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 ‫‪Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik‬‬
‫‪ ‬‬

‫‪EFFECT OF pH AND CHLORIDE CONCENTRATION ON‬‬

‫‪THE CORROSION OF DUPLEX STAINLESS STEEL‬‬
‫*‪Yunan Prawoto‬‬
‫‪Faculty of Mechanical Engineering‬‬
‫‪Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia‬‬
‫‪K. Ibrahim‬‬
‫‪ExxonMobil Exploration and Production Malaysia Inc.‬‬
‫‪15:041E, Menara ExxonMobil, Kuala Lumpur City Centre‬‬
‫‪50088 Kuala Lumpur, Malaysia‬‬
‫‪and W. B. Wan Nik‬‬
‫‪Faculty of Maritime Studies and Marine Science‬‬
‫‪University Malaysia Terengganu, 21030 Kuala Terengganu, Malaysia‬‬

‫اﻟﺨﻼﺻــﺔ‪:‬‬
‫إن إﺳﺘﺨﺪام ﻓﻮﻻذ اﻟﺤﺪﻳﺪ ﺑﻜﺜﺮة آﻤﺎدة ﺑﻨﺎﺋﻴﺔ ﺣﺘﻰ ﻓﻲ ﻇﺮوف ﺑﻴﺌﻴﺔ ﻗﺎﺳﻴﺔ ﻳﺮﺟﻊ إﻟﻰ ﺟﻮدة ﺧﻮاﺻﻪ اﻟﻤﻴﻜﺎﻧﻴﻜﻴﺔ و اﻟﺘﺂآﻠﻴﺔ و ﺗﺨﺼﻴﺼﺎ ﻓﻮﻻذ اﻟﺤﺪﻳﺪ‬
‫)‪ (austenitic–ferritic‬اﻟﻤﺰدوج اﻟﺬي أﺻﺒﺢ ﻣﺎدة ﻣﻌﺮوﻓﺔ ﻓﻲ ﺗﻄﺒﻴﻘﺎت اﻟﻨﻔﻂ و اﻟﻐﺎز ﺧﺼﻮﺻﺎ اﻟﻤﻨﺸﺄت اﻟﺘﻲ ﺑﻨﻴﺖ ﺑﻌﺪ ﻓﺘﺮة اﻟﺴﺒﻌﻴﻨﻴﺎت‪ .‬هﺬا اﻟﺘﻮﺳﻊ ﻓﻲ‬
‫إﺳﺘﺨﺪام هﺬﻩ اﻟﻤﻮاد ﻳﻤﻜﻦ إرﺟﺎﻋﻪ إﻟﻰ ﺧﻮاص ﻣﺠﺘﻤﻌﺔ ﻣﻤﺘﺎزة آﺎﻟﻤﺘﺎﻧﺔ اﻟﻌﺎﻟﻴﺔ‪ ,‬اﻟﻤﻘﺎوﻣﺔ اﻟﺠﻴﺪة ﻟﺘﺼﺪع اﻟﺸﺪ اﻟﺘﺂآﻠﻲ واﻟﺘﻜﻠﻔﺔ اﻟﻤﻘﺎرﺑﺔ ﻟﻔﻮﻻذات اﻟﺤﺪﻳﺪ‬
‫ﺗﻘﻠﻴﺪﻳﺔ اﻟﺼﻨﻊ‪.‬‬
‫هﺬا اﻟﺒﺤﺚ ﻳﻬﺪف ﺑﺎﻷﺳﺎس إﻟﻰ ﻓﻬﻢ أداء اﻟﺘﺂآﻞ ﻟﺴﺒﻴﻜﺔ اﻟﻔﻮﻻذ اﻟﻤﺰدوج ﺗﺤﺖ ﻇﺮوف ﻣﺨﺘﻠﻔﺔ ﻣﻦ درﺟﺔ اﻟﺤﻤﻮﺿﺔ‪ ,‬ﺗﺮاآﻴﺰ اﻟﻜﻠﻮراﻳﺪ و درﺟﺎت‬
‫اﻟﺤﺮارة‪ .‬ﻟﻘﺪ ﺗﻢ ﺗﻘﻴﻴﻢ ﺳﺮﻋﺎت اﻟﺘﺂآﻞ و ﺗﺸﻜﻞ اﻟﺘﺠﺎوﻳﻒ ﻟﻠﻔﻮﻻذ اﻟﻤﺰدوج ﺑﺸﻜﻞ ﻧﻈﺎﻣﻲ ﺧﻼل هﺬﻩ اﻟﺪراﺳﺔ‪ .‬ﺗﻢ إﺟﺮاء دراﺳﺔ ﺗﺄﺛﻴﺮات درﺟﺎت اﻟﺤﻤﻮﺿﺔ و‬
‫ﺗﺮاآﻴﺰ اﻟﻜﻠﻮراﻳﺪ ﻋﻠﻰ ﺗﺂآﻞ اﻟﻔﻮﻻذ اﻟﻤﺰدوج وﻓﻘﺎ ﻟﻠﻄﺮﻳﻘﺔ اﻟﻤﻌﻴﺎرﻳﺔ ‪ . UNS S32205‬ﻟﻘﺪ ﺗﻢ ﺗﺤﺪﻳﺪ ﺗﺄﺛﻴﺮ درﺟﺔ اﻟﺤﻤﻮﺿﺔ ﺑﺎﺳﺘﺨﺪام ﻣﺤﺎﻟﻴﻞ ﻓﺤﺺ‬
‫ﻣﺨﺘﻠﻔﺔ و درﺟﺎت ﺣﺮارة ﻣﺨﺘﻠﻔﺔ‪ .‬ﻟﻘﺪ آﺎن اﻟﻮﻗﺖ اﻟﻤﺨﺼﺺ ﻟﻔﺤﺺ اﻟﺘﻐﻄﻴﺲ ﻣﺘﻮاﻓﻘﺎ ﻣﻊ اﻟﻄﺮﻳﻘﺔ اﻟﻤﻌﻴﺎرﻳﺔ ‪ , ASTM G48‬ﻣﻊ اﻟﻌﻠﻢ ان ﺗﺤﺪﻳﺪ ﺗﺄﺛﻴﺮ‬
‫ﺗﺮاآﻴﺰ اﻟﻜﻠﻮراﻳﺪ ﻋﻠﻰ ﺗﺂآﻞ اﻟﺴﺒﻴﻜﺔ اﻟﻤﺨﺘﺎرة ﺗﻢ ﺑﻘﻴﺎﺳﺎت ﺣﻔﺮ اﻟﺘﺂآﻞ ﺑﺪراﺳﺔ اﻟﺘﺮآﻴﺐ اﻟﻤﻌﺪﻧﻲ اﻟﻤﺒﺴﻂ و ﺑﺎﺳﺘﺨﺪام اﻟﺘﺤﻠﻴﻞ اﻟﺒﺮﻣﺠﻲ ‪. PREN‬‬

