PROBLEMS IN UTILIZING ASTM G 48 TO EVALUATE

HIGH-ALLOY STAINLESS STEELS

Richard A. Corbett
Corrosion Testing Laboratories
60 Blue Hen Drive
Newark, DE 19713
Copyright by NACE International
ABSTRACT
The ASTM G 48 test evaluates an alloys resistance to pitting and crevice corrosion using severe test
conditions. Unlike most other ASTM standards, which are cut and dry in their test procedures, this
standard has loopholes, which allows test-to-test and laboratory-to-laboratory variation, which makes
comparison of data difficult. Modifications are often used to improve the standard, but these are not adopted
universally.
This paper identifies the problems associated with using G 48, and the impact these problems have on
evaluating high-alloy stainless steels. Recommendations to correct these problems to standardize the test are
made. Attention to the use of electrochemical measurement techniques for improved reproducibility are
discussed.
KEYWORDS: ASTM G 48, critical crevice temperature, critical pitting temperature, crevice
corrosion, electrochemical testing, ferric chloride, pitting, stainless steel,
temperature, testing
INTRODUCTION
The shortage of capital project money for building new process facilities that require highly corrosion
resistant materials is forcing design and project engineers to more precisely assess performance versus
pricing, now more than anytime since World War II. The heavy global competition among the companies
producing high performance alloys and stainless steels require those companies to make their products
yet more attractive to the end users.
The recognized need for materials suitable for the fabrication of equipment employed in corrosive
environments has stimulated research and development of new stainless steels and nickel-based alloys, as
well as modification of the existing ones. However, it is becoming more evident that usually if failure of
a high performance alloy occurs, it is due to localized attack, i.e., pitting and crevice corrosion. Although
significant attention has been given to the design of alloy composition and marketing with respect to
specific industries, the overall rating of high performance alloys on the basis of an objective standard
criterion for localized attack still remains open.
The principal alloying elements for corrosion resistance of the high-alloyed stainless steels are increased
chromium content, which provides progressive resistance to general attack; and increased molybdenum
(together with small additions of nitrogen), which enhances resistance to localized attack. Considering
the higher prices commanded by the materials with high alloy content, the selection of material for a given
service would not necessarily be based only on corrosion resistance, but on cost effectiveness! Thus, the
most common high performance alloys and stainless steels on the market, having 16-28% Cr and 1-16%
Mo, vary in price from approximately $2.00/lb (Type 316L SS) to approximately $10.00/lb (Alloy C276).

Some of these alloys, despite high nickel, chromium, and molybdenum contents, may be susceptible to
localized corrosion in certain environments. Comparison studies performed in the past ten years to rank the
wide variety of commercially available high performance alloys are usually either oriented to a specific
newly developed alloy, or are "industry specific" and based on specific "in-situ" field data rather than
standardized laboratory results.

