SwRI has successfully reproduced the test method and results of
tests conducted at the John Deere facility and can provide this test method on a commercial basis.
Appendix: Use of the John Deere Engine Dyno Test to Determine Liner Pitting Protection
Provided by Non-Nitrite Engine Coolants
The following is an internal engineering report by Cummins/Fleetguard. This report documents a series of
engine coolant cavitation tests, as described in this paper and test procedure, conducted at Southwest
Research Institute as part of an actual coolant approval program.
This copy has been altered to protect confidential, proprietary information. Our thanks go to Cummins/
Fleetguard for sharing this very important information with ASTM.
Introduction
There is an increasing customer preference for coolants without nitrite. This is true in some geographical
areas, such as Europe and Japan. It is true for some OEMs, such as Komatsu, and also for some end-user
fleets. The current heavy-duty coolant specs both TMC and ASTM require the use of nitrite or nitrite/
molybdate for liner pitting protection. Some coolants without nitrite are now available that may perform
well enough for liner pitting protection to allow their use in heavy-duty diesel wet sleeve engines. The
problem is this: How can liner pitting protection of these coolants without nitrite be measured?
In the late 1980s, fully formulated coolants for heavy duty HD engines became more generally
available. Before that time it was common practice to use a not fully formulated coolant ASTM D 4985
and precharge it with a large dose of supplemental coolant additive SCA to achieve liner pitting protection, along with other performance features needed for successful use in HD engines. In the same time
frame, propylene glycol PG base coolants became generally available. 2
Both these factors highlighted a serious problem with the ultrasonic cavitation bench test, 3 which
had been used since the late 1970s to evaluate liner pitting performance of SCAs. 4 When glycol base,
fully formulated coolants were tested in the ultrasonic test rather than SCA treated water, lab test results
did not correlate well with field performance. 3 When propylene glycol base coolants were compared to
ethylene glycol base coolants in the ultrasonic cavitation test, 5,6 again lab results did not correlate well
with field performance. 7
A large part of the problem with the ultrasonic cavitation bench test was that it overstated the effect of
glycol compared to the effect of additives. Thus, it showed only a small difference in cavitation performance for glycol coolants with a known large difference in performance in field test. Figure 2 shows this.
The light-duty coolant is a universal low silicate conventional coolant ASTM D 4985 with no nitrite or
molybdate. This type coolant was used for many years in heavy-duty diesel engines, but it required use of
a precharge SCA package which contained nitrite/molybdate for liner pitting protection. The heavy-duty
coolant is a fully formulated hybrid coolant meeting ASTM D 6210 liner pitting chemistry levels.
Note that the ultrasonic cavitation bench test showed only about a 25-mg greater 2-1/2 times damage
for the light-duty coolant compared to the John Deere engine dynamometer test which gave a ratio of 11
and a pit count difference of over 700.
This lack of correlation and poor discrimination of the ultrasonic cavitation lab test compared with
performance in engines prompted the development of the John Deere engine dynamometer cavitation test.
1 Meanwhile, in 1995 The Maintenance Council TMC coolant specs were developed for fully formulated coolants using chemistry nitrite and molybdate requirements for liner pitting protection. 8,9 These
were followed in 1998 by similar ASTM specs. 10,11 Note that ASTM D 6210 is being modified to
incorporate D6211.
ASTM D15 Committee on Engine Coolants is now in the process of writing an ASTM Research
Report on the John Deere engine dynamometer cavitation test and will then develop an ASTM test method
based on the Research Report information.
At the urging of coolant and engine manufacturers, in 1997, John Deere provided an engine to
Southwest Research Institute SwRI to make the test available to the public. ASTM D 6210-98 Standard
Specification for Fully-Formulated Ethylene-Glycol-Base Engine Coolant for Heavy-Duty Engines, 10
already states that the John Deere test is acceptable as proof of performance for meeting the cavitation
requirement. However, CES 14603, 11 Cummins coolant spec, requires a field test if the nitrite and
molybdate chemistry does not meet ASTM D 6210 specifications.
This creates a dilemma. Current Cummins engines are generally very mild for liner pitting. How can
a valid, severe, Cummins engine field test for liner pitting be currently run? At this point, it cannot.
Therefore we need to look at some previous field tests in more severe Cummins engines and use that
information to calibrate the results from the John Deere engine dynamometer test.
Background
In 1996/1997, Fleetguard ran field tests at the BTI fleet in Wyoming using three coolants in two engine
models. The six engines were all rebuilt with new cylinder kits before the test started. Three engines were
91N14s, which had proven to be severe for liner pitting, and three engines were 94N14s, which had proven
to be mild for liner pitting. The test ran about one year, which was approximately 200 000 miles per
engine. All six trucks were maintained at one facility and all ran the same route with the same duty cycle.
The three coolants were G, E, and D see Table 1 for description of coolants.
In the BTI field test, D did not prevent liner pitting in either the mild or severe engine. E prevented
liner pitting in the mild engine but not in the severe engine. G containing nitrite prevented pitting in both
the mild and severe engines. The results of this test were reported to the ASTM D 15.11, Subcommittee on
Coolants for Heavy Duty Engines, on August 27, 1997. 12
After developing the John Deere engine test for liner pitting, John Deere personnel continued to run
many tests in their facility for their own use, which data has not been published. However, a portion of
their data has been shared with Fleetguard and Cummins to allow better calibration of the test results from
SwRI on a series of tests jointly funded by SwRI/Cummins, Fleetguard, and Old World coolant supplier
to Fleetguard.
John Deere engine dynamometer test results are shown in Table 1.
The John Deere engine dynamometer test results show good repeatability and rank coolants for
cavitation liner pitting protection in the same order as their performance in the field. OAT and hybrid

TABLE 1John Deere Liner Pitting dyno test data.
Coolant
A
Description
Hybrid HD-6210
good Ref fluid
LD universal,
conventional
bad Ref fluid
Deere
71/77/71
SwRI
78a
Average
74
Std/Dev
3.8
699/757/956
836a
812
111
Conventional light duty
688
Non-nitrite European
hybrid used in some
HD engines
305
LD US non-nitrite
2 ethyl hex OAT
270a
HD Japanese/US
non-nitrite OAT
143a
E above with nitrite

for HD-6210
No data
These results were obtained using the second method of counting pits.
coolants without nitrite perform much better than conventional coolants without nitrite. Among hybrid and
OAT coolants without nitrite, F gave twice the liner pitting protection, compared to D and E.
Although it is not possible to run a meaningful field test for liner pitting in current, mild Cummins
engines, the F coolant has been used to factory fill over 800 Cummins C series wet sleeve engines since
April 2001, with no liner pitting problems having been reported.
Furthermore, F has been approved for their heavy duty engines and is being sold by Detroit Diesel.
More recently, F has been approved for the Cat EC-1 coolant spec.
References
1
2
3
4
Davis, G. D. and Christ, R. J., A Comparison of Engine Coolants in an Accelerated Heavy Duty
Engine Cavitation Test, Engine Coolants and Cooling System Components, SP-1162, SAE 960883,
1996, pp. 145160.
Hercamp, R. D., Hudgens, R. D., and Conghenour, G. E., Aqueous Propylene Glycol Coolant for
Heavy Duty Engines, Worldwide Trends in Engine Coolants, Cooling System Materials and Testing, SP 811, SAE 900434, 1990, pp. 4777.
Hercamp, R. D. and Hudgens, R. D., Cavitation Corrosion Bench Test for Engine Coolants, SAE
881269, 1988, pp. 117.
Hudgens,R. D. et al., Refinement of the Vibratory Cavitation Erosion Test for the Screening of
Diesel Cooling System Corrosion Inhibitors, Engine Coolant Testing: State of the Art, ASTM STP
7
8
9
10
11
12
705, W. H. Ailor, Ed., ASTM International, West Conshohocken, PA, 1980, pp. 233269.
Hercamp, R. D., An Overview of Cavitation Corrosion of Diesel Cylinder Liners, Engine Coolant
Testing: Third Volume, ASTM STP 1192, R. E. Beal, Ed., ASTM International, West Conshohocken,
PA, 1993, p. 121.
Scott, L. F. Jr. and Weir, T. W., Comparing the Performance of Ethylene Glycol and Propylene
Glycol Coolants in Heavy Duty Vehicles, Engine Coolants and Cooling System Components,
SP-1162, SAE 961039, 1996, p. 181.
Fleet Purchasing Specification for Nitrite-Containing Ethylene Glycol Base Coolant, RP 329,
TMC, March 1995, pp. 14.
Fleet Purchasing Specification for Nitrite-Containing Propylene Glycol Base Coolant, RP 330,
TMC, March, 1995, pp. 14.
D6210-98a, Standard Specification for Fully-Formulated Ethylene-Glycol-Base Engine Coolant
for Heavy Duty Engines, Annual Book of ASTM Standards, Volume 15.05, ASTM International,
West Conshohocken, PA, 2002, pp. 266268.
D6211-98a, Standard Specification for Fully-Formulated Propylene Glycol-Base Engine Coolant
for Heavy Duty Engines, Annual Book of ASTM Standards, Volume 15.05, ASTM International,
West Conshohocken, PA, 2002, pp. 269272.
CES 14603, Coolant, Engine, Cummins Engineering Standards, pp. 1114.
Minutes ASTM D15.11 Subcommittee Meeting 8/27/97 at J.I. Case, Hinsdale, Dated September
4, 1997, R. D. Hercamp, Acting Secretary, 8 pp.

Paper ID JAI100616
Paul O. Fritz,1 Leonard S. Bartley, Jr.,1 Regis Pellet,1 Virginia Moser,2 and Carmen Ulabarro2
Component Durability and High Mileage Performance of a

Full Carboxylate Coolant in Heavy Duty Diesel HDD
Engines
ABSTRACT: Performance of a full carboxylate coolant has been demonstrated in engine bench cavitation
testing, fleet testing, and post fleet testing coolant corrosion tests. Performance in the proposed ASTM
Heavy Duty Cavitation Test was established and found to satisfactorily exceed performance limits. Fleet
testing of a full carboxylate coolant technology in Class 8 trucks, using Caterpillar C-12 engines demonstrated minimal inhibitor depletion to 400 000 miles under controlled zero coolant top-off conditions with no
refortification. In a second fleet, vehicles accumulated high mileages under real world conditions. In this
test, Caterpillar 3406E engines were torn down and inspected demonstrating extended corrosion protection
and superior component durability to beyond 700 000 miles, without the addition of supplemental coolant
additives or extenders. Coolants from these vehicles were removed and tested in the laboratory to verify
their extended life properties.
KEYWORDS: extended life coolant, field test, fleet testing, organic additive technology, carboxylate,
inhibitor
Introduction
This paper is based on an SAE paper number 2005-01-3579. The fleet test data from this SAE paper will
be discussed here with an additional focus on bench cavitation results as well as data from coolant
corrosion testing performed on coolants taken from vehicles after fleet testing.
Fleet testing in heavy duty diesel HDD vehicles in the U.S. of the aliphatic carboxylate coolants
described in this paper started in the late 1980s. The early field trial performance of these coolants in
automotive and HDD vehicles was thoroughly documented by Washington et al. 1,2. In 1998, based on
over 50 000 000 miles of fleet test experience, coolant life was deemed acceptable for use to 600 000 miles
if extender was added at the half-life. Critics of carboxylate-based coolants were quick to point out that
conventional coolants can last just as long as extended life carboxylate-based coolants with proper top up
and supplemental coolant additives SCA addition 3. And while this is a valid point, the purpose of this
paper is to establish and document that there are fundamental differences in these technologies that lead to
benefits for the end users. While this is not a new concept, the data in this paper further extends the
boundaries established in the literature, and combines field data with engine test data and laboratory
corrosion testing to complete the story. Since its introduction in the U.S. in 1995, this technology has
collected well over 350 000 000 000 miles of field experience in the U.S. alone based on rough estimates.
Certainly coolant life can be extended using SCAs. This requires some amount of time, testing, and
cost to do it properly. While any cooling system should be examined regularly, the prescribed maintenance
for extended life coolants can be done quickly and easily. Recommended maintenance typically includes
checking the coolant level regularly usually automatic with level sensor, but can be checked to make sure
that this is functioning properly, topping up with the correct 50/50 extended life coolant, and checking the
coolant on a regular basis with a refractometer to determine the glycol/water concentration checking the
pressure cap to make sure it is holding the proper pressure once in a while is also a good practice.
Manuscript received April 21, 2006; accepted for publication January 18, 2007; published online February 2007. Presented at
1
Senior Staff Chemist, Chevron Corporation, New Windsor, NY 12553.
2
Marketing Specialists, Chevron Corporation, Houston, TX
c
Based, with permission, on a previously published SAE paper 2005-01-3579.
96
FRITZ ET AL. ON PERFORMANCE OF FULL CARBOXYLATE COOLANT IN HDD ENGINES 97
Checking with a refractometer not only ensures that the correct freeze and boil protection is maintained,
but also that the heat capacity of the coolant is near the design limit. As well, this paper will provide
further evidence that when using the proper coolant for top-up, checking the glycol level will also be a
good measure of your inhibitor level since inhibitor depletion is minimal with this type of extended life
coolant. Besides carboxylate inhibitor levels, limiting factors on coolant life include low or high pH
usually drop due to glycol breakdown, and depletion of noncarboxylate inhibitors such as nitrite and
tolyltriazole. These three areas will also be addressed in this paper.
Field testing of this extended life coolant technology in Class 8 trucks, equipped with Caterpillar C-12
engines, revealed excellent coolant life with negligible inhibitor depletion to 400 000 miles with no
refortification and no coolant top-off in most of the vehicles. In separate evaluations in Caterpillar 3406E
equipped trucks, extended corrosion protection and component durability were established out to 700 000
miles, again without the need for refortification other than top-off. The used coolant was then subjected to
glassware corrosion testing which showed that inhibitors in the coolant were still able to provide similar
protection to that of a new coolant, verifying the extended life nature of this technology.
Experimental
The extended life coolant examined in this work is based on a synergistic combination of aliphatic monoand dicarboxylate corrosion inhibitors. This composition has been described previously 4 and is available
commercially. This heavy duty coolant contains the carboxylates described above, as well as tolyltriazole,
molybdate, and nitrite, and these components will be examined in more detail during the discussion that
follows. All coolants were evaluated as 50/50 mixtures with deionized water.
HD Diesel Cavitation Test
For many years the coolants industry has been trying to develop a cavitation test that would correlate with
field performance. The ultrasonic test has been used by many laboratories for evaluating liner pitting but
due to the variability of the test there has not been any successful correlation made from bench to field data
5. However, an accelerated heavy duty engine cavitation was developed by John Deere and presented at
SAE 6. This test utilizes a six-cylinder, 10.1 L diesel engine that is turbo-charged, intercooled, direct
injected, with specially-modified thinned liners. The test utilizes an open cooling system with the thermostats removed. In this test, the thrust side is affected most where typically a large area is scuffed with
various degrees of pitting depending on the coolant. To evaluate the coolant performance, a transparent
grid approximately 2.16 mm by 2.16 mm is placed over the liner and the number of grids that touch the
pits are counted using a 10-powered microscope. Here pits may be actual pits or simply deeply
roughened surface. Once all liners are evaluated the individual pit counts actually grid counts are
combined to obtain a total count for the test. This test which had been a Deere proprietary test is now
available commercially at an independent testing facility. A research report D15-1023 documenting the
setup and referencing of the stand has been filed with ASTM. A test method is being written for consideration by ASTM and currently what constitutes a passing amount of pits/grids is under discussion. At
the time of this writing, less than 200 total pits is under consideration as acceptable, although one OEM
specification requires less than 100 pits. The stand is referenced using a good coolant which is a fully
formulated conventional coolant that typically gives between 70 and 90 pits and a bad reference which
is a low-silicate, conventional coolant which gives between 750 and 900 pits. All coolants give rise to
pits in this test.
Fleet Testing
Two separate fleet tests are examined in this paper. In the first fleet, top-off was eliminated by using
specially designed impermeable hoses with heat shrink hose clamps to greatly repress coolant loss to
accurately test the rate of inhibitor depletion. In the second fleet, trucks from a fleet that had operated to
high mileages without supplemental coolant additives SCAs were torn down and evaluated.
A fleet test was started with 32 trucks 28 trucks finished the test equipped with Caterpillar C-12
engines. These trucks were fitted with specially designed, impermeable hoses which minimized throughhose evaporation. A commercial extended life coolant containing the mono- and dicarboxylate combina-