‫*‬
‫‪Corresponding Author:‬‬
‫‪E-mail: yunan.prawoto@gmail.com‬‬

‫‪December 2009‬‬ ‫‪The Arabian Journal for Science and Engineering, Volume 34, Number 2C‬‬ ‫‪1‬‬
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 
 
ABSTRACT
Stainless steels are widely used as structural materials even in aggressive environments due to their good
mechanical and corrosion properties. In particular, duplex (austenitic–ferritic) stainless steels are becoming common
materials for oil and gas applications, specifically facilities that were built after the 1970s. This expansion in the
utilization of such materials can be attributed to their excellent combination of properties, such as higher strength,
good resistance to stress corrosion cracking, and comparable cost to conventional austenitic stainless steels. This
research is mainly concerned about the corrosion performance of a duplex stainless steel alloy under several
conditions using various pH and chloride concentrations at different temperatures. Corrosion rates and pitting
morphology of the selected duplex stainless steel were systematically evaluated during this study. The effects of pH
and chloride concentrations on the corrosion behavior of duplex stainless steel were carried out in accordance with
UNS S32205. The effect of pH was has been determined by using different test solutions at different test
temperatures. The duration of immersion tests were set in accordance to the ASTM G48 standard. However, the
effect of chloride concentrations on the corrosion of the selected alloy is determined by pitting corrosion
measurements using simple metallography and software analysis as well as PREN (Pitting Resistance Equivalent
Number).
Key words: duplex stainless steel, pH, chloride concentration, corrosion