Often the need for immediate results precludes the luxury of testing candidate alloys in plant tests (which
may require months) or the use of laboratory tests especially designed to simulate plant conditions. For
example, standardized tests, such as ASTM G 48 ("Standard Test Methods For Pitting And Crevice
Corrosion Resistance Of Stainless Steels And Related Alloys By The Use Of Ferric Chloride Solution"),
often provides results on performance under very severe testing conditions in a short length of time. This
particular test is based on the knowledge of the localized corrosion mechanism.
There are two test methods currently covered in the present G 48 standard: Method "A" calls for the total
immersion of a test specimen in a 6 wt.% ferric chloride solution (10% FeCl 3 6H2O) and evaluates the
susceptibility to pitting corrosion; Method "B" utilizes a creviced test specimen immersed in a 6 wt.% ferric
chloride solution and evaluates crevice corrosion susceptibility. Unfortunately, using this standard test does
not always achieve standard testing conditions. Considerable variability has been observed for the newer
high-alloy stainless steels from test-to-test and between laboratories. These situations are attributable to
variance in: solution pH, specific test temperature, specific testing times, criteria for failure, compressive
pressure on the crevice washer, etc. Additionally, many modifications to these test methods are frequently
employed, such as, deionized water replacing distilled water; weight loss criteria instead of pit
presence/density/depth; alternate crevice devices/composition. It is problems such as these, which this
paper will address, plus alternative uses/refinements of the standard.
OVERVIEW OF GENERIC PROBLEMS
The Ferric Chloride Solution
Water. The G 48-76 standard states that distilled water be used to make up the test solution, however it does
not specify to what purity or pH. ASTM D 1193 3, "Standard Specification for Reagent Water," specifies
four Types of water based on purity and pH. For the purposes of testing to G 48, either Type III or IV may
be suitable, however these waters include those produced by either distillation, ion exchange, or reverse
osmosis. Likewise, the pH may range from 6.2 to 7.5 for Type III, or from 5.0 to 8.0 for Type IV.
Since the current standard G 48 only specifies "distilled" water, the purity can be somewhat assured, but the
pH could be as low as 5 or as high as 8.0, depending upon how much carbon dioxide is dissolved in the
water. Although carbon dioxide is driven out of the water during boiling, it dissolves back into solution
upon condensing lowering the pH of the water.
pH. The pH of the as-made ferric chloride solution has been reported4-10 to range from 1.0 to 2.05 and even
greater than 3.4 This much of a variance may greatly affect the alloys pitting or crevice susceptibility. In
addition, during the course of testing, the pH of the bulk solution has been known to change, particularly
when temperatures change. For example, increasing the temperature of the ferric chloride solution
decreases its pH. At a critical temperature of 45 C ferric hydroxide begins to precipitate and the solution
rapidly becomes more acidic, see Figure 1. This change in solution pH will affect its corrosivity,
particularly to lesser alloyed stainless steels.
In the ASTM G01.05.07 Task Group on Critical Pitting and Crevice Temperature Round Robin testing11 ,
the addition of hydrochloric acid to a 1% concentration was used to control and normalize the 6 wt.%
ferric chloride solution pH to approximately 0.4 throughout the testing time.

Others believe this solution is too severe to evaluate sigma phase in UNS S31803, and wish to adjust the
pH to a constant 1.312 by either the addition of HCl or NaOH.
Duration Of Test
The G 48 standard suggests a "reasonable test period of 72 hours," although this is not a
requirement, and a number of researchers 2, 4-7 , 9 ,13-20 have reported using other test periods in the
generation of pitting and crevice corrosion susceptibility data.
Temperature For Evaluation
The results of G 48 immersion tests (carried out at fixed temperatures of 22 or 50 C) , with rare
exceptions, are judged to be a "go/no-go" criterion, and are not alloy specific.
In order to be able to rank a material of interest, or select a temperature criterion for material acceptance, it
is common to determine the lowest temperature at which pitting/crevice initiates. This criterion is called the
Critical Pitting or Critical Crevice Temperature (CPT or CCT, respectively13, 16). The development of
standard immersion testing methods using this concept are the subject and charge of the ASTM
G01.05.07 Task Group.
Criteria For Failure
ASTM G 48 does not address a criterion for either acceptance or rejection, only the examination of the
tested specimen for the presence or absence of pitting/crevice attack. Currently, the criterion is left to the
vendor and user to agree upon.
SPECIFIC PROBLEMS ASSOCIATED WITH METHOD A -- THE PITTING TEST
Method A is designed to determine the relative pitting resistance of stainless steels and nickel-base,
chromium-bearing alloys. It may also be used to determine the effects of alloying additives, heat treatment,
and surface finishes on pitting resistance.
While no specific problems are associated with this test method, it does lack a specific evaluation criteria.
The examination and evaluation section of the standard recommends an ocular review of the
exposed specimen under low-power magnification with the subsequent recording of pit depth and pit
density. Weight loss calculations are to be reported as grams per square meter. Comparisons between alloys
are to be ranked according to these results, however this method is generally applied as a "go/no-go" test.
Because of the possible subjectiveness in identifying a pit, it has been recommended 10 that a corrosion
rate criterion be adopted. This would not only create a specific numerical acceptance criterion, but
would also eliminate problems associated with mis-identification of a mechanically damaged site as
corrosion pitting.
Almost 20 years ago, Brigham and Tozer13 proposed using temperature as a means to rank certain
molybdenum containing alloys, and to determine their critical pitting temperature below which the alloy
would not pit regardless of exposure time or potential. Although several chloride containing test media
were used giving statistically identical results, the ferric chloride solution was preferred owing to its simplicity.
Their continued work, plus the works of others 4, 21, contributed to the development of the G 48 standard.
Unfortunately, the criterion of the critical pitting temperature was not developed. However, this is exactly
the charge of the ASTM G01.05.07 Task Group, who will hopefully have a proposed revision/addition to
the G 48 standard in 1993.