TABLE 1Heavy duty cavitation test results.
Coolant Type
Fully Formulated Conventional Coolants
Fully Formulated Synergistic Carboxylate System
Nonnitrited Synergistic Carboxylate System
Nonnitrited Aromatic Carboxylate System
Label
From research
report
A
B
C
Total Pit Count

78
83
131
144
tion was used in this fleet. Coolant samples were approximately every 50 000 miles from each truck out to
about 400 000 miles. The trucks were not refortified with SCAs or with extender and minimal top-off. The
coolant samples were analyzed for water content Karl Fisher, pH, inhibitors HPLC, IC, and corrosion
metals ICP.
In the second test potential candidate trucks for teardown were identified from a large national truck
leasing fleet. Vehicles with Caterpillars 3406E engines factory-filled with extended life coolant having
accrued a minimum of 650 000 miles in long haul service without refortification over this period were
sampled. Normal top-off with extended life coolant occurred throughout the life of the vehicle; however,
dilution with other coolant technologies would exclude a candidate from consideration. Using these criteria, and coolant analyses, 100 potential trucks were identified. Of these, four trucks were selected based
on ease of availability, proximity, and minimal disruption to customer service.
After selection, engines were disassembled and the cooling system components were inspected and
photographed. Parts examined included all liners, water pumps, thermostat housing and thermostats, radiators, hoses, seals, heads, and oil coolers. Appropriate components were examined by a metallurgist.
Coolant Testing
The coolant from the Caterpillar engines that were torn down was retained, and this coolant was used to
conduct standard ASTM glassware corrosion tests designed to evaluate new coolants. ASTM Standard
D-1384 15 and ASTM D-4340 16 were run on the used coolant. These tests were run as specified with
the level of corrosive salts adjusted properly to account for the fact that the test was starting with
prediluted coolant.

Heavy Duty Cavitation Test
The carboxylate-based coolant system described in this paper has been commercially available in the
marketplace for over ten years with excellent cavitation protection performance. The HD cavitation test
was run on both the fully formulated nitrite and molybdate version and the nonnitrited version of the
synergistic two carboxylate system described above. For comparison purposes a commercially available
carboxylate coolant system using aromatic carboxylates and no nitrite was included. The three carboxylate
coolant samples were sent blind to the test laboratory and the results are reported in Table 1 alongside
previously reported results for a fully formulated conventional coolant.
The John Deere company, who originally developed this test, has set a pit/grid count of 100 as a pass.
Both of the fully formulated coolants performed equally well in this test, passing this stringent limit. The
nonnitrited carboxylate coolants are over the John Deere limit but are well within the limit of 200 pits set
by Cummins in Engineering Standard Number 14603 and this limit is also being discussed by ASTM as a
passing result. Recall that the bad reference, which is a low-silicate coolant that meets ASTM D 4985
17, generally gives between 750 and 900 pits. The test results show that although the full carboxylate
coolant can provide protection against cavitation in this test, there can be an additional improvement in
cavitation protection when nitrite or nitrite/molybdate is used. This may become relevant if one is concerned about engines known to severely cavitate since the presence of the nitrite and molybdate does
improve the anti-cavitation performance in this test. As well, as the nitrite depletes, or disappears through
FIG. 1The #1 Liners for the three carboxylate coolantsclose up of thrust side damage.
other reactions, it is clear that the aliphatic carboxylates will impart a high level of cavitation protection.
Although very likely these results are within experimental error, directionally the aliphatic carboxylate has
less total pits than the aromatic carboxylate coolant.
One of the drawbacks with this test is the way the pits are measured. As described in the Experimental
section, currently a grid is laid over a pit area under a microscope and then it is up to the operator to
determine the number of grids that are touching a pit area. With a well trained operator, this technique
may be repeatable but it does not account for pit depth. A pit that has just started or severely roughened
the surface has the same value as one that has almost perforated the liner. Figure 1 shows a close up of
the #1 Liners, and Fig. 2 shows a close up of the #6 liners for the three different carboxylate technologies
evaluated. Liners #1 and #6 were selected, since according to the test operators and developers, these liners
generally show the worst cavitation. The #2 Liners are also shown in Fig. 3 because this was the worst
liner for Coolant B as shown in Table 2 and is shown to present a balanced perspective. As well, the results
for the #2 Liner seem to illustrate why this test may yield slightly misleading results.
Figure 3 shows the results for the #2 Liners and clearly Coolant A yields the best result, in agreement
with the pit/grid count data. For the #2 Liner, Coolant C yields a much better pit count result than Coolant
B, since the measuring technician counted more grids touching pits for this liner. What is not counted,
however, is the fact that although Coolant B had a bigger surface area with pits and roughening that
touched the grid lines, the deepest pit was measured to be 1.0 mm for Coolant B. This was the same as for
Coolant A, which also had a deepest pit depth of 1.0 mm. Coolant C had several pits exceeding 1.0 mm,
with the deepest being 1.2 mm. Since pitting through the liner is the failure mode, it is possible that the
manner in which this test currently evaluates coolants does not weigh all the factors appropriately.
FIG. 2The #6 Liners for the three carboxylate coolantsClose up of thrust side damage.
FIG. 3The #2 Liners for the three carboxylate coolantsclose up of thrust side damage.
There are a few important notes to make. First, notice that the Pit Count from this test, which again
is really the grid count is actually much higher than the real number of pits in the liner for these
carboxylate based coolants. This may not be true for conventional coolants, we have not seen enough data
to verify. Second, it is clear from the comparative pictures that if pit depth were a factor for consideration,
Coolant B might be considered much closer to Coolant A in performance than to Coolant C. Clearly
the actual pitting measured for Coolant C is much worse more pits and deeper pits than both aliphaticbased carboxylates in this test. Finally, in all cases, the pitting occurred essentially exclusively in a small
area on the thrust side.
Based on these data, while not all carboxylate coolants are equivalent in performance, it is clear that
these carboxylate coolants provide much better protection against cavitation than nonnitrited low-silicate
universal coolants. Directionally the aliphatic carboxylate provides better cavitation protection than the
aromatic based carboxylates.
Fleet TestingInhibitor Depletion
To best measure inhibitor depletion rates, it is essential to minimize coolant top-off. Top-off is required to
replace coolant lost due to leaks and evaporation. It has been reported that top-off can replenish an entire
cooling system in as little as one year 3. With extended life technologies, such as those based on
carboxylates like the ones used in these studies, there are published claims of minimal depletion over the
course of several years service 1,2. In order to further verify these claims and continue to understand the
limitations of these inhibitor systems, the effects of top-off must be accounted for when determining
inhibitor depletion rates.
A fleet of 32 Freightliner Century Class trucks equipped with Caterpillar C-12 engines was modified
to minimize coolant losses. EPDM hose designed to be especially resistant to water loss/evaporation due
to water permeation through the hose wall were used in combination with hose connections that were
sealed with heat-shrink hose clamps. These clamps work to eliminate leakage by applying uniform pressure around the entire hose fitting. The fleet was filled with the previously described organic additive
TABLE 2Pit count per Liner.

Cylinder Liner Pit/Grid Count
Coolant
A
B
C
#1
17
31
36
#2
15
38
24
#3
13
18
19
#4
12
16
15
#5
11
19
16
#6
15
9
34
Total
83
131
144

TABLE 3Disassembly candidate repair histories.a
Engine Number
Mileage
Coolant Comments
Component
Coolant Level Sensor
Coolant T Indicator
Core and Tank Assembly
Cylinder Head
Heater Core
Heater Hose
High Temperature Switch
Hose Clamps
Injectors
Low Coolant Probe
Radiator Hose
Radiator Inlet
Repair Block - Cylinder
Tank Top, repair
Temperature Sensor
Thermostat
Water Gasket
Water Pump
355655
728 635
Good
357809
748 102
Good
357813
660 845
Good
357814
679 577
Good
434 468
435 373
58 041
432 922
435 818
170 310, 434 302
508 247
58 041
46 968
117 537
647 814
156 900
161 030
195 743
693 829
279 822, 411 828
250 171
119 875
202 453
542 440
599 865
2005 SAE International, used with permission.
Figure 7 plots coolant tolyltriazole levels as a function of coolant age. Significant tolyltriazole depletion was observed in this fleet where top-up was carefully eliminated. As coolant age approaches 400 000
miles, tolyltriazole levels were observed to drop as low as 20 % of fresh. Tolyltriazole protects yellow
metals, including copper and brass. Although tolyltriazole levels have dropped dramatically, this is not
unexpected. Tolyltriazole behaves similarly to layer forming inhibitors; the tolyltriazole interacts with the
yellow metal surfaces and forms a protective layer.
This mechanism was examined in an earlier study 12 and this protective layer was found to be quite
resilient; electrochemical studies were able to demonstrate that a piece of copper radiator removed from a
previously used radiator and exposed to a corrosive salt solution behaved similarly to a new piece of
copper in solution with a coolant containing tolyltriazole, and then this was compared to fresh copper with
no tolyltriazole. Even though the piece had been removed from the radiator, exposed to air, mechanically
handled, it still was fully protected by the tolyltriazole. The protective layer that tolyltriazole provides can
be quite robust. As well, carboxylates can also provide some level of protection to copper in the absence
of TTZ. These facts taken together demonstrate why the yellow metals are completely protected even
though the TTZ levels are as low as 20 % of fresh, which is confirmed by the copper levels.
Results of this analysis for the presence of copper are presented in Fig. 8. From the plot we can see
that in fact the copper content has remained quite constant over the course of the test. Early data found the
copper content to be between 0 and 1.5 ppm and as the test progressed the copper continued to hover
around 2 ppm or less. The plot shows the upper limit to 30 ppm, this is to be consistent with the proposed
TMC RP 1416 which puts the condemning limit for copper at 30 ppm.
Metal content is often used as an indicator for active corrosion. All coolant samples were analyzed for
the corrosion metals: aluminum, iron, and lead. All values for all metals for all samples were 1 ppm
indicating that corrosion is well controlled by the carboxylate inhibition.
Fleet TestingComponent Protection
Perhaps more important than the actual inhibitor depletion is the corrosion protection imparted by the
coolant. Repair histories were obtained for all candidates prior to disassembly and these were reviewed to
identify coolant system repairs. A summary of the repairs for each of the trucks is provided in Table 3.
Note that all liners, all radiators, blocks and heads are original equipment. Two of the water pumps were
original, despite over 700 000 miles of service. Coolant samples were obtained from each candidate and