2 The Arabian Journal for Science and Engineering, Volume 34, Number 2C December 2009
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 

EFFECT OF pH AND CHLORIDE CONCENTRATION ON THE CORROSION OF

DUPLEX STAINLESS STEEL

1. INTRODUCTION
Stainless steel is one of the most important materials in the engineering world. The material’s wide applications
in chemical, petrochemical, off-shore, and power generation plants prove that it is one of the most reliable materials.
In particular, duplex (austenitic–ferritic) stainless steels are very popular in the oil and gas industries built after the
1970s. This expansion is associated with their excellent combination of properties, such as higher strength than
austenitic stainless steel, better stress corrosion resistance, and similar price to conventional stainless steels [1]. With
the aging of those structures, quantification of all factors that can contribute to the failure became more important.
Two of those factors are the chloride effect and the effect of pH. These two factors are essential components of a
failure analysis tool since a lot of the failures related to environments are linked to corrosion. Understanding the
effect of the pH and the chloride concentration is a key factor in life assessment as well as in the failure analysis of
structures utilizing duplex stainless steel.
As in other metals, corrosion in duplex stainless steel breaks down essential properties due to chemical reactions
with its surroundings. Certain environments offer opportunities for these metals to combine chemically with
elements to form compounds and return to their lower energy levels. Ultimately, it corrodes on contact with water
(and moisture in the air), acids, bases, salts, oils, aggressive metal polishes, and other solid and liquid chemicals. It
can also corrode when exposed to gaseous materials like acid vapors, formaldehyde gas, ammonia gas, and sulfur
containing gases.
Duplex stainless steel
Traditionally, the word duplex stainless steel refers to a mixture of body-centered cubic (BCC) ferrite and face-
centered cubic (FCC) austenite crystal structures. Most duplex stainless steels are intended to contain similar
amounts of ferrite and austenite phases in the annealed condition. Duplex stainless steels generally have similar
corrosion resistance to austenitic alloys and they typically have better stress corrosion cracking resistance than
austenitic stainless steel.
They have existed for more than 60 years. The early grades were simple alloys of chromium, nickel, and
molybdenum. The first wrought duplex stainless steels were produced in Sweden in 1930 and were used in the
sulfite paper industry. These grades were developed to reduce the intergranular corrosion problems in the early,
high-carbon austenitic stainless steels. One of the first duplex grades developed specifically for improved resistance
to chloride stress corrosion cracking (SCC) was 3RE60. AISI type 329 became well-established after World War II
and was used extensively for heat exchanger tubing for nitric acid service. In subsequent years, both wrought and
cast duplex grades have been used for a variety of process industry applications, including vessels, heat exchangers,
and pumps. Duplex stainless steels also generally have greater tensile and yield strengths, but poorer toughness than
austenitic stainless steels. Nowadays, type 2205 is the most widely used duplex stainless steel grade. It finds
applications due to both excellent corrosion resistance and high strength [2].
2. METALLURGICAL PROPERTIES AND MAIN ALLOYING ELEMENTS IN DUPLEX STAINLESS
STEELS
Compared to conventional austenitic stainless steels, duplex stainless steels are stronger and more resistant to
localized corrosion, particularly pitting, crevice corrosion, and stress corrosion cracking. They are characterized by
high chromium (19–28%), molybdenum (up to 5%), and lower nickel content than austenitic stainless steels. They
can be divided into four groups. The first group is Lean Duplex, such as 2304, which contains no deliberate
molybdenum addition. The second group is 2205, the “work-horse grade” accounting for more than 80% of duplex
usage. The third group is 25% chromium duplex, such as Alloy 255 and DP-3. The fourth group is Super Duplex,
with 25–26% chromium and increased molybdenum and nickel compared with 25% chromium grades, including
grades such as 2507, Zeron 100, UR 52N+, and DP-3W [3].
Compared to austenitic stainless steels, duplex stainless steels differ mainly in their chromium, nickel, and
molybdenum contents. Chromium is a ferrite former. At higher chromium content, more nickel is necessary to form
an austenitic or duplex structure. Higher chromium also promotes the formation of intermetallic phases. There are
usually at least 18% Cr in austenitic stainless steels and at least 22% in second-generation duplex stainless steels.
Chromium also increases the oxidation resistance at elevated temperatures. This chromium effect is important
because of its influence on the formation and removal of oxide scale or heat tint resulting from heat treatment or
welding.