SPECIFIC PROBLEMS ASSOCIATED WITH METHOD B THE CREVICE CORROSION TEST

In 1974, both Streicher4 and Brigham16 published works on establishing a crevice test using the ferric
chloride solution. The work of Streicher became the basis of Method B, where two tetrafluoroethylene
(TFE-fluorocarbon) blocks were assembled, one on each side of the test specimen, and held in place by Orings or rubber bands. Unfortunately, this assembly, as described in G 48, has several drawbacks, namely: the
breakage of an O-ring or rubber band which invalidates the test; non-uniform compressive pressure
associated with the O-ring or rubber band; the creviced area-to-bold area ratio 22 cannot be accurately
measured; the TFE-block surface finish is not specified; and the crevice attack almost always initiates on the
edges of the specimen in contact with rubber bands rather than under the TFE blocks.
In 1976, Anderson22 published results obtained using a multiple crevice washer that was bolted to the test
specimen. This assembly is generally accepted as an improvement to the TFE blocks because it eliminates
the use of rubber bands, which can break during testing, a precise creviced area-to-bold area ratio can be
calculated, and the edges of the test specimen are not disturbed. This assembly has- been adopted by MTI 20
as the method for evaluating the relative resistance of alloys to crevice corrosion. But even this method
does not go without problems. For example, there has not been an established standard torque to which to
tighten the crevice assembly, the use of various materials of construction (e.g., TFE, acetal resin,
polycarbonate, methyl methacrylate, ceramic alumina) for the crevice washer is not defined, and the
relaxation of torque during the test23-25 is not addressed.
Compressive Pressure Of The Crevice Device
As mentioned above, the G 48 standard utilizes cylindrical TFE-fluorocarbon blocks and fluorinated
elastomer O-rings or rubber bands. The degree of pressure exerted by the O-rings/rubber bands is not
precise or reproducible, and hence non-standard. In an attempt to standardize the degree of crevice tightness
for the multi-crevice washer assembly, the use of a torque wrench was used to tighten the bolts. But, here
again, the standardization vanishes. Torques ranging from 0.28 N-m (2.5 in-lb) to 8.5 N-m (75 in-lb) have
been reported 2 , 5 , 6 , 9 , 2 0 , 2 4 - 2 8 in use with the ferric chloride solution.
The limitations of using torque as a mean of controlling crevice tightness have been discussed by
Oldfield.23 He has concluded that "the torque cannot be related to a force between the sample and the
crevice former." And secondly, the torque can relax with time resulting in a variable force over the
duration of the test. The new crevice assembly described by Oldfield 23 shows promise, and hopefully
additional test results on high-alloy stainless steels will be forthcoming.
Another concern in using artificial crevice formers is their geometrical configuration (i.e., its height
versus the diameter at the metallic washer, the dimensions of the crevicer, the width of the serration, depth
of the serration, etc.). Again, as with the use of torque tightness, there is no standard and crevice geometries
vary from laboratory-to-laboratory and even time-to-time by the same experimenter.18
REPRODUCIBILITY
There are many factors, which are known5 to cause localized corrosion of stainless steels, among these are
low pH, high chloride concentrations, solutions with noble redox potentials, oxygen differential
concentrations, and elevated temperature. Previous workers4, 7 , 9, 1 3 - 1 5 , 2 7 have published that the use of
the ferric chloride test will result in the critical pitting temperature varying within the range of 2.5 C.
However, using the ferric chloride test, and a variety of crevice-type devices, the best reproducibility for
the critical crevice temperature test is within the range of 10 C.5, 6 , 9 , 1 5 , 1 6 Therefore, this immersion test
has draw-backs when it comes to ranking the crevice corrosion resistance of the high-alloy stainless steels.
These drawbacks limit the reliability of using G 48 as an accelerated laboratory test.