TABLE 4Disassembled Engines Coolant Compositionsa
Vehicle ID
Recent Mileage
Coolant Water Quality
pH
Reserve Alkalinity
Water Content %
Calcium ppm
Magnesium ppm
Chloride ppm
Contaminants and Inhibitors
Boron ppm
Silicon ppm
Nitrite ppm
Nitrate ppm
Phosphate ppm
Molybdenum ppm
Tolyltriazole ppm
Diacid % full dosage
Monoacid % full dosage
Corrosion Metal Analysis
Aluminum ppm
Copper ppm
Iron ppm
Lead ppm
355655
728 635
357809
748 102
357813
660 845
357814
679 577
7.87
2.61
42
10
6.2
75
7.98
2.17
49.14
1.7
2
79
7.83
2.03
48.42
13
6.7
61
8.2
2.19
50.25
6.7
4.1
90
6.1
80
319
990
27
427
140
146
107
3.5
72
133
632
71
515
181
119
90
7.1
55
192
497
0
575
418
125
95
2.3
33
268
435
0
562
690
126
102
1
9.5
1
1
1
4.2
1
1
1
3.7
1
1
1
1.5
1
1
2005 SAE International, used with permission.
analyzed to determine inhibitor content, extent of contamination with other coolant and to determine
corrosion metal content if present. Coolant analyses for all trucks are provided in Table 4 and the analysis
confirms the presence of the factory fill extended life coolant with minimum contamination. In this fleet
there was no controlled effort to limit top-off.
All engines were torn-down so that all cooling system components could be inspected for signs of
corrosion. As well, all major components were retained and sent for metallurgical analysis.
None of the 24 cylinder liners examined six per four engines showed signs of any pitting or scuffing.
For additional pictures refer to SAE 2005-01-3579. Fig. 9.
The liner seals on the coolant side are fabricated from EPDM. They are subjected to high temperatures
as well as mechanical stress due to vibrations. All liner seals were in excellent condition with no signs of
leaks. Laboratory examination indicated less than 75 % compression set for all seals with excellent elasticity retention, see Fig. 10.
The radiators were examined on-site and they were in excellent condition, with no signs of leaks. Two
of the radiators were retained for further inspection. In laboratory testing, it was determined that all
radiator tubes were free from plugging. Metallurgical analysis found that the solder joints were free of
corrosion; see Fig. 11 for radiator tubes and decks.
Thermostat housings are aluminum and subject to high temperature and erosive damage if not properly
protected. The thermostat housings were in excellent condition and showed minimal aluminum corrosion
and no corrosion was observed at the junction of the dissimilar metals of the housing with the thermostat
itself. All thermostats were operational, see Fig. 12.
Before the introduction of extended life coolants it would have been very rare for a water pump to last
500 000 miles. In this test every water pump lasted at least 500 000 miles and two were still in service
after 700 000 miles or more. The water pump seal, the most common failure point in a water pump, was
still functional and not leaking, indicating that dissolved solids which typically build up from continuous
SCA use were not a problem. The aluminum pump cover showed only minor erosive damage and the
impeller was like new Fig. 13, indicating extended aluminum and cast iron protection. Inspection of the
block and head determined that there was no observable corrosion and minimal flash rust in any of the
coolant head and block passages.
FIG. 9Cylinder liners from vehicle 357814; thrust side (Caterpillar 3406E engine) (2005 SAE International, used with permission.)
Coolant Corrosion Testing After 748 102 Miles (with Top-up)
Coolant from the vehicles that were torn down for inspection was collected and sent to the lab for full
analysis and glassware corrosion testing. The full analysis of the coolants is shown in Table 4. From the
analysis we see that there is some level of contamination in all the trucks, but we estimate the contamination to minimal. Since there was no effort made to control top-up, or to monitor top-up, these are real
world samples. No extender was added to these vehicles according to their maintenance records and the
coolant analysis agrees.
ASTM D-4340 16 testing was carried out on the highest mileage coolant and the result agrees with
earlier reported findings 1 that this extended life coolant formulation is able to provide excellent results
at this test even after 748 102 miles in the vehicle. While the result obtained was slightly above the limit
of 1.0 mg/ cm2/week set by ASTM D-3306 18 for new coolants at 1.28 mg/ cm2/week, this is an excellent result for a used coolant. The presence of extra chloride in the sample, copper, and low levels of borate
and phosphate which are known to be aggressive in this test 13,14, verify that the carboxylates are
working hard to protect the aluminum. This result combined with the appearance of the aluminum parts is
proof of performance.
FIG. 10O-rings on cylinder liner from Vehicle 357814 (Caterpillar 3406E engine).
FIG. 11Radiator tubes and decks, Vehicle 357809 (Caterpillar 3406E engine).
FIG. 12Thermostats and housing, Vehicle 357809 (Caterpillar 3406E engine). (2005 SAE International, used with permission.)
FIG. 13Water pump impeller and aluminum pump cover, Vehicle 357809 (Caterpillar 3406E engine).
(2005 SAE International, used with permission.)
FIG. 14ASTM D-1384 data for new carboxylate-based coolant and for used coolant at 748 102 miles.
ASTM D-1384 15 testing was also conducted and the data are shown in Fig. 14. As can be seen from
the data, the coolant passes this test for all metals.
Conclusion
This study has examined coolant inhibitor life as well as corrosion protection for an extended life coolant
based on mono- and dicarboxylate corrosion inhibitors. The results presented indicate that this coolant
technology allows users to take advantage of the extended life corrosion inhibition performance far longer
than previously reported for coolants.
Testing in the proposed heavy duty cavitation test verifies the excellent performance of the nitritecontaining aliphatic carboxylate-based coolant technology and validates its proven track record. The performance of the nitrite-free version is also good; however, clearly there are advantages to a belt and
suspenders system that contains multiple solutions to the known issue of cavitation. Relatively speaking,
the nitrite-free aliphatic carboxylate formulation outperformed the nitrite-free aromatic carboxylate formulation in this test with slightly fewer pits, and with much less deep pits overall.
Used coolant analysis conducted on samples taken from a fleet test using Caterpillar C-12 engines
demonstrated that the corrosion inhibitor levels remained acceptable to at least 400 000 miles without
top-off and without the use of extenders or supplemental coolant additives that would be required by most
conventional coolant systems. Analysis also indicated that the coolants pH, remained constant and well
above 7, far from an acidic regime throughout the test.
A separate field test using Caterpillar 3406 equipment, demonstrated excellent corrosion protection to
700 000 miles and beyond through engine disassembly and component inspection. With respect to water
pumps, all survived to 500 000 miles and two pumps were still functional after 700 000 miles of service.
Protection of aluminum, iron, and copper components; solder joints, and elastomers were excellent.
Glassware corrosion testing verified acceptable corrosion prevention performance of the used coolant
out to 748 102 miles.
Not all carboxylate-based coolants behave similarly; however, these data verify that the aliphatic
carboxylate-based coolants evaluated in this study are capable of providing cooling system protection with
minimum maintenance out to a half-million miles and beyond in heavy duty diesel applications.
References
1
2
3
Washington, D. A., Miller, D. L., Maes, J.-P., Van de Ven, P., and Orth, J. E., Long Life Performance of Carboxylic Acid Based Coolants, SAE 940500, 1994.
Washington, D. A., Miller, D. L., Valkovich, P. B., Amrstrong, R. A., McMullen, F. A., Quinn, M.
J., Kelly, F. A., McWilliams, E. J., Performance of Organic Acid Based Coolants in Heavy Duty
Applications, SAE 960644, 1996.
Hudgens, R. D., Comparison of Conventional and Organic Acid Technology OAT Coolants in
Heavy Duty Diesel Engine Service, SAE 1999-01-0139, 1999.
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Miller, D. L., Bade, R. T., and Orth, J. E., Corrosion Mechanism of High Lead Solder and
Correlation to Dissolved Oxygen, SAE 940497, 1994.
Kelley, F. A. and McWilliams, E. J., A Bench Test Procedure for Evaluating the Cylinder Liner
Pitting Protection Performance of Engine Coolant Additives for Heavy Duty Diesel Engine Applications, SAE960879, 1996.
Davis, G. D. and Christ, R. J., A Comparison of Engine Coolant in an Accelerated Heavy Duty
Engine Cavitation Test, SAE960883, 1996.
Darden, J. W., Triebel, C. A., Maes, J. P., and VandNeste, W., Monoacid/Diacid Combination as
Corrosion Inhibitors in Antifreeze Formulations, SAE 900804, 1990.
Pellet, R. J., Bartley, L. S., and Hunsicker, D. P., The Role of Carboxylate-Based Coolants in Cast
Iron Corrosion Protection, SAE 2001-01-1184, 2001.
Pellet, R. J. and Hunsicker, D. P., Solder Protection with Extended Life, Carboxylate-Based Coolants, SAE 2000-01-1979, 2000.
Hudgens, R. D. and Hercamp, R. D., A Perspective on Extended Service Intervals and Long Life
Coolants for Heavy Duty Engines, SAE 961818, 1996.
Pellet, R. J., Van de Ven, P., Amaez, D., Fritz, P. O., Bartley, L. S., and Hunsicker, D., The Role
of Nitrite and Carboxylate Ions in Repressing Diesel Engine Cylinder Liner Cavitation Corrosion,
Paper No. 545, Corrosion 98, NACE meeting, San Diego, CA, 1998.
Bartley, L. S., Fritz, P. O., Pellet, R. J., Taylor, S. A., and Van de Ven, P., Engine Coolant Testing,
4th Volume, ASTM STP 1335, R. E. Beal, Ed., ASTM International, West Conshohocken, PA, 1999,
pp. 7688.
Wiggle, R. R., Hospadaruk, V., and Tibaudo, F. M., Corrosion of Cast Aluminum Alloys Under
Heat Transfer Conditions, SAE 810038, Society of Automotive Engineers, Feb. 1981.
Fritz, P. O., Bartley, L. S., Maes, J. P., and Van de Ven, P., Extended Life Carboxylate Coolant
Compatibility with Other Coolant TechnologiesExamining the Data, SAE 2000-01-1977.
ASTM D 1384, Test Method for Corrosion Test for Engine Coolants in Glassware, Vol. 15.05,
ASTM International, West Conshohocken, PA.
ASTM D 4340, Test Method for Corrosion of Cast Aluminum Alloys in Engine Coolants Under
Heat-Rejecting Conditions, Vol. 15.05, ASTM International, West Conshohocken, PA.
ASTM D 4985, Standard Specification for Low Silicate Ethylene Glycol Base Engine Coolant for
Heavy Duty Engines Requiring a Pre-Charge of Supplemental Coolant Additive SCA, Vol. 15.05,
ASTM International, West Conshohocken, PA.
ASTM D 3306, Standard Specification for Glycol Base Engine Coolant for Automobile and LightDuty Service, Vol. 15.05, ASTM International, West Conshohocken, PA.

Paper ID JAI100367
Yasuaki Mori,1 Michael L. Abel,2 and Yuji Miyake2
Cavitation Protection Performance of Nitrite-Free Organic

Acid Based Coolant for Heavy-Duty Engines
ABSTRACT: For decades, most all heavy-duty engine coolants contain nitrites in order to protect against
cavitation erosion/corrosion. So much so that many industry specifications require nitrites by name as well
as minimum concentration quantities as they have been found to be very effective in minimizing cavitation
erosion/corrosion of heavy-duty engine cast iron cylinder liners. However, the use of nitrites has become an
issue because it is commonly known that nitrites could produce carcinogens when mixed with amine-type
coolants. Legislation in some countries recommend not using it. This paper introduces nitrite-free, organic
acid based, long-life coolant technology that gives the desired cavitation protection.
KEYWORDS: aromatic carboxylate, aliphatic carboxylate, organic acid, cavitation, heavy-duty, ultrasonic cavitation, elastomer compatibility testing, engine dynamometer testing, fleet testing
Introduction
In recent years there are increased demands on reducing the impact on the environment and the push to
recycling and reusing vehicle parts is increasingly moving forward. Also, end-users are demanding the
decrease of maintenance costs and frequency; hence the desire for longer-life products is becoming stronger.
There are mainly two categories of heavy-duty truck coolants. The historically dominant type is the
conventional coolant based on inorganic salts including nitrite, silicates, borates, phosphates, etc., and the
other type coolant is based on organic acid technologies. These days the latter is becoming increasingly
more mainstream because the maintenance interval of the former is shorter and costs over the useful life
of the engine can be higher.
Even though the base inhibitor systems are somewhat different borate versus phosphate based, all
traditional heavy-duty coolants contain nitrites. Nitrite is the low cost alternative in the protection of
cylinder liner pitting. SAE paper 1999-01-0140 introduces how nitrites prevent cylinder liner pitting by
conducting the fleet testing using organic acid based coolant with nitrite and without nitrite, and it shows
that the organic acid based coolant without nitrite does not sufficiently protect cylinder liner pitting 1.
Nitrite is quite effective against cylinder liner cavitation corrosion; however, this anticorrosive additive has
extremely high toxicity. Also there is the argument that nitrites can react with amines to produce carcinogenic nitrosamine. The toxicity of nitrite is the highest of the generally used anticorrosive additives of
coolants as the LD50 for oral toxicity for rats is rated at 85 mg/ Kg, and is similar to the toxicity of arsenic
2. This report introduces a nitrite-free aromatic carboxylate based coolant that has superior cavitation
protection performance.
Outline of Composition
Aromatic carboxylate based coolant introduced in this report is composed of aromatic carboxylate benzoate, p-toluate, and p-tert butyl benzoate, tolyltriazole, molybdate, and nitrate but does not contain
nitrite, silicate, borate, or amine 3. Phosphate is quite effective against the corrosion of aluminum, but
some regions restrain the use because diluting with hard water traditionally has produced an insoluble
Manuscript received February 1, 2006; accepted for publication January 4, 2007; published online February 2007. Presented at
1
CCI Corporation, 12 Shin-hazama, Seki City, Gifu 501-3923, Japan.
2
CCI MANUFACTURING IL CORPORATION, P.O. Box 339, Lemont, IL 60439.
109
phosphate. Because of this reason, this paper introduces coolant without phosphate, but its addition is
recommended for corrosion protection of aluminum even in constrained regions, since using premixed
coolant or stabilized phosphates removes the concern 4. The phosphate concern is based more on
historical perspectives and misconceptions than on factual performance issues.
The reason for the use of aromatic carboxylates as the organic acid is that they have better performance against cavitation than aliphatic carboxylate used for the organic acid type coolant that is currently
becoming mainstream. It is also known that aliphatic carboxylate based coolant is aggressive towards
silicone rubber 5,6, while it is shown in this paper that the aromatic carboxylates used here have good
compatibility with silicone rubber materials.
Test Results
Ultrasonic Cavitation Corrosion Test
Ultrasonic cavitation corrosion test results are shown in Fig. 1. Although the weight change of nitrite-free
aliphatic carboxylate based coolant is larger than nitrite containing conventional heavy-duty coolant, if
nitrite is added, cavitation protection performance becomes better than that of the nitrite containing conventional heavy-duty coolant. While the cavitation protection effect of nitrite is well documented, even
when the aromatic carboxylate based coolant does not have the nitrite, its cavitation protection performance is better than nitrite containing aliphatic carboxylate based coolant and nitrite containing conventional heavy-duty coolant.
FIG. 1Ultrasonic cavitation corrosion test results.

Elastomer Compatibility Test
These tests were conducted in accordance with test method CES 14603 Cummins Engineering Standards
to evaluate the aromatic carboxylate based coolant elastomer compatibility and are compared against the
nitrite containing aliphatic carboxylate based coolant and nitrite containing conventional heavy-duty coolant. Compatibility was checked against five elastomer types NBR, H-NBR, Silicone, EPDM and Viton.
Test conditions are shown in Table 1. Each type of elastomer was tested separately in its own vessel. Each
specimen type test pieces for tensile/elongation, hardness/volume, and compression set were combined
together in one vessel.
The aromatic carboxylate based coolant shows good compatibility with all elastomers tested. Especially with respect to the silicone rubber, the aliphatic carboxylate based coolant shows large physical
property changes, while the aromatic carboxylate based coolant shows good compatibility basically
equivalent to conventional heavy-duty coolant. Also, remarkable cracks were confirmed on the surface of
the tensile/elongation specimen after testing in an aliphatic carboxylate based coolant. There was no
significant difference between the aromatic carboxylate based coolant and the conventional heavy-duty
coolants. Silicone rubber compatibility test results are shown in Figs. 28.
MORI ET AL. ON CAVITATION PROTECTION 111

TABLE 1Elastomer compatibility test condition.
Items
Vessel material
Vessel capacity, L
Coolant amount, L
Coolant concentration, vol. %
Coolant aging terms, hours
Coolant aging temperature, C
NBR
H-NBR
Silicon
EPDM
Viton
Shape of tensile/elongation specimen
Size of vulcanized specimen
Size of compression set
Conditions
Carbon Steel
4.8
1.6
50
168 not for tensile/elongation, 500, 1000
120
150
150
150
150
According to ASTM D 412 die C
0.63 in. 0.63 in. 0.08 in. more than 0.5 g
0.25 in. 0.25 in. 0.08 in.
FIG. 2Appearance of silicone rubber test specimen after compatibility test.
FIG. 3Elongation change.
FIG. 4Tensile change.
FIG. 5Volume change.
FIG. 6Hardness change.
FIG. 7Weight change.
FIG. 8Thickness change.