December 2009 The Arabian Journal for Science and Engineering, Volume 34, Number 2C 3
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 
 
On the other hand, nickel is an austenite stabilizer. That means that the addition of nickel to iron-based alloys
promotes a change of the crystal structure of stainless steel from body-centered cubic (ferritic) to face-centered cubic
(austenitic). Ferritic stainless steels contain little or no nickel, duplex stainless steels contain an intermediate amount
of nickel, such as 4 to 7%, and the 300-series austenitic stainless steels contain at least 8% nickel (see Figure 1). The
addition of nickel delays the formation of detrimental intermetallic phases in austenitic stainless steels but is far less
effective than nitrogen in delaying their formation in duplex stainless steels. The face-centered cubic structure is
responsible for the excellent toughness of the austenitic stainless steels. Its presence in about half of the
microstructure of duplex grades greatly increases their toughness relative to ferritic stainless steels [4].

Figure 1. Schematic of the microstructural change due to nickel increment. Increasing the nickel content changes the
microstructure of a stainless steel from ferritic to duplex to austenitic

The addition of nitrogen promotes structural hardening by the interstitial solid solution mechanism, which raises
the yield strength and ultimate strength values without impairing toughness. Moreover, the two-phase microstructure
guarantees higher resistance to pitting and stress corrosion cracking in comparison with conventional stainless
steels [5].
3. PROPERTIES AND CHARACTERISTICS
Coinciding with the 1970s development of offshore gas and oilfields in the North Sea, a second-generation
duplex was introduced and quickly became the duplex steel of choice. With the deliberate addition of nitrogen as an
alloying agent, both improved toughness in the heat-affected zones of welds and excellent chloride corrosion
resistance was achieved, thus, quickly becoming the workhorse of stainless steels, accounting for more than 80% of
duplex use. Its popularity is also cost-based with the replacement of the nickel content with the less-expensive
addition of nitrogen [5]. Duplex alloys are essentially a compromise possessing some of the ferritic stress corrosion
cracking resistance and much of the superior formability of the common austenitic stainless alloys, at a cost saving
over the high nickel alloys. Duplex stainless steels generally have similar corrosion resistance to austenitic alloys
except they typically have better stress corrosion cracking resistance. Duplex stainless steels also generally have
greater tensile and yield strengths, but poorer toughness than austenitic stainless steels. A significant feature of
duplex stainless steel is that its pitting and crevice corrosion resistance is greatly superior to that of standard
austenitic alloys. Pitting resistance equivalent numbers (PREN), a standard industry measure, are often in the high
30s, while the latest duplex alloys have a PREN in excess of 40. This is an increasingly common specification for
certain offshore duties. However, PREN numbers only provide an approximate grading of alloys and do not account
for the microstructure of the material. An acceptance corrosion test on material in the supply condition is so much
more meaningful [6].

4 The Arabian Journal for Science and Engineering, Volume 34, Number 2C December 2009
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 