Electrochemical measurement techniques for evaluation of crevice corrosion are not new9, 13, however, they
are tedious to run manually. However a personal computer system has been developed which automatically
apply potentials and measure the resulting corrosion current, while ramping and controlling solution
temperature. Critical pitting and critical crevice temperatures can now be determined in less than one hour.
Plus, the use of such instruments has resulted in both the critical pitting and crevice temperature
determination varying only 2.5 C. These preliminary results5, 6, 29, 30 are significant enough to rank not only
high-alloy stainless steels of different families (i.e., 2% Mo, 4% Mo, 6% Mo, 8% + Mo), but alloys within
the same family.
RECOMMENDATIONS
The specific use of "distilled water" in G 48 is limiting and without justification. As observed in our
laboratory, Table 1, the purity of deionized water can often exceed that of distilled water. Therefore, as an
improvement to G 48, it is recommended that the standard solution be composed of 100 g of reagent grade
ferric chloride hexahydrate (FeCI3 6H2O), in 900 ml of reagent water (ASTM D 1193, Type IV). [NOTE:
Current balloting for the revision/reapproval of ASTM G 48-76 will specify the use of ASTM D1193
instead of "distilled water."31]
Furthermore, since the pH of the as-made ferric chloride solution appears to vary from laboratory-tolaboratory, it is also recommended to adjust the pH of the above solution with 15.6 mls of reagent grade
concentrated hydrochloric acid. This will produce a solution containing 6% ferric chloride by weight and
1% hydrochloric acid, resulting in a stable and buffered pH (below pH 1) environment for temperatures
ranging from ambient to 85oC, as determined from our laboratory test results, Table 2.
The G 48 standard only suggests a test time of 72 hours, while a number of others 2, 4-7, 9, 13-20, 32 have
successfully used anywhere from 23 hours to 30 days to achieve desired results. Based on the analysis of
these results, and our work presented in Table 3, it is recommended that a standard test time of 48 hours be
adopted.
Because G 48 is specifically related to localized attack, one could assume that most, if not all, corrosion is
associated with pitting/crevice attack. The unpublished results of an extensive testing program for a nuclear
facility, suggest that during a 48 hour test the degree of pitting attack is directly related to molybdenum
content for properly annealed material. When the molybdenum content is above 4% the pits are shallow
and occluded. This made pit depth measurements difficult and subjective. Thus to evaluate the high-alloy
stainless steels in the pitting test, Method A, a mass loss per unit area per time of exposure criteria would
normalize a small number of deep pits or a massive amount of shallow pits. As such, certain industries have
stipulated a criteria of less than 10 mdd (milligrams loss per square decimeter per day) as an acceptable
degree of attack for the acceptance or rejection of material for chloride service. In order to rank alloys, a
comparison of this rate should be made.
For crevice attack evaluation, MTI20 has established the criterion of the number of crevice sites, which are
attacked to a depth greater than 1.0 mils during the 24 hour test. Certain other industries 28 accept material
only if all of the crevice sites are attacked to a depth of less than 1.5 mils in a 72 hour test. Since the attack
of one (1.0) mil is readily observed by ocular examination, and the measurement of one mil is easily
achieved by either a needle-point micrometer or a calibrated fine-focus microscope33, it is recommended
that this criteria be accepted for the test period used.
Crevice assemblies vary from TFE blocks held in place with either O-rings or rubber bands, to serrated
washers of a non-metallic material bolted through a hole in the test specimen, to non-metallic washers with
a controlled annulus, spring loaded to the test specimen. There are advantages and disadvantages to each
design, however, the most popular, widely used, and recommended by the author is the multiple crevice
assembly consisting of two TFE serrated washers (16 mm in dia., 6.7 mm dia. center hole, with 12 crevice
pads of 1.45 mm in width by 0.8 mm in height), which are attached to the test specimen with a nut, bolt and
washers of Alloy C-276 (UNS N10276). An insulating sleeve should be used around the bolt to electrically