Engine Dynamometer Testing
In order to check the cavitation protection performance of an aromatic carboxylate based coolant, engine
dynamometer testing was performed using a Navistar 530E engine in accordance with test conditions
shown in Table 2. The appearance of the cylinder liner after the test is shown in Fig. 9. Pitting was not
observed on any of the cylinder liners after the test and the appearance of the cylinder liners was essentially the same as new.
TABLE 2Engine dynamometer test conditions.
Item
Test cycle
Step 1
Step 2
Step 3
Step 4
Test duration, hour
Coolant concentration, vol. %
Coolant volume, G
Coolant flow rate, G/min
Engine outlet temperature, C
Condition
Low idle: 30 s
Rated speed and load: 120 s
High idle: 60 s
Peak torque: 120 s
2000
50
18
85
93
FIG. 9Appearance of cylinder liners after engine dynamometer testing.
Fleet Testing
Fleet testing was performed using a total of more than 100 vehicles utilizing Detroit Diesel and CAT
engines. The highest mileage at time of tear down was nearly 600 000 miles although the fleets continue
to accumulate mileage. The coolant was sampled during the test from all vehicles and analyzed for pH,
metal ion concentration, inhibitor content, and degradation product generation. For this evaluation ten sets
of parts four Detroit Diesel engines and six CAT engines were chosen to be removed from the vehicles.
Parts taken included the cylinder heads, cylinder liners, radiators, water pumps, thermostats, thermostat
housings, and fuel injector sleeves. Fleet performance results were excellent as there were no problems,
such as overheating or LLC leakage, reported in any truck during the fleet testing.
TABLE 3Summary of inspected engine.
Engine/Vehicle #
DD
#31520
#31525
#31433
#31430
CAT 3406 series
#226
Test Mileage
Mile
372
373
548
577
Test Duration
Month
500
006
216
226
38
38
34
34
379 742
34
#231
427 829
32
#233
372 761
34
#236
360 110
44
#237
#238
243 048
372 021
19
26
Contamination
47 %, 53 586 177 192

miles
55 %, 294 245 427 829
miles
33 %, 284 862 348 113
miles
20%, 289 624 355 263
miles
State of Coolant
Although the pH of this type of coolant falls to about 6.5 by 100 000 miles, it is maintained at 6.5
thereafter. Since this coolant inhibitor system is not using an inhibitor that has a buffering effect in weak
alkali domains i.e., phosphates or borates, the pH fall is early; however, this type of technology has
sufficient anticorrosion and anticavitation performance at a pH level of 6.5 and performs satisfactorily at
this level. By using an organic acid to protect iron that has essentially no depletion rate, even when the pH
moves to 6.5 early in its life, there is a minimum conservative protection life of 300 000 or more miles. It
is difficult to corrode iron at higher pH ranges. However, for amphoteric metals i.e., aluminum, when the
pH is moderately high, corrosion is accelerated. This coolant exhibits good and compatible protection of
metals from iron to aluminum so it can be said to be in a desirable pH range.
Tolyltriazole decreases as expected and remains above 10% at 300 000 miles. This quantity is sufficient for copper and brass protection.
The State of Cooling System Parts
The summary of the vehicles that collected cooling system parts is shown in Table 3. The cooling parts of
an engine running with a nitrite-type conventional heavy-duty coolant were also collected at
420 000 miles for comparison.
No extender was added during the test even though test parameters allow for its addition. In vehicles
#31520 372 500 miles and #31525 373 006 miles, light pitting was observed on only one cylinder
liner, liner No. 3. The maximum depth of #31525 was 6 %, and the maximum depth of #31520 was 10 %.
This is considered to be completely satisfactory.
In vehicles #31433 548 216 miles and #31430 577 226 miles, light pitting was observed on all
cylinder liners with a maximum depth of 3 to 14 %. However, these trucks were run 500 000 or more miles
FIG. 10pH change.
FIG. 11Tolyltriazole concentration change.
FIG. 12Aromatic carboxylate concentration change.

with no extenders used, and it is considered very acceptable and a pitting state of this level is better than
FIG. 13Molybdate concentration change.
FIG. 14Appearance of cylinder liners after fleet testing (DD engine).

the state of the cylinder liners which out of the vehicle that accumulated 420 000 miles with a nitrite-type
conventional heavy-duty coolant.
Vehicle #226 379 742 miles was contaminated to a level of approximately 47 % of the concentrated
coolant level with conventional coolant in the period between 53 586 177 192 miles. Though in best
practice this coolant is not intended to be mixed with conventional coolants, this vehicle was chosen to
investigate compatibility issues and shows what has been seen in the laboratory; that the aromatic carboxylate based coolant and conventional coolants are compatible as there were no abnormalities found in
the collected parts and coolant performance, properties, inhibitor depletion, or metal ion accumulation.
Vehicles # 231 337 039 miles, #233 427 829 miles, and #236 360 110 miles were also contaminated with a conventional coolant after 280 000 miles. Pitting was not observed on any cylinder liners of
all vehicles, therefore it is suggested that a nitrite-free aromatic carboxylate based coolant completely
inhibits pitting for over 280 000 miles and is not adversely affected by contamination with borated/nitrited
coolants.
FIG. 15Appearance of cylinder liners after fleet testing (CAT engine).
In vehicles #237 243 048 miles and #238 351 496 miles, pitting was not observed on any cylinder
liners and there were no abnormalities found in the collected parts cylinder head, cylinder liners, radiator,
water pump, thermostat, thermostat housing, and fuel injector sleeves. Moreover, there were no abnormalities found in the coolant performance, such as properties, inhibitor depletion, or metal ion accumulation up to the point that the components were collected. see Figs. 1015.
Conclusions
The aromatic carboxylate based coolant presented has good compatibility with elastomers including silicone rubber and has general performance characteristics more than equivalent with nitrited heavy-duty
conventional coolant.
Although the aromatic carboxylate based coolant presented in this paper does not contain nitrite, it
exhibits good cavitation protection performance and the cavitation protection performance is maintained
without performing SCA additions during service intervals.
References
1
2
3
4
5
6
Hudgens, R. D., Composition of Conventional and Organic Acid Technology Coolant in Heavy
Duty Diesel Engine Service, SAE Paper 1999010140, 1999.
Hudgens, R. D., and Bustamante, R. B., Toxicity and Disposal of Engine Coolants, Engine
Coolant Testing: 3rd Volume, ASTM STP 1192, 1993, pp. 149164.
United States Patent 6126851.
Osawa, M., Morita, Y., and Nagashima, T., A Study of Extension of Engine Coolant Life Using
Low Phosphate Organic Acid Inhibitors, SAE Paper 2003-01-2023, 2003.
Automotive Cooling Journal, May 1999, pp. 1620.
Radiator Reporter, Vol. 27, No. 7, August 1999, pp. 7376.

Paper ID JAI100366
Fred C. Alverson,1 Steven L. Balfe,1 and Anthony P. Skrobul1
Accelerated Oxidation and Corrosion Testing of Engine

Coolants Using a Rotary Pressure Vessel Oxidation Test
ABSTRACT: Todays modern engines are exposing engine coolants to more severe operating conditions
involving higher coolant temperatures, greater heat rejection requirements, greater metal to coolant heat
fluxes, higher coolant flow rates, higher cooling system pressures, and slower deaeration. These conditions
will have a tendency to accelerate oxidation/thermal degradation, reduce corrosion protection, and shorten
coolant life. In efforts to simulate the increased severity in operating conditions, an accelerated oxidation
and corrosion test, using a rotary pressure vessel oxidation test, was developed and evaluated to assess
the oxidation/thermal stability and corrosion protection of conventional, hybrid, and extended life coolants.
The test involves exposing the coolant to a high temperature oxygen rich environment under pressure with
six different metal corrosion coupons. The test allows a quantitative assessment of corrosion protection of
the coupons and the effects on coolant chemistry. Test results are provided on conventional, hybrid, and
extended life coolants. The test has also been found to be a promising predictive tool to screen satisfactory
versus unsatisfactory coolant formulations, including recycled coolants.
KEYWORDS: conventional coolants, hybrid coolants, extended life coolants, oxidation, corrosion,
inhibitor depletion
Introduction
Engine manufacturers are continuously striving to develop new automotive and diesel engine technology
that will provide improved performance/productivity, lower emissions, greater fuel economy, and longer
service life. Engine coolants used in these engines are generally exposed to more severe operating conditions including higher coolant temperatures, greater heat rejection requirements, smaller cooling systems,
higher coolant flow rates, higher cooling system pressures, slower deaeration, tighter tolerances/narrower
coolant passages which are thermally stressing the coolant. All of these factors will tend to accelerate
oxidation/thermal degradation, reduce corrosion protection, and shorten coolant life.
Ethylene glycol-based engine coolants continue to be the most widely used heat transfer fluid for
automobile and truck applications. While these coolants provide the basic functions for freeze protection,
boil over protection, and heat transfer, these coolants are susceptible to oxidation and thermal degradation
under severe operating conditions. The oxidation reaction involves reaction of ethylene glycol
HO-CH2-CH2-OH with oxygen to form glycolic acid HO-CH2-COOH, formic acid HCOOH, and
other glycol degradation acids. Certain additives may also undergo oxidation such as nitrites NO2 may
react to form nitrates NO3. Glycol degradation acids are extremely corrosive and can cause premature
failure of engine and cooling system components 1.
Oxidation stability of engine coolants is affected by many parameters. Among the most critical are:
fluid temperature, aeration rate, pressure, cooling system corrosion metals catalysts, and the engine
coolant corrosion inhibitors. Similar to lubricants, fluid temperature is probably the most critical parameter. The oxidation rate of coolants increases exponentially with temperature. Slight increases in temperature can have significant effects on engine coolant oxidation stability and corrosion protection, especially
at higher temperatures. The second most critical parameter is the type and amount of corrosion inhibitors
contained in the coolant. As will be shown in this paper, different types of engine coolant corrosion
inhibitor technology inorganic only, organic only, hybrid inorganic, and organic exhibit different levels of
Manuscript received March 7, 2006; accepted for publication March 17, 2007; published online May 2007. Presented at ASTM
Symposium on Engine Coolant Technologies: 5th Volume on 17 May 2006 in Toronto, Canada; W. Matulewicz, Guest Editor.
1
Coolants Advisor, Technology Manager, and Coolants Advisor, respectively, Shell Global Solutions US Inc., 3333 Highway 6
South, Houston, TX 77082.
119
oxidation stability and corrosion protection performance when exposed to high temperature oxygen rich
environments.
ASTM D 3306-05 Standard Specification for Glycol Base Engine Coolant for Automobile and Light
Duty Service and ASTM D 6210-04 Standard Specification for Fully Formulated Glycol Base Engine
Coolant for Heavy Duty Engines define the physical, compositional, and performance requirements for
gasoline, diesel, and natural gas engines. With the increase in severity of operating conditions in modern
engines, these test protocols do not currently include performance tests that adequately assess the oxidation
effects on coolant corrosion protection. Therefore, an accelerated oxidation and corrosion test was developed using a rotary pressure vessel to assess oxidation/thermal stability and corrosion protection of coolants.
Experimental
Test Apparatus and Procedure
A literature review showed that the ASTM D 2272-02 Standard Test Method for Oxidation Stability of
Steam Turbine Oils by Rotating Pressure Vessel test has been used to some extent to evaluate coolant
antioxidant and anticorrosion properties 2. The Accelerated Oxidation and Corrosion Test uses a combination of the ASTM D 2272-02 and ASTM D 1384-05 Standard Test Method for Corrosion Test for
Engine Coolants in Glassware tests. The test procedure involves placing a 55-mL coolant sample 50/50 by
volume in DI water in ASTM D 2272-02 glassware with a six metal coupon bundle copper, solder, brass,
steel, cast iron, and cast aluminum. The coupon bundle is the same as used in ASTM D 1384-05, except
that Teflon spacers electrically isolate each coupon in the bundle. The legs on the bundle are also Teflon
rather than brass to minimize etching of the glass Fig. 1. The test solutions are prepared with deionized
water, rather than the ASTM D 1384-05 corrosive water. The metal coupons are prepared, cleaned, and
weighed before and after the test as specified in ASTM D 1384-05.
The glassware is then placed in the pressure vessel, charged with oxygen to a pressure of 620 kPa
90 psi, 6.2 bar and rotated axially at 100 r / min at a 30 angle from horizontal in a bath at 121 150 C
250 302 F for 168 h Fig. 2. The volume of fluid 55 mL was chosen to maximize the amount of fluid
in contact with the metal coupons while at the same time preventing overflow of the fluid into the pressure
vessel while rotating in the bath. A small upper portion of the metal coupons is exposed to the oxygen-rich
environment during the test. The corrosion-inhibitive properties of the test solutions are evaluated on the
basis of weight changes incurred by the specimens. The oxidation-inhibitive properties of the test solutions
are evaluated on the basis of changes in pH, corrosion inhibitor contents, and the presence of glycol
degradation acidsglycolates and formates.
FIG. 1ASTM D 2272-02 pressure vessel with ASTM D 1384-05 metal coupon bundle.
ALVERSON ET AL. ON OXIDATION AND CORROSION TESTING 121
FIG. 2ASTM D 2272-02 bath.
Test Temperatures
Test temperatures of 121, 135, and 150 C 250, 275, and 302 F were utilized in the test. A previous
Union Carbide study reported that the rate of ethylene glycol degradation doubled for every 15 C increase
in temperature under their test conditions 35. The results of this study tend to show greater rates of
oxidation at higher temperatures for certain coolants, which may be due to the severe test conditions. The
results also indicate that the type of corrosion inhibitor technology significantly affects oxidation stability
performance of the coolant.
Test Fluids
The following types of engine coolants were evaluated in the Accelerated Oxidation and Corrosion Test:
light duty extended life coolant LD ELC, light duty hybrid coolant LD HC, light duty conventional
coolant LD CC, heavy duty extended life coolant HD ELC, heavy duty extended service interval
coolant HD ESI, heavy duty traditional fully formulated coolant HD TFF, and recycled conventional
coolant RCC. Table 1 provides compositional information on the inhibitors contained in engine coolants
tested. The Appendix provides additional information on engine coolant and inhibitor terminology referenced in this paper.
TABLE 1Engine coolants and corrosion inhibitors.
Inorganic Inhibitors
Coolant
Inhibitors
LD ELC
LD HC 1
LD HC 2
LD CC
HD ELC 1
HD ELC 2
HD ESI
HD TFF
RCC 1
RCC 2
Borate
Nitrite
Nitrate
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Phosphate
Organic Inhibitors
Molybdate
X
X
X
Silicate
X
X
X
OAT
X
X
X
X
X
X
X
X
Azole
X
X
X
X
X
X
X
X
X
ALVERSON ET AL. ON OXIDATION AND CORROSION TESTING 127
Acknowledgments
The authors wish to thank Mr. Terry Charles for conducting the numerous Accelerated Oxidation and
Corrosion Test runs and Amalgatech for conducting the coolant analyses. The authors are also grateful to
Shell Global Solutions and Shell Oil Products for permission to publish the paper.
Appendix
Tables 4 and 5.
TABLE 4General engine coolant terminology.

Conventional coolant
An engine coolant containing primarily inorganic corrosion inhibitors

such as borate, molybdate, nitrate, nitrite, phosphate, silicate.
Sometimes also referred to as a traditional coolant.
Coolant
A fluid typically consisting of water, glycol, and corrosion inhibitors
which functions to transfer heat from an engine and to provide
corrosion protection of the engine and cooling system components.
Extended life coolant
An engine coolant with longer recommended change out
intervals light duty: 100 000 miles, five years/4000 operating hours;
heavy duty: 300 000 miles, 6000 h.
Extended service interval
An engine coolant that can go beyond 100 000 miles in on-highway
operation between service intervals without the need to replace depleted
chemicals. These coolants may contain delayed release Supplemental
Coolant Additives SCAstypically through the use of corrodibledissolvable membrane or slow-release pellets in a filter casing or
organic additive technology corrosion inhibitors, or both.
Fully formulated coolant
A conventional coolant containing an initial dosage of SCA. These
coolants require periodic addition of SCAs and provide a service life
of 200 250 K miles 23 years with the proper addition of SCAs.
Heavy duty
Service duty characterized by average speeds, power output, and
internal temperatures that are generally close to maximum such as Class 5 to 8
over the road trucks, off-highway equipment, high output stationary engine
applications, and locomotive-marine applications.
Hybrid coolant
An engine coolant containing a combination of inorganic
and organic corrosion inhibitors.
Light duty
Service duty characterized by average speeds, power output, and
internal temperatures generally much lower than potential maximum
such as automobiles, pick-up trucks, vans, sport utility vehicles, small
farm tractors, and lawn maintenance equipment.
Organic Additive Technology OAT Any group of carboxylic acids including aliphatic mono and diacids
and aromatic acids applicable as corrosion inhibitors in coolants.
Supplemental Coolant
A chemical additive that is periodically added to the coolant
Additive SCA
to maintain protection against general corrosion, cylinder liner pitting,
and scaling in heavy duty engines.
Traditional coolant
An engine coolant containing primarily inorganic corrosion inhibitors
such as borate, molybdate, nitrate, nitrite, phosphate, and silicate.
Sometimes also referred to as a conventional coolant.
TABLE 5Inhibitors and primary function(s).
Azole
Borate
Phosphate
Molybdate
OAT
Nitrate
Nitrite
Silicate
Copper and brass protection

pH buffer
pH buffer and iron protection
Cavitation-erosion and cast iron protection
General corrosion protection except yellow metals
Light alloy and solder protection
Cavitation and cast iron protection
Aluminum protection
References
1
2
3
4
5
Eaton, E. R., Boon, W. H., and Smith, C. J., A Chemical Base for Engine Coolant/Antifreeze with
Improved Thermal Stability Properties, SAE Paper 2001-01-1182, Society of Automotive Engineers, Warrendale, PA, 2001.
Karol, T. J., and Donnelly, S. G., Functional Additive Composition Based on Organic Amine Salts
for Coolants, U.S. Patent 5,637,251, June 10, 1997.
Gershun, A. V., and Mercer, W. C., Predictive Tools for Coolant Development: An Accelerated
Aging Procedure for Modeling Fleet Test Results, Engine Coolant Testing: Fourth Volume, ASTM
STP 1335, R. E. Beal, Ed., ASTM International, West Conshohocken, PA, 1999, pp. 113132.
Neddenreip, R. J., Status Report, Ethylene Glycol Oxidation, Technical Report C-133, Linde Company, 1960.
Neddenreip, R. J., Status Report, Ethylene Glycol Oxidation, Technical Report C-135, Linde Company, 1961.

Paper ID JAI100325
Sandra Claeys1 and Serge Lievens1
Coolants at Elevated Temperatures

ABSTRACT: Over the years, new performance requirements and environmental regulations have driven
engine manufacturers to design new engines. The new engine technologies have resulted in different
operating conditions in cooling systems. In general, a trend towards higher coolant temperatures is observed, which is expected to have an implication on the coolant stability and corresponding lifetime. In
heavy duty applications, this trend is even more pronounced as engines are running longer and under more
severe conditions. In this paper, a selection of different current coolant technologies available in the market
have been tested to obtain more information on the influence of the coolant additive package on the
thermal stability of the most commonly used coolant base fluid, mono ethylene glycol MEG. For this
reason glycol oxidation products have been measured after subjecting the coolants to high temperature
oxidative conditions. In addition the physical/chemical stability of the coolants and corrosion protection level
of the additive packages have been evaluated.
KEYWORDS: engine coolant, high temperature, glycol oxidation, corrosion inhibitors
Introduction
Looking into the evolution of engine developments, it has always been a challenge for engine manufacturers to create more powerful and efficient engines. During the past couple of years, this general trend
towards increasing engine power is combined while striving to improve fuel economy and reduce harmful
emissions in order to meet environmental regulations 1. These additional requirements have resulted in
changing engine designs and operating conditions, increasing demands on the cooling system and the
coolant. The following examples illustrate this trend:
increasing the engine power results in a higher heat flux through the cooling system affecting the
local coolant temperature;
weight reduction to improve fuel economy demands smaller coolant volumes, resulting in higher
coolant temperatures;
introduction of an exhaust gas recirculation EGR system to reduce certain emissions results in
25 35 % increased heat energy to the coolant 2. Under those demanding conditions, proper
coolant selection and maintenance are more vital than ever to ensure satisfactory engine life.
Long ago the selection of mono ethylene glycol MEG as a base fluid for coolants was established
because of its balanced performance properties like heat transfer, freezing protection, flammability, aggressive nature, and toxicity 3. Despite the many advantages for coolant applications, glycols are susceptible to degradation at higher temperatures. Under these conditions in the presence of oxygen, a radical
oxidation reaction takes place resulting in the formation of glycol decomposition acids, such as formic and
glycolic acid 4,5. These changes in the base fluid illustrate the potential risk of high temperatures on
coolant properties such as pH, additive stability, and corrosion protection performance. Taking into account the electrophilic character of metallic ions, catalytic action on the oxidation process is expected. The
results are inefficient corrosion protection of metallurgies in the cooling system leading to a more rapid
degradation of the base fluid. Many people have been focusing on new coolant additive technologies
610 to assist engine manufacturers in their selection of new mechanical designs or material selections.
At least one study was undertaken to evaluate the performance and potential oxidation degradation of the
base fluid under more extreme temperature conditions 11.
Manuscript received January 26, 2006; accepted for publication September 22, 2006; published online November 2006. Presented
at ASTM Symposium on Engine Coolant Technologies: 5th Volume on 17 May 2006 in Toronto, Canada;
1
Chemist and Manager, Global Coolants Technology, respectively, Chevron Technology Ghent, Technologiepark-Zwijnaarde 2,
Ghent, Belgium
129
In the following work, a selection of MEG-based engine coolants representing current technologies
has been evaluated for high temperature oxidative stability. For that purpose an in house test setup is used
to simulate the high temperature areas in the cooling system. Next to the study of the breakdown products,
the work also looks to stability and corrosion protection level of coolant additive packages. Measurements
of pH during the oxidation test and changes in reserve alkalinity provide more information on the additive
stability under the applied conditions. The corrosion protection properties, before and after being subjected
to high temperature conditions, were evaluated electrochemically by a cyclic polarization technique and a
static corrosion test. The main focus goes to studying the influence of the additive package on the thermal
stability of the MEG-based fluid. Electrophoresis was used as an analytical technique to determine the
amount of glycol decomposition acids.
Experimental Results
High Temperature Oxidation Test
The high temperature oxidation resistance of the MEG-based coolants was tested by heating the diluted
products 50 vol % in deionized water to a high temperature 185 C, liquid temperature in a pressure
resisting stainless steel container for twelve days. The heat is transmitted to the liquid through a cast iron
coupon type ASTM A 48, class 40, simulating the effects of high temperature areas in an internal
combustion engine cooling system. A valve in the test apparatus allowed for samples to be taken Fig. 1.
The coolant dilutions were prepared according to ASTM Test Method for Sampling and Preparing Aqueous Solutions of Engine Coolants or Antirusts for Testing Purposes D 1176-98/reapproved 2002.
FIG. 1High temperature oxidation test.

In order to evaluate the influence of the coolant additive packages on the thermal glycol stability, the
other testing parameters such as coolant temperature, coolant volume, pressure, were kept constant for
each tested coolant. By running the test in a sealed container, the influence of air oxygen on the glycol
degradation process was limited.
Coolant Physical and Chemical Properties
During the high temperature oxidation test, samples were taken at regular time intervals and pH was
measured according to ASTM Test Method for pH of Engine Coolants and Antirusts D 1287-91/
reapproved 2002.
Before and after the oxidation test, the reserve alkalinity was determined according ASTM Test
Method for Reserve Alkalinity of Engine Coolants and Antirusts D 1121-98/reapproved 2003.
Capillary electrophoresis CE was the analytical technique used for the determination of the MEG
degradation products, such as formic and glycolic acids. Separations were done with a P/ACETM MDQ
Beckman Coulter apparatus. Electrophoresis is a technique used for separation and quantification of
charged molecules. The separation is accomplished under the influence of an electric field, which is the
result of a potential difference between an anode and a cathode . In capillary electrophoresis, a
narrow-bore fused silica capillary is used as the stationary phase. As a liquid phase, and carrier of the
CLAEYS AND LIEVENS ON COOLANTS AT ELEVATED TEMPERATURES 131
analyzing sample, a conductive medium a buffer is critical to obtain a good separation. When passing
through an electric field in a conductive medium, molecules with a positive charge move to the cathode,
while those with a negative charge move to the anode. Separation of the ions is determined by their
difference in mobility, which is largely influenced by their charge and radius.
Corrosion Protection Performance
Electrochemical TestA potentiokinetic cyclic polarization technique was used to accelerate the electrochemical corrosion process of a metal in a coolant. The details of the test setup apparatus and conditions have been described previously 10. The corrosion protection performance of a coolant corrosion
inhibitor package was evaluated by increasing the potential difference between a working electrode the
metal alloy to be tested and an auxiliary electrode a platinum electrode. For this study, aluminum USA
AA 6063 and carbon steel UNS G10180 were used as the working electrode. An all-metal silver
electrode was used as the reference electrode. The working electrodes were freshly polished on 600 mesh
abrasive paper prior to testing in order to obtain reproducible results. The testing solutions were a
50/ 50 vol % coolant/water dilution, to which corrosive salts 15.70 mg sodium sulfate Na2SO4,
17.50 mg sodium chloride NaCl, 14.64 mg sodium bicarbonate NaHCO3, and 38.61 mg calcium chloride dihydrate CaCl2 H2O to 105 g of 50 vol % coolant were added. The solutions were stirred until all
salts dissolved. The electrodes were immersed in the solution and allowed to equilibrate in the test
solutions for 1 h at ambient temperature prior to testing. Special care was taken to avoid the formation of
air bubbles on the electrode surface. During this stabilization period no potential difference is forced on the
system. Under these conditions an equilibrium is established between oxidation of the metal and reduction
of the solution. The equilibrium corrosion potential Ec Fig. 2 is measured relative to the reference
electrode. It is the potential at which oxidation and reduction rate are equal. After stabilization, a positive
potential is applied, increasing the corrosion rate which is reflected in an increase of the current density.
When a good passivation protective layer is formed on the metal, the current density remains constant
during a certain potential interval. When the potential difference becomes too high, the protective film will
finally rupture. At a current density of 200 mA/ cm2 the potential is reversed. Under the influence of the
protective mechanism of the corrosion inhibitors, the corrosive sites are repassivated, resulting in a decrease of the current density. The result of this test is a potentiokinetic cyclic polarization scan, in which
several coolant parameters were monitored. They are as follows Fig. 2:
Passivation current density I0the current density at which the passivation protective film is
formed. High current densities correspond with high corrosion rates.
Pitting or rupture potential Erthe potential at which the passivation film breaks down.
Stability passivation potential Es values reported Tables 3 and 4 are calculated by subtracting the
potential at start I0 from the rupture potential Er see arrow in Fig. 2.
Repassivation potential Epthe potential at which active regions are repassivated.
FIG. 2Example of a potentiokinetic cyclic polarization scan.