isolate it from the test specimen. The pads of the washer in contact with the test specimen should be
polished to a 600-grit finish prior to assembly. The torque on the bolt should be 0.28 Nm (2.5 in-lb), unless
crevice tightness characteristics are being studied. Furthermore, unless a specific surface condition of the
test specimen is to be evaluated, the specimen should be ground to a 120-grit finish. For each temperature
of evaluation, a new specimen and fresh solution should be used.
CONCLUSIONS
The ASTM G 48 standard needs to be improved, and loopholes in the testing conditions and procedures
eliminated. Specific problems with the make-up of the ferric chloride test solution, the duration of the test,
evaluation temperatures, and a criterion for failure have been addressed and recommendations to improve
the standardization the test are made.
The ASTM G01.05.07 Task Group is working on revisions/additions, which will provide versatility in
using this standard under clearly defined test parameters.
The use of personal computers, programmed to control many test parameters concurrently, in combination
with the ferric chloride test solution, offers a rapid determination of either the CPT or CCT, with excellent
reproducibility.
REFERENCES
1.

2.
3.
4.
5.
6.
7.
8.
9.
10.

ASTM G 48-76 (Reapproved 1980):Standard Test Methods for Pitting and

Crevice Corrosion Resistance of Stainless Steels and Related Alloys by the
Use of Ferric Chloride Solution (Philadelphia, PA:American Society for
Testing and Materials).
E.L. Hibner, "Evaluation of Test Procedures for Critical Crevice
temperature Determination for Nickel Alloys in a Ferric Chloride
Environment," Corrosion/86, paper no. 181, (Houston, TX:NACE, 1986).
ASTM D 1193-77 (Reapproved 1983):Standard Specification for Reagent
Water.
M.A. Streicher, CORROSION, 30, 3 (1974): p. 77.
N.S. Nagaswami, M.A. Streicher, "Accelerated Laboratory Tests for
Crevice Corrosion of Stainless Alloys," Corrosion/83, paper no. 71,
(Anaheim, CA:NACE, 1983).
G.O. Davis, M.A. Streicher, "Initiation of Chloride Crevice Corrosion on
Stainless Alloys," Corrosion/85, paper no. 205 (Boston, MA:NACE, 1985).
A. Garner, Pulp & Paper Can. 82, 12 (1981): p. T414.
M.A. Streicher, J. Electrochem. Soc., 103, 7 (1956): p. 375.
M. Renner, U. Heubner, M.B. Rockel, E. Wallis, Werkstof f e und Corrosion,
37 (1986): p. 183.
R.M. Davison, private communication (1990).

11.

ASTM G01.05.07, "Round Robin Test Methods as Additions to G 48,"

revision 4, 4/91, presented at the ASTM Spring Meeting, Atlantic City, NJ,
1991.

12.

ASTM Subcommittee A01.14, draft Standard Methods for Detecting

Detrimental Intermetallic Phases in Wrought Duplex Stainless Steels,
September 1991.

13.

R.J. Brigham, E.W. Tozer, CORROSION, 29, 1 (1973): p. 33.

14.
15.

R.J. Brigham, E.W. Tozer, CORROSION, 30, 5 (1974): p. 161.

R.J. Brigham, MATERIALS PERFORMANCE, 13, 11 (1974): p. 29.

16.

R.J. Brigham, CORROSION, 30, 11 (1974): p. 396.

17.

R.J. Brigham, E.W. Tozer, CORROSION, 32, 7 (1976): p. 274.

18.
19.
20.

R.J. Brigham, CORROSION, 37, 10 (1981): p. 608.

R.J. Brigham, MATERIALS PERFORMANCE, 24, 12 (1985): p. 44.
R.S. Treseder, MTI Manual No. 3: Guideline Information on Newer Wrought
Iron-and Nickel-Base Corrosion Resistant Alloys (Columbus, OH: Materials
Technology Institute of the Chemical Process Industries, 1980), p. 19.

21.

A.P. Bond, H.J. Dundas, S. Ekerot, M. Semchyshen, STAINLESS STEEL '77

(Climax Molybdenum Company, 1978), p. 197.

22.

D.B. Anderson, ASTM STP 576 (Philadelphia, PA: American Society for
Testing and Materials, 1976), p. 231.

23.

J.W. Oldfield, "Effect of Crevice Geometry on the Corrosion of AISI 304 and
316 in Marine Environments," Corrosion/89, paper no. 290 (New Orleans,
LA:NACE, 1989).
M.A. Streicher, MATERIALS PERFORMANCE, 22, 5 (1983): p. 37.