Glassware Corrosion TestThe static corrosion test is run according ASTM Test Method for Corrosion Test for Engine Coolants in Glassware D 1384-05. The post oxidation test coolants were diluted to
33 vol % as required by D 1384, to which the corrosive salts were added. This test evaluates the
corrosion protection provided by coolants to different metallurgies by measuring the weight changes of the
metal test specimen. The test was run in duplicate.
Coolant Selection
For both heavy duty and automotive engines, MEG-based coolants have been the preferred choice for
many years. Driven by changes in engine designs and regional requirements, coolant manufacturers have
been developing new additive packages, resulting in a broad range of coolant technologies. For this study,
automotive coolants from different regions characterized by a certain corrosion inhibitor technology Table
1 have been selected.
Coolants A and B represent the organic acid technology. These coolants typically contain carboxylic
acid corrosion inhibitors providing aluminum and ferrous metal protection in combination with an azole
for copper and brass protection. An overview of this type of coolant technology was earlier given by Weir
and Van de Ven 12. Coolant A contains aliphatic monocarboxylic acids in combination with dibasic
acids. Coolant B is a combination of different dibasic aliphatic acids. By testing both technologies under
high temperature oxidative conditions, the thermal stability of various carboxylic acid formulations was
studied. Selected silicate containing coolant technologies are coolants C, D, E, and F. Coolant C is a
combination of monocarboxylic/aromatic acids with silicates and other inorganic inhibitors usually present
in a class of coolants known as hybrid technology. Coolants D, E, and F are conventional silicate-borate
technology without any aliphatic acids. E and F can be considered more traditional coolants from Europe
containing nitrite in combination with silicate. As coolant E also contains an organic compound aromatic
acid salt rather than aliphatic in the United States, it is sometimes considered a hybrid coolant. The
phosphate-containing coolant technologies are represented by coolants G and H. Coolant G contains a
combination of aromatic acid with phosphate. Coolant H is characterized by additional aliphatic dibasic
acid.
TABLE 1Coolant inhibitor formulations.

Coolant
Organic Acid
Based
Inhibitor
Monoacid
Dibasic acid
Aromatic acid
SiO2
3
NO3
B4O2
7
PO3
4
Triazole
MoO2
4
NO2
Silicate Based
B
Phosphate Based
Note: indicates the presence of this inhibitor by analysis

Determination of MEG Decomposition Products in Selected Coolants
During the high temperature oxidation test, coolant samples were taken at six and twelve days at the end
of the test, respectively, in order to follow the breakdown process of the MEG base. Formic and glycolic
acid were identified as the main decomposition products. Due to the alkaline nature pH 7 of the
coolants, these compounds are present in the coolant samples as formate and glycolate. Electrophoresis

TABLE 2MEG degradation products present in coolant samples after six and twelve days in test
apparatus.
Formate, mg/L
Coolant
A
B
C
D
E
F
G
H
6 Days
67
65
81
16
401
1067
72
62
12 Days
63
65
91
28
429
1332
95
81
Glycolate, mg/L
6 Days
122
199
147
1802
454
1372
243
153
12 Days
117
223
166
2037
512
1752
391
232
Total Amount of
Degradation Products, mg/L
6 Days
189
264
228
1818
855
2439
315
215
12 Days
180
288
257
2065
941
3084
486
313
FIG. 3Total amount of MEG degradation acids during high temperature oxidation test.
was used for the separation and quantification of these decomposition products. The analysis results Table
2 and Fig. 3 provide information on how the additive package affects the thermal stability of the base
fluid.
When comparing coolants A, B, C, H containing aliphatic organic acid corrosion inhibitors with
coolants D, E, F, and G which do not contain aliphatic organic acid corrosion inhibitors, the lowest
amount of decomposition products were measured for the coolants containing aliphatic carboxylic acid
corrosion inhibitors. The effect was observed for different coolant class technologies, the pure organic
acid-based coolants A and B, the hybrid silicate containing coolant C and the hybrid phosphate containing
coolant H. It also appears that coolants containing aliphatic acids are more thermally stable over time.
From all of the tested coolants, the organic acid-based coolant A, containing a combination of aliphatic
monocarboxylic acids and dibasic acids, produced the smallest amount of MEG degradation acids. The
high temperature oxidative stability of the base fluid in this type of coolant could be explained by a
combination of characteristics linked to this coolant technology. Earlier work has shown that this synergistic aliphatic monoacid/diacid corrosion inhibitor combination found in coolant A provides superior
corrosion protection performance in laboratory and field tests, compared with more traditional engine
coolant formulations 13. This may be explained by a difference in corrosion protection mechanism for
these coolant additives. Study of the metal surface protective film 1315 has shown that the aliphatic
carboxylate inhibitors form a selective at anodic sites thin protective layer, where inhibitors interact with
the metal surface through a strong chemical bond. Thicker layers of additives, characteristic for the
uniform corrosion protection mechanism of traditional inhibitors such as silicates, can result in higher
metal surface temperatures and higher corrosion rates. As the presence of corrosive metallic ions in
in the organic acid-based coolants A and B, it can be observed that the pH changes differently. For coolant
A, the pH change is very small, while for coolant B, a larger decrease in pH is observed at the beginning
of the test, then over time, the pH becomes more constant. The limited change of the reserve alkalinity can
be an extra indication for the high stability of this coolant technology. For the silicated coolant C, and the
phosphated coolant G, pH variations are small even though larger amounts of degradation acids are formed
compared to the OAT coolants. This can be explained by the working mechanism of a buffer such as
borate and phosphate. The larger change in reserve alkalinity for both coolants is an indication of an
important change in coolant composition.
Influence of High Temperatures on Corrosion Protection Properties of Selected Coolants
As the coolant is in contact with many metals in the engine, one of its important functions is to protect the
engine materials against corrosion. This is mainly determined by the stability of the additive package and
the physical and chemical properties of the coolant. In this work, the effect of high temperatures on the
corrosion protection performance of coolants was studied by a potentiokinetic polarization scan, which
was run on the coolants before and after high temperature oxidation test. Two metals, aluminum Table 3
and carbon steel Table 4 were evaluated for this purpose.
For the organic acid-based coolant technology A, high stability passivation potentials above
3300 mV were determined on aluminum. This is an indication for low probability of pit formation 16.
The exact value of this potential cannot be reported as the passivation layer remains stable under the
applied conditions. For the same reason repassivation potentials cannot be determined Fig. 6a. On
carbon steel it is preferable to describe the pitting potential as the potential at which the protective
passivation layer is destabilized. No pitting corrosion is observed as no repassivation potential can be
measured Fig. 6b. Although the corrosion protection behavior on aluminum and carbon steel for the
FIG. 6Potentiokinetic polarization scan of coolant A before high temperature oxidation test; (a) on
aluminum, (b) on carbon steel.
organic-based coolants A and B is different, both remain unaffected under high temperature oxidation
conditions.
For the silicate-based coolants C, D, E, and F significant decreases in stability passivation potential
FIG. 7Potentiokinetic polarization scan of coolant D on aluminum; (a) before oxidation test, (b) after
oxidation test.
on aluminum and/or carbon steel were observed e.g., Fig. 7 after the oxidation test. This can be explained
by changes in the stability of the additive package or by the formation of high amounts of glycol degradation acids, or both.
Although high stability passivation potentials were measured for the phosphate-based coolants G and
H on both metals, strong decreases in pitting protection and repassivation ability on aluminum were found
FIG. 8Potentiokinetic polarization scan of coolant G on aluminum; (a) before oxidation test, (b) after
oxidation test.
after aging of the coolant under extreme conditions Fig. 8. Together with the large variations in reserve
alkalinity found for this technology Fig. 5, the loss of corrosion protection performance could be attributed to additive instability.
Next to rupture potential and repassivation potential, the current density at which passivation occurs
TABLE 3Potentiokinetic polarization scan characteristics of coolants before and after high temperature oxidation test on aluminum.
Stability Passivation
Potential
mV
Coolant
A
B
C
D
E
F
G
H
BeforeTest
3300
1070
1710
1680
2240
1185
3040
3230
AfterTest
3300
1070
1640
950
2180
734
720
1880
Repassivation Potential
mV
BeforeTest
283
551
430
1430
117
1790
168
AfterTest
224
492
430
1420
329
350
52
Passivation Current
A / cm2
BeforeTest
11
12
11
11
11
12
9
10
AfterTest
11
12
13
11
11
12
9
10
TABLE 4Potentiokinetic polarization scan characteristics of coolants before and after high temperature oxidation test on carbon steel.
Stability Passivation
Potential
mV
Coolant
A
B
C
D
E
F
G
H
BeforeTest
720
630
1030
728
270
698
1540
1495
AfterTest
720
630
1030
536
156
180
1565
1350
Repassivation Potential
mV
BeforeTest
310
159
284
AfterTest
574
310
178
273
Passivation Current
A / cm2
BeforeTest
8
9
9
13
2
8
16
21
AfterTest
8
9
9
14
10
13
19
21
Taking into account that the same base fluid is used for all coolant compositions, it can be shown that
the additive package has an effect on the amount of degradation acids formed. Although the exact causes
for the results are not always fully understood, it can be concluded that the use of aliphatic acid corrosion
inhibitors provides greater protection against thermal breakdown of the base fluid. Coolants containing
only aliphatic acid corrosion inhibitors appeared to have the highest resistance to thermal breakdown.
When the same class of additives are used e.g., organic acid-based coolants or hybrid type coolants
differences could be observed for various coolant parameters, emphasizing the fact that coolant performance, as it relates to oxidative stability or corrosion protection, or both, cannot be predicted by coolant
class alone.
The study has also shown the importance of looking at several different coolant characteristics, such as
physical/chemical properties, the formation of glycol breakdown products, as well as corrosion protection
properties in order to get a better understanding of the high temperature stability performance of a coolant.
References
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3
4
5
6
7
8
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13
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Paper ID JAI100634
Yu-Sen Chen,1 R. Doug Hudgens,2 and Edward R. Eaton3
Comparison of Bench Test Methods to Evaluate Heavy Duty

Coolant Thermal Stability
ABSTRACT: The past 10 to 15 years have seen a dramatic change in heavy duty coolants and cooling
system maintenance practices. Controversy exists about the relative merits of newer organic acid OAT
coolants and more conventional products, especially in the area of thermal stability. Coolant life has been
extended from two years/240 K miles to at least five years/600 K miles. It is not uncommon for the same
charge of coolant to remain in the cooling system until engine rebuild. Further, there has been an equally
significant increase in the coolant service intervals. Reinhibition of the coolant was once tied to the oil
change interval at 15 to 25 K miles. Now this additive addition has been extended in many cases to one
year/150 K miles to two years/300 K miles. Along with these dramatic increases in coolant life and service
interval, strategies to reduce exhaust emissions such as EGR have increased and will continue to increase
coolant temperatures. Sorting out coolant stability issues in the field is both expensive and time consuming.
Further, it is very difficult to control a field test so as to obtain reliable data. In this environment, a bench test
method that can quickly simulate high temperature, severe field service conditions is of vital importance.
This paper compares four bench test methods as far as their ability to sort out thermal stability issues based
on results from five coolants representing different additive packages and glycol qualities.
KEYWORDS: heavy duty engine coolants, oxidation stability, corrosion, extended service coolants,
conventional fully-formulated coolants, supplemental coolant additives, antifreeze, glycol, glycol
esters, off-spec glycol, antifreeze grade glycol
Introduction
For several decades the producers of ethylene and propylene glycols were also the major blenders and
suppliers of automotive antifreeze in North America and other parts of the world. These included companies such as Dow Chemical, Union Carbide, Texaco, and Shell Chemical. In the past 20 years corporate
changes that have occurred in the glycol industry have changed the way in which antifreeze/engine coolant
products come to market. Many major brands that were previously owned by the glycol producers have
been sold to companies that do not produce glycol, resulting in glycol availability and price fluctuations
that have opened the door to many alternate avenues of antifreeze/engine coolant base fluid supplies.
In some cases, these alternative lines of supply have proved most satisfactory. For example, technologies have been developed to successfully gather and recycle used engine coolants, often resulting in
coolants that performed essentially the same as new products 1. More recently, high demand for
antifreeze/coolant products has enabled the entry of unsatisfactory base fluids. They have caused many
premature failures in new power systems including radiator, water pump, and general corrosion issues.
These experiences have resulted in unnecessary warranty costs to OEMs and very irate end-users. Unfortunately, some of these problematic coolants might even pass ASTM coolant performance requirements on
two of the commonly employed corrosion screening tests, ASTM D 4340 Standard Test Method for
Corrosion of Cast Aluminum Alloys in Engine Coolants Under Heat-Rejecting Conditions and ASTM D
1384 Standard Test Method for Corrosion Test for Engine Coolants in Glassware. While these tests are
certainly not adequate to prove the overall capability of the coolants, they give false comfort to users and
some marketers who do not look deep enough into the properties of the coolants.
Responding to concerns in the marketplace that seriously problematic coolants are being marketed to
Manuscript received May 8, 2006; accepted for publication March 17, 2007; published online May 2007. Presented at ASTM
Symposium on Engine Coolant Technologies: 5th Volume on 17 May 2006 in Toronto, Canada; W. Matulewicz, Guest Editor.
1
Research Director, Fluid Management Division, Dober Chemical, 333 West 195th St., Glenwood, IL 60425.
2
Chief Chemist, Fleetguard, Inc., 1200 Fleetguard Road, Cookeville, TN 38506.
3
Chief Engineer, Amalgatech, 2965 West Osborn Road, Phoenix, AZ 85017.
139
consumers and bulk users alike, ASTM Committee D-15 minutes record initial tests performed on a
number of coolants employing a modified turbine oil test, ASTM D 2272, which evaluates the oxidation
resistance of turbine oils 2. The minutes record that the oxidation stability of coolants was demonstrated
to be significant as a property that might affect customer satisfaction and protection of the system. Many
of the suspect/problematic coolants may be blended with glycols that are described as virgin because
they have not previously been used as automotive antifreeze/coolant. However, these fluids have either
been used for aircraft deicing, some other manufacturing process, or may be recovered from glycol still
bottoms that have been observed to have undesirable oxidation properties compared to antifreeze grade
ASTM E 1177 virgin ethylene glycol provided by major EG suppliers.
Therefore, if a method could be developed that correctly ranks coolants as to their observed field
performance it may provide a good indication of prospective coolant service interval or total life, or both.
Further, ASTM Subcommittee D15.21 on Long-Life Coolants has been struggling to agree on a definition,
test methods, and performance specification that differentiates between serviceable conventional service
interval technologies from those capable of significantly longer service intervals. We also hope to better
understand the mechanisms of coolant degradation, specifically how the glycol and additive package
contribute to overall corrosion protection as the coolant ages, and to develop methods that best model
those mechanisms. To that end, as we proceed with the investigation, we will compare the behaviors of the
coolants against published 3 information that describes the depletion behavior of fully-formulated conventionally inhibited coolants as well as the authors current experience with other technologies. For
convenience, principal graphs from the Hudgens-Mitchell paper in ASTM STP 1335 are attached for
reference in the Appendix following the main body of this paper. These are useful tools for readers who
may not be familiar with the depletion behaviors of the conventional technology components in engine
applications.
It will be useful to define some terms that will be used in this paper, see Table 1.
What we looked for in selecting coolant samples for testing:
1. A cross section of OEM-branded and aftermarket-branded antifreeze coolants, including coolants
defined by the authors as true virgin coolants, concentrated and prediluted recycled coolants, and
at least one example of a coolant marketed by the supplier as a virgin coolant that has characteristics different than true virgin coolants and that has caused severe and widespread damage to
engines in actual use.
2. Conventionally-inhibited, Long Life also known as Extended Life style technologies that
incorporate inorganic, carboxylate, and various forms of hybrid philosophies are represented.
More than 15 coolants were tested. The authors have selected five coolants for discussion in this paper
that best illustrate the strengths and weaknesses of each of the prototype test methods. They are coded and
described as follows:
FFCA virgin conventionally-inhibited, fully-formulated OEM-recommended EG coolant with a
decades-long track record of satisfactory performance when properly serviced at recommended intervals
i.e., oil change intervals with SCAs.
NOATA virgin nitrite-molybdate-carboxylate NMOAT inhibited, fully-formulated OEMrecommended EG coolant with a track record of satisfactory performance when properly serviced at
recommended intervals i.e., 300,000 miles with OAT extender.
NVCA questionably-identified virgin conventionally inhibited, claimed to be fully-formulated
coolant, apparently blended from off-spec EG with a track record of very unsatisfactory performance and
widespread rapid damage to customers equipment. This coolant is reported by the supplier to be made
with EG recovered from glycol bottoms.
H-1A virgin American hybrid, fully-formulated OEM-recommended EG coolant with a good track
record of satisfactory performance when properly serviced at recommended intervals.
H-2A virgin European-style hybrid inhibited, fully-formulated OEM-recommended EG coolant with
a decades-long track record of satisfactory performance when properly serviced at recommended intervals.
CHEN ET AL. ON COMPARISON OF BENCH TEST METHODS 141

TABLE 1Terms used.
Term
Conventional Inhibition
Organic Acid Inhibition
Hybrid Inhibition
Virgin Glycol
Questionable Virgin
Glycol
Fully-formulated
Antifreeze/Coolant
Recycled Glycol or
Engine Coolant
Long Life or Extended

Life Coolant
Extended Service
Interval
Explanation
Corrosion inhibition with traditional packages. Such
chemicals may include nitrite, nitrate, silicate, borate,
phosphate, molybdate, and azoles.
Packages that rely primarily on aliphatic carboxylic
acids and azoles. Heavy-duty versions may also
contain nitrite or molybdate, or both, but they still fall in
the
OAT family.
These are packages that frequently employ benzoate,
an aromatic carboxylate, as their primary organic acid
and also heavily depend on various inorganic
supplements such as silicate, nitrate, phosphate, and
molybdate. Heavy-duty versions may contain nitrite.
Three substantial subcategories exist: American
hybrids may not use benzoate, but a different
carboxylate and otherwise look similar to conventional
fully-formulated approaches. European styles rarely
use phosphate; Asian styles rarely use silicate and may
use multiple carboxylates in combination.
Glycol produced by an ethylene glycol manufacturer
that meets ASTM E 1177 and that has never been
used for any purpose whatsoever and not reprocessed
from still bottoms.
A product marketed as nonrecycled but that did not
come directly from a traditional glycol supplier. These
fluids may be used in some other process, then sold as
a byproduct or waste stream fluid, or may be recovered
from glycol bottoms. ASTM coolant specifications do
not include coolants formulated from these sources of
glycols, and their use as automotive antifreeze/coolant
has been observed to be highly unsatisfactory in some
cases.
A product that conforms to ASTM D 6210 or TMC
RP329 or RP330 heavy-duty coolant specifications, or a
combination thereof.
These products do not require, and should not receive,
a precharge of SCA before initial use. There exists
conventional, OAT, and hybrid examples of fullyformulated coolants.
Glycol or engine coolant that has usually been
recovered from used engine coolant by a capable
technology such as distillation, ion exchange,
membrane separation, or a combination of these
technologies. The base fluid is usually reinhibited with
the same type of additive technologies as are used for
true virgin antifreeze/coolant.
A coolant technology that does require frequent
maintenance with supplemental coolant additives, and
may generally stay in service well in excess of 300 000
miles. Most now publish change intervals of 600 000
miles.
A coolant chemical service interval that is at least twelve
months or 150 000 miles and is not tied to the oil drain
interval. Conventional coolants are generally treated
with supplemental coolant additives every 12 000
20 000 miles in the form of charged filters or liquid
additives.
The Test Methods and Experimental Conditions

Reaction Kettle
This is a modification of the accelerated aging procedure originally developed by Gershun and Mercer of
Honeywell for light-duty conventional and extended life coolant that was designed to predict coolant
composition and performance after 100 K or more miles of use 4.
FIG. 1Reaction kettle used by Dr. Chen.

1. The 2000-mL reaction kettle Fig. 1 was equipped with a condenser, a gas dispersion tube, and a
thermometer. A total of 1800 mL of EG 85/15 premix solution was added into the kettle and mixed
with a magnetic stir bar. Aluminum, iron, and copper turnings obtained from Metaspec in San
Antonio, TX, 3.333 g each, was placed in a 316 stainless steel basket. Subsequently, the basket
was suspended into the reaction kettle in the test solution using a thin nichrome wire.
2. To start the test, the hot plate was turned on and the test solution was heated at 115 C 240 F.
The solution was purged with air at 100 mL/ min. The test lasted for 14 days. Additional water was
added to make up the water loss. Samples were collected at 2, 5, 7, 9, 12, and 14 days and
measured for pH, RA, EG, inhibitors concentrations, metals, and glycol degradation acids formic
and glycolic.
Modified ASTM D 4340
This test method modification was developed by Valvoline and has been used previously to evaluate the
stability of silicate in coolant. It has also been used to successfully demonstrate the oxidation stability
differences between uninhibited coolant base chemistries 5.
1. This test method uses all of the equipment/apparatus specified in ASTM D 4340.
2. This test method covers a laboratory screening procedure for evaluating the effectiveness of
engine coolants in combating corrosion of aluminum casting alloys and coolant degradation under
heat-transfer conditions that may be present in aluminum cylinder head engines.
3. In this test method, a heat flux is established through a cast aluminum alloy somewhat higher than
typical of that used for engine cylinder heads while exposed to an engine coolant under a pressure
of 193 kPa 28 psi. The temperature of the aluminum specimen is maintained at 150 C 300 F
and the test is continued for one week 168 h. The coolant concentration is 50 % and there are
100 ppm each of chloride and sulfate added to the test fluids. The effectiveness of the coolant for
preventing corrosion of the aluminum under heat-transfer conditions hereafter referred to as
heat-transfer corrosion is evaluated on the basis of the weight change of the test specimen and
change in coolant chemistry including both glycol and inhibitor package degradation.
4. Post Modified ASTM D 4340 testing: The coupons are cleaned and corrosion rate determined
according to D 4340 see Fig. 2. The used coolant sample is tested for physical properties,
corrosion inhibitor levels, and coolant degradation/metal corrosion levels. Results are suspect if
significant change in water content occurred.
PARR Reactor Test
Fleetguard and Dober developed this method to model primarily the nitrite stability of heavy-duty coolants
in 300 to 400 K miles of actual field service see Fig. 3 and Fig. 4.
1. A total of 1200 mL EG 50/50 premix solution was added into the Parr reactor cylinder. A 10-ft
copper wire was wrapped around the cooling coils so that the copper wire would be in contact with
the test solution. The reactor head was placed on top of the reactor cylinder and the reactor split
ring collar was tightened. The type J thermocouple was placed into the reactor heads thermowell.
FIG. 2ASTM D 4340 test rigs at Amalgatech.
FIG. 3The PARR reaction vessel used by Dr. Chen.
2. To start the test, the display, motor, and heater were turned on. The motor speed was set to 40 %
maximum for good mixing and the temperature set to 129 C 265 F. Air pressure is about
25 psi, generated from the heating of the coolant. The test lasted for 14 days. Samples were
collected at 2, 5, 7, 9, 12, and 14 days. They were measured for pH, RA, EG, copper and glycol
degradation acids formic and glycolic. After each sample collection, heat was stopped and the
test solution was cooled with cold water to 25 C. Subsequently, the reactor was refilled with air
by pumping air through the reactor for 20 min before the heat was turned back on to continue the
test.
FIG. 4Internal view of the PARR reaction vessel.
Rotating Pressure Vessel Oxidation Test (RPVOT)

This test method is a modification presented by Alverson of Shell Oil Products, USA. It is being investigated as a possible tool by the authors and is continuing to be developed at Shell simultaneously.
1. The modified RPVOT uses all of the equipment/apparatus specified in ASTM D 2272 with exception of the copper catalyst coil which is replaced with a modified ASTM D 1384 glassware
corrosion metal bundle.
2. Modified ASTM D 1384 glassware metal coupon bundle: In place of the copper catalyst coil, a
modified ASTM D 1384 metal coupon bundle is used as the catalyst and to assess corrosion
protection performance of the coolant. The modified ASTM D 1384 metal coupon holder consists
of two Teflon legs in place of brass legs with the ASTM D 1384 six metals coupon bundle
copper, solder, brass, steel, cast iron, and cast aluminum. The metal coupon bundle is assembled
in the order as specified in ASTM D 1384 using 2 small Teflon spacers between each metal, rather
than the brass and steel spacers. Thus, the metals in the coupon bundle are not galvanically
coupled with each other. Due to the small ASTM D 2272 glassware size opening. Teflon spacers
are not used between the Teflon legs and end metals copper and cast aluminum. The metal
bundle after assembly with the brass screw/bolt and insulating tube will be shorter than the
standard ASTM D 1384 bundle and will require snipping the bolt and insulating tube to allow
insertion of the metal bundle in the ASTM D 2272 glassware. The objective is to provide Teflon
on the all sides and bottom of the metal coupon bundle to minimize etching of the glass. Used
coolant test results after RPVOT testing indicates that the holder/metal coupon still removes some
silicon from the ANTM D 2272 glassware see Fig. 5.
3. Test conditions: EG 50/50 coolant dilution is prepared with deionized water rather than corrosive
water, 55 mL coolant sample, 90 psi O2 initial charge at room temperature 77 F, 250 F, 168 h,
and 100 r / min. The sample size 55 mL was selected to maximize the amount of coolant in
contact with the metal coupon bundle while attempting to minimize leakage from the glassware
into the steel pressure vessel while rotating at 100 r / min at a 30 angle.
4. Post RPVOT testing: The coupons were cleaned and weight changes determined according to
ASTM D 1384. The used coolant sample was tested for physical properties, corrosion inhibitor
levels, and coolant degradation/metal corrosion levels. Results are suspect if significant change in
water content occurred.
FIG. 5RPVOT test rig.
Results
Summary of Reaction Kettle Test Data
TABLE 2Reaction Kettle Table of Data
FFC
Component
Total Acids
NaNO2
NaNO3
Na2HPO4
Na2MoO4
Na2B4O7
Na2SiO3
NaTT
BZT
NaMBT
Sebacic Acid
2-EH Acid
Benzoic Acid
Cu
PH
RA
NVC
First
9
3,471
1,009
0
0
1,764
860
599
Last
1,596
2,055
1,214
0
0
1,555
99
427
564
0
10.8
5.6
16
8.2
3.1
First
471
3,780
27
0
0
409
0
698
0
10.0
5.7
H1
Last
3,153
0
1,335
0
0
367
52
363
225
6.7
0.6
H2
First
13
3,045
1,030
7,552
1,450
1,793
1,015
1,278
Last
1,440
2,817
1,101
3,965
1,329
1,653
522
1,132
825
823
0
10.6
12.4
22
8.7
9.3
FIG. 6Kettle behavior graphs.
First
73
1,498
5,513
0
0
9,822
1,114
0
947
19,960
0
7.0
12.6
NOAT
Last
1,035
65
5,481
0
0
8,626
591
0
881
17,650
1
7.4
11.8
First
47
1,564
20
0
2,219
0
0
2,158
Last
2,314
100
175
0
1,825
0
0
1,640
2,009
28,900
2,904
25,530
0
9.1
4.4
7
8.0
1.1
Summary of Modified ASTM D 4340 Test Data
TABLE 3D4340 (Modified) Table of Data

Coolant ID
Color
pH
Glycolate
Formate
Nitrite
Nitrate
Phosphate
Mo
Boron
Silicon
BZT
MBT
TTZ
Benzoate
2-eh
Sebacic
Al
D4340 R Value
FFC
Before
Pink
10.67
0
0
1467
445
0
0
189
116
0
290
277
0
0
0
0
FFC
After
Pink
8.12
165
160
1385
475
0
0
193
129
0
0
266
0
0
0
0
R = 0.07
NVC
Before
Green
9.89
150
140
1527
13
0
0
56
0
0
0
297
0
0
0
0
NVC
After
Green
9.18
470
355
1215
110
0
0
55
0
0
0
241
0
0
0
0
R = 0.20
H1
Before
Blue
10.90
0
0
1317
485
3085
392
188
139
0
0
574
0
0
468
0.0
H1
After
Blue
10.02
220
110
1215
635
2845
358
175
167
0
0
593
0
0
469
0.0
0.03
H2
Before
Yellow
7.77
0
0
960
1787
0
0
1100
135
0
0
0
12740
0
0
0
FIG. 7Modified ASTM D 4340 behaviors.
H2
After
Yellow
7.42
208
136
913
1699
0
0
1086
113
0
0
0
12700
0
0
0
R = 0.13
NOAT
Before
Red
9.01
0
0
577
0
0
637
0
0
0
0
952
0
15810
1353
0
NOAT
After
Red
8.25
210
0
470
85
0
688
0
0
0
0
973
0
19120
1349
0
R = 0.02
FIG. 8ASTM D 4340 aluminum corrosion rate (R value).
Summary of Parr Reactor Test Data