24.
25.

R.A. Corbett, "Critical Crevice Corrosion Tests: Torque Retention Study,"

presented at the NACE T-5A-28 Task Group Meeting, Cincinnati, OH, 1991.

26.

Allegheny Ludlum Corporation, Product Information Bulletin: Corrosion

Testing AL-6XN Alloy (1989).

27.
28.

A. Garner, Met. Soc. CIM, 1977 Annual Vol. (1977): p. 48.

PSE&G Specification S-C-MPOO-VDS-0007-1, Rev. 1, "Shop Fabrication
Specification for 6% Moly Stainless Steel," dated May 16, 1989, and
amended by PSE&G letter PMZ-89-0693, "Crevice Corrosion and Pitting
Corrosion Test Procedures," dated December 13, 1989.
S. Bernhardsson, R. Mellstrom and J. Oredsson, "Properties of Two Highly Corrosion
Resistant Duplex Stainless Steels," Corrosion/81, paper no. 124 (Toronto,
ONT:NACE, 1981).
S. Bernhardsson, R. Mellstrom, B. Brox, "Limiting Chloride Contents and
Temperatures With Regard to Pitting of Stainless Steels," Corrosion/80,
paper no. 85 (Chicago, IL:NACE, 1980).
Minutes of ASTM G-1 Meeting, San Diego, CA, November 8, 1991.

29.
30.
31.
32.
33.

ARCO Alaska, Inc., Doc. No. SPC-PT-NS-30014, "Duplex Stainless Steel

Pipe," (1991).
ASTM G 46-76 (Reapproved 1986): Standard Practice for Examination and
Evaluation of Pitting Corrosion.

TABLE 1
COMPARISON OF WATER MEETING ASTM D 1193 STANDARDS
MADE FROM DELAWARE ARTESIAN WATER AND
ITS EFFECT ON THE CRITICAL CREVICE TEMPERATURE
OF HIGHALLOY STAINLESS STEELS

DISTILLED WATER

pH

TDS (1)

(2)

5.5

0.31

0.2

Cond. (3)
4.7
3.6

DEIONIZED WATER
5.2
(1) total dissolved solids, parts per million
(2) resistivity, ohm-cm
(3) electrical conductivity, siemens

0.24

0.3

CRITICAL CREVICE TEMPERATURE (4)

DISTILLED WATER

DEIONIZED WATER

ALLOY
<0

<0

<0

<0

S31603
2.5
S31703

2.5
5.0

5.0
N08904

5.0
30.0

N08925

5.0
30.0

30.0
30.0

N08367

30.0
30.0

32.5
32.5

N06625

35.0
30.0

35.0
65.0

N10276

2.5
5.0

35.0
65.0

65.0

65.0

(4) multiple crevice washer, 0.28 Nm torque, 48hr. test, 10% FeC13 6H2O, pH =
1, each number represents a single test specimen.

TABLE 2
10% FeC13 6H2O pH versus TEMPERATURE

SOLUTION - ASTM G 48, 10% FeC13.6H 2 0

pH - taken with a automatic temperature compensation Accumet pH meter and
combination probe.
TEMP
AS-MADE
PLUS 1% HC1
25 C
1.30
0.41
30
1.26
0.41
35
1.23
0.41
40
1.22
0.40
45
1.21
0.40
50
1.14
0.39
55
1.13
0.39
60
1.11
0.39
65
1.11
0.38
70
1.08
0.38
75
1.03
0.38
80
0.94
0.37
85
0.86
0.36
A (25 to 85)
0.44
0.05

TABLE 3
INFLUENCE OF TEST PERIODS ON CREVICE CORROSION(1)
ALLOY,

24hrs.

48hrs.

S31603
12
12
12
12
12
S31703
9
10
10
11
10
N08925
3
4
4
6
4
N06625
1
2
2
2
2
N 10276
0
0
0
0
0
(1) 10% FeC13 6H2O at 35 C, multi-crevice washer with 12 pads, 0.28 Nm torque

72hrs.
12
10
7
2
0

(2) results are the number of pads which experienced crevice attack after exposure for the given test
period, each number represents a single test specimen

Figure 1.
Effects of temperature on the pH of as-made G 48 ferric chloride solution