TABLE 4PARR Reactor Data Table
FFC
Component
Total Acids
NaNO2
NaNO3
Na2HPO4
Na2MoO4
Na2B4O7
Na2SiO3
NaTT
NaMBT
2-EH Acid
Cu
Fe
PH
Delta pH
RA
Delta RA
NVC
H1
H2
NOAT
First
1
2,038
579
0
0
1,043
543
356
337
Last
2,419
1,073
1,294
0
0
1,087
460
267
0
First
185
2,246
8
0
0
223
0
Last
2,901
0
246
0
0
239
86
First
45
1,824
580
4,519
798
918
482
Last
1913
1,635
751
3,147
793
896
332
First
51
1,698
2,215
0
0
6,105
668
Last
1,116
1,298
2,414
0
0
6,184
635
0
0
10.0
118
0
6.9
3.1
0.5
2.8
0
1
10.2
96
1
8.1
2.1
1.0
2.7
0
0
10.4
22
13
7.8
2.6
4.3
2.1
0
0
8.0
95
2
7.6
0.4
6.0
1.3
3.3
3.7
6.4
7.3
First
94
3,706
68
0
0
0
0
Last
1,107
3,055
364
0
0
0
0
18,300
0
0
8.5
18,770
0
0
7.4
1.1
1.7
0.6
2.3
FIG. 9PARR reactor behaviors.
TABLE 5RPVOT Data Table

ID Code
Additive Family
Color
pH
Glycolate
Formate
Total Acids
Nitrite
Nitrate
Phosphate
Mo
B
Si
MBT
TTZ
Benzoate
2-eh
Sebacic
Cu
Pb
Fe
Al
FFC
FFC
FF Conventional
Before
Pink
10.47
0
0
0
1403
440
0
0
184
113
265
275
0
0
0
0
0
0
0
After
Brown
4.88
3835
2750
6585
0
310
0
0
208
69
0
25
0
0
0
411
50
1093
40
NVC-1
NVC-1
FF Conventional
Before
Green
9.89
150
140
290
1527
12
0
0
55.5
0
0
298
0
0
0
0
0
0
0
After
Black
4.94
6750
5400
12150
0
0
0
0
108
60
0
0
0
0
0
437
0.0
4915
54.0
H-1
H-1
NM HOAT
Before
Clear
10.90
0
0
0
1317
485
3085
392
187
139
0
573
0
0
420
0
0
0
0
After
Yellow
6.94
3410
440
3850
915
1080
2380
389
238
161
0
645
0
0
380
0
5
2
0
H-2
H-2
FF HOAT
Before
Yellow
7.77
0
0
0
960
1787
0
0
1100
135
0
0
12740
0
0
0
0
0
0
After
Yellow
7.00
1692
502
2194
526
2323
0
0
1140
108
0
0
13160
0
0
5
16
0
0
NOAT
NOAT
NMOAT
Before
Red
8.32
0
0
0
573
4
0
697
0
0
0
1144
0
18420
1712
0
0
0
0
After
Orange
6.71
735
0
735
290
325
0
648
0
40
0
923
0
18490
1445
1
0
0
0
Summary of RPVOT Data

Discussion and Comparison of the Test Methods
How the data from each of the tests compare to user experiences and generally understood degradation
mechanisms.
FIG. 10RPVOT weight and corrosion losses of metal specimens.

1. Reaction Kettle: While the test did deplete nitrite, especially in the most problematic coolant, the
mechanism was not that observed in the field. The NOAT and H-2 lost all of their nitrite with no
nitrate increase or only very slight nitrate increase. The results were somewhat counter to field
experience. Additive packages made significant differences. The other conventional coolants FFC
and H-1 lost nitrite with nitrate increase in an expected way. The NVC coolant lost all nitrite after
about ten days into the test see Table 2.
Glycol does not degrade faster in NOAT coolants than other virgin coolants. Actual observa-
FIG. 11RPVOT behaviors.

tions suggest that the reverse is true. The copper attack by the NVC coolant was dramatic, which
is consistent. The kettle test showed slow loss of 2-EH acid, benzoic acid, borate and molybdate,
consistent with field observations, but depleted phosphate far faster than is observed in actual
operating coolants see Fig. 6.
Overall, this test was not a good model of the coolant aging process as we observe it in real
vehicles.
2. Modified ASTM D 4340: The types of reactions that are occurring are consistent with the aging
behaviors observed in the field. Nitrite is usually oxidizing to nitrate; phosphates and molybdate
are stable. Slow-depleting carboxylates and azoles also behave normally.
Unfortunately, the amount of aging developed in one week is insufficient to serve the purpose
of the test and to adequately sort the coolants. The NVC coolant lost only 20 % nitrite and all
after-test coolant samples passed the ASTM D 4340 test see Table 3.
This test would need to give more glycol degradation, some silicate depletion and more nitrite
oxidation. Extending the term of the test may provide the desired results. Data from the PARR test
reflects that the degradation behavior is not linear, there is an induction period after which it
begins, and the rate of degradation thereafter increases exponentially see Fig. 7 and Fig. 8.
3. PARR Reactor Test: The more advanced inhibition packages withstood the test better than the
OEM approved conventional coolants and all performed better than the known negative controls.
The nitrite nitrate change was observed, and other aging properties are consistent with realworld experiences. The exposure did not affect the carboxylates, borates, or molybdate concentrations. Glycol was degraded, and formates and glycolates formed but the negative control NVC
was somewhat differentiated see Table 4.
PARR tests were able to differentiate the quality of coolants and glycols. Results are consistent
with field experiences and directionally encouraging, with the potential for improvement. It is the
best of the four tests studied in this project see Fig. 9.
4. Rotating Pressure Vessel Oxidation Test RPVOT: This test proved to be a torture chamber test.
It was so severe that there were reactions being driven that do not occur in typical cooling systems.
In particular, in FFC and NVC coolants, the nitrite nitrate reaction is nitrite NOx we
speculate and there is even a nitrate NOx reaction. Similarly, other reactions are totally
depleting phosphate and molybdate; behaviors not observed in the real world see Table 5.
Nevertheless, coolants H-1, H-2, and NMOAT performed well with good corrosion coupon
weight loss data, while NVC and FFC performed poorly with much worse coupon weight loss
results.
This test method does have promise in that with modifications to reduce its severity, it might
very well prove to be the most capable in both ranking the various coolant technologies oxidation
stabilities and might also provide a useful test to predict if a coolant may be considered for
extended service interval applications see Figs. 1012.
Future Directions
Modifications to the Test Methods
A. Reaction Kettle
1. The data from these tests were the least consistent and encouraging of the four alternatives. It
may not be worthwhile to continue work in the development of this method.
B. Modified ASTM D 4340
1. Extending the term of the test to at least two weeks.
2. Increase the antifreeze concentration to 70 or 85 %.
C. PARR Reactor Test
1. Pressurize the reactor with air.
2. Add an ASTM D 1384 coupon bundle and study corrosion characteristics through weight
losses.
D. Rotating Pressure Vessel Oxidation Test RPVOT
1. Run the test under air instead of O2.
2. Reduce the test temperature to 230 F or lower.
Conclusions
The modified ASTM D 4340 at one week duration was clearly not long enough to adequately degrade and
satisfactorily rank the coolants. Continuing research will investigate if an acceptable longer duration can
succeed at ranking the coolants. With this new condition, the modified ASTM D 4340 may turn out to be
a very useful test.
The PARR reactor generally modeled the field observations quite satisfactorily. The two-week term is
convenient, monitoring the chemical changes well. It is degrading and ranking the coolants to an encouraging degree. It is the best of the four tests studied. Future research will include the use of an ASTM D
1384 style coupon bundle in the reactor to see if RPVOT-type data can be generated.
The current RPVOT test conditions appear too severe. Future research with re-engineered test conditions hopefully will create aging that more closely models field observations.
The reaction kettle test was the least encouraging of the four methods evaluated see Table 6.

TABLE 6Summary.
Test
Kettle
Modified ASTM D 4340
PARR
RPVOT
Pros
Obtained modest depletion
of additive such as
molybdate, borate, silicate,
and organic acids.
Monitored chemical
changes with time.
Simple apparatus and
procedure. Depletion
reactions consistent with
real-world experience.
Good correlation to field
results. Nitrite converted to
nitrate in a manner very
similar to the field.
Monitored chemical
changes with time.
Short duration test that
also gives information on
corrosion protection as
well as add package
changes. May be able to
predict required coolant
service interval.
Cons
Excessive, unrealistic
nitrite depletion in
coolants H-2 and NOAT
plus excessive
phosphate depletion in
coolant H-1.
The test at one week is
too mild with a low
depletion rate of most
additives. NVC stood
up well to the test.
Depletion rate or
concentration reduction
of molybdate, borate,
silicate, and organic
acids are too low.
Too severe as the test
crushes FFC that has a
history of good field
performance. Also
reactions such as
nitrate destruction are
not seen in the field.
Appendix
Depletion Behaviors of Conventionally Inhibited Coolants [6]
see Fig. 12 and 13
FIG. 12Additive depletion in field test.
Changes for Further

Research
The authors have
no current plans for
further development
of this method.
Extend time to two

to four weeks and
increase coolant
concentration to 70
85% by volume.
Pressurize the
reaction vessel with
air 50 psi and
include ASTM D 1384
coupon bundles.
Reduce test
temperature or
pressurize with air, or both,
instead of pure
oxygen.
FIG. 13Nitrite depletion in various field tests.

References
1
2
3
4
5
6
Haddock, M. E. and Eaton, E. R., Recycling Used Engine Coolant Using High-Volume Multiple
Technology Equipment, Engine Coolant Testing, 4th Volume, ASTM STP 1335, R. E. Beal, Ed.,
ASTM International, West Conshohocken, PA, 1997.
Eaton, Edward R., Engine Reliability of Mixed Vehicle Fleets Operating on Engine Coolant Recycled with Reverse Osmosis Technology, SAE Technical Paper 962239, Society of Automotive
Engineers, Warrendale, PA 1996. October 2004 ASTM Committee D-15 minutes.
Mitchell, W. A. and Hudgens, R. D., Development of an Extended-Service Coolant Filter, Engine
Coolant Testing, 4th Volume, ASTM STP 1335, R. E. Beal, Ed., ASTM International, West Conshohocken, PA, 1997, pp. 412414.
Gershun, A. V. and Mercer, W. C., Predictive Tool for Coolant Development: An Accelerated
Aging Procedure for Modeling Fleet Test Results, Engine Coolant Testing, 4th Volume, ASTM STP
1335, R. E. Beal, Ed., ASTM International, West Conshohocken, PA, 1997.
Eaton, E., Boon, W., and Smith, C., A Chemical Base for Engine Coolant/Antifreeze with Improved Thermal Stability Properties, SAE Technical Paper Series 2001-01-1182, Society of Automotive Engineers, Warrendale, PA, 1996.
Hudgens, R. D., Comparison of Conventional and Organic Acid Technology OAT Coolants in
Heavy Duty Diesel Engine Service, SAE paper 1999-01-0130, p. 3 and Figs. 1 and 2.

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STP 1491

Engine Coolant Technologies: 5th

ASTM Stock Number: STP1491

Library of Congress Cataloging-in-Publication Data

Copyright 2008 AMERICAN SOCIETY FOR TESTING AND MATERIALS

Peer Review Policy

Fifth International Symposium on Engine Coolant

Coolant Development in AsiaH. EGAWA, Y. MORI, AND M. L. ABEL

Field Test for Carboxylate Inhibitor Levels in OAT CoolantsR. J. PELLET,

A Comparison of Membrane Technologies for Engine Coolant RecyclingR. HUDGENS,

New Electrochemical Methods for the Evaluation of Localized Corrosion in Engine

Compatibility Testing of Multi-Vehicle Coolant ChemistriesA. P. SKROBUL,

Investigation of Interaction Between Coolant Formulations and Flux Loading/

Effect of Fluoride on Corrosion of Cooling System Metals in Ethylene Glycol-Based

Heavy-Duty Diesel Engine Cavitation Test

Component Durability and High Mileage Performance of a Full Carboxylate Coolant

Cavitation Protection Performance of Nitrite-Free Organic Acid Based Coolant

Accelerated Oxidation and Corrosion Testing of Engine Coolants Using a Rotary

Coolants at Elevated TemperaturesS. CLAEYS AND S. LIEVENS

Comparison of Bench Test Methods to Elevate Heavy Duty Coolant Thermal

Journal of ASTM International, Vol. 4, No. 6

Hiroshi Egawa,1 Yasuaki Mori,1 and Michael L. Abel2

Coolant Development in Asia

Technical Direction of Engine Coolant in Asia

2 ENGINE COOLANT TECHNOLOGY

FIG. 1Current status of engine coolant.

EGAWA ET AL. ON COOLANT DEVELOPMENT IN ASIA 3

JIS K2234 LLC

Note: data have been converted.

Direction of Japanese Coolant Specifications

4 ENGINE COOLANT TECHNOLOGY

TABLE 3Heat test results.

Characteristics of Coolant Technology in Japan

Note: After final cleaning Pack 1/Pack 2.

EGAWA ET AL. ON COOLANT DEVELOPMENT IN ASIA 5

FIG. 2Aging tendency of LLCs.

Note: OOContained as a Main Component; OContained;; Not Used.

Technical Direction of Next Generation Coolant

6 ENGINE COOLANT TECHNOLOGY

FIG. 3Dynamic corrosion test results.

FIG. 4Appearance of test specimen (cast aluminum) after chemical treatment.

FIG. 5Appearance of after hard water compatibility test.

EGAWA ET AL. ON COOLANT DEVELOPMENT IN ASIA 7

Journal of ASTM International, Vol. 4, No. 1

Heather J. DeBaun1 and Fred C. Alverson2

Heavy Duty Diesel Engine Coolant Technology: Past,

DEBAUN AND ALVERSON ON HEAVY DUTY DIESEL TECHNOLOGY

FIG. 1U.S. emissions regulations.

FIG. 2Heat rejection history [3].

10 ENGINE COOLANT TECHNOLOGY

DEBAUN AND ALVERSON ON HEAVY DUTY DIESEL TECHNOLOGY

TABLE 1Plugged hose-coolant compatibility results.

Contains inorganic corrosion inhibitors such as

12 ENGINE COOLANT TECHNOLOGY

FIG. 3Engine coolant nitrite results.

FIG. 4Engine coolant pH results.

DEBAUN AND ALVERSON ON HEAVY DUTY DIESEL TECHNOLOGY

TABLE 3Metal flow rate limits [10].

Flow Rate Limit

14 ENGINE COOLANT TECHNOLOGY

FIG. 5Erosion-corrosion studypH effects.

FIG. 6Erosion-corrosion studynitrite conversion.