Duplex stainless steels have exceptional mechanical properties. Their room temperature yield strength in the
solution-annealed condition is more than double that of standard austenitic stainless steels not alloyed with nitrogen.
This may allow the design engineer to decrease the wall thickness in some applications. The typical yield strengths
of several duplex stainless steels are compared with that of 316L austenitic stainless steel between room temperature
and 300°C (570°F). Because of the danger of 475°C (885°F) temper-embrittlement of the ferritic phase, duplex
stainless steels should not be used at temperatures above those allowed by the applicable pressure vessel design code
for prolonged periods of time.
The mechanical properties of wrought duplex stainless steels are highly anisotropic. This is mainly the result of
the elongated grains and the crystallographic texture that results from hot or cold rolling. While the solidification
structure of duplex stainless steel is typically isotropic, it is rolled or forged and subsequently annealed with both
phases present. The appearance of the two phases in the final product reveals the directionality of the processing.
The strength is higher perpendicular to the rolling direction than in the rolling direction. The impact toughness is
higher when the crack propagates perpendicularly to the rolling direction than in the rolling direction. The measured
toughness will be higher for a “longitudinal” (L-T) Charpy test specimen than for other test directions. The impact
energy of a transverse specimen from a duplex stainless steel plate will typically be 1/2 to 2/3 that of a longitudinal
specimen. Despite the high strength of duplex stainless steels, they exhibit good ductility and toughness. Compared
with carbon steel or ferritic stainless steels, the ductile-to-brittle transition is more gradual. Duplex stainless steels
retain good toughness even to low ambient temperatures, for example, -40°C/F; however, ductility and toughness of
duplex stainless steels are lower than those of austenitic stainless steels. Austenitic stainless steels typically do not
show a ductile-to-brittle transition and maintain excellent toughness down to cryogenic temperatures.
3.1. Usage in Corrosive Environment
Following the rule of material selections, attention at every stage of the design, construction, and operation must
be given for any application. For duplex stainless steels, mostly their usage is for offshore oil and gas application.
Thus, the specification and use of materials which combine corrosion resistance with high mechanical strength is a
fundamental requirement [7].
Metals manufacturers have spent much time and effort in developing alloys specifically to meet offshore needs.
The alloys developed have had to be suitable for shafts and bolting, as well as many other applications. These have
included sea water and process pipework, water injection and booster pumps, line shaft pumps, emergency shutdown
valves, anchorages and tensioners for riser protection systems, multiphase pumps, and remotely operated vehicle
components.
The most significant contribution to the fight against corrosion offshore has been made by duplex stainless steels.
These have often been adopted on offshore structures in preference to carbon steel or other stainless steels. The value
of the duplex stainless steel is that it combines the basic toughness of the more common austenitic stainless steels
with the higher strength and improved corrosion resistance of ferritic steels. The optimum chemical composition of
these steels provides a high level of corrosion resistance in chloride media together with high mechanical strength
and ductility. Other benefits include the ability of some duplex stainless steels to be used at quite low sub-zero
temperatures and to resist stress corrosion cracking [8].
Offshore structures themselves present different requirements of materials depending upon whether their
application is topside, splash zone, or subsea. Topside, duplex materials are suitable for a wide range of bolting
applications, and materials such as Ferralium alloy 255 provide up to B7 steel strength, excellent corrosion resistance,
and a service life equal to the life of the system, thereby contributing to reduced maintenance costs. In the splash
zone, the alloy has already demonstrated its suitability for sea water resistance with over 15 years service on North
Sea installations, and has been widely employed for riser bolting and components on riser protection systems [9].
Other applications which can benefit from the use of these high alloy super duplex steels involve piping systems,
pumps (where the good erosion and abrasion resistance is employed), valves, heat exchangers, and other equipment.
There are many other applications for duplex stainless steel, such as heat exchangers, tubes and pipes for the
production and handling of gas and oil, and desalination plants. Also, this stainless steel is applied to pressure
vessels, pipes, tanks, and heat exchangers for the processing and transport of various chemicals, or in process
industries handling solutions containing chlorides. In addition, duplex stainless steel is applied in rotors, fans, shafts,
and press rolls where the high corrosion fatigue strength can be utilized. It also applied to cargo tanks, piping, and
welding consumables for chemical tankers. Table 1 summarizes the performance of the duplex stainless steels in
various environments [10, 11].

December 2009 The Arabian Journal for Science and Engineering, Volume 34, Number 2C 5
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 
 
Table 1. Performance of Different Alloys in Different Environment
Environment Problem Poor Good Best
Chlorides Pitting, crevice 300 Series SS Duplex alloys Alloy 276
corrosion 317L
Chlorides/Halides Stress corrosion 300 Series SS Duplex alloys Alloy 600/625
cracking
Hydrochloric Pitting, crevice Titanium, Duplex, 20 Alloy 22, 276 Zirconium,
Acid corrosion Cb-3 Tantalum
Hydrofluoric Pitting, crevice Duplex Alloys Silver, Gold Copper, Alloy
Acid corrosion 400
Sulfuric Acid Pitting, crevice Copper-Nickel (Alloy 20 Cb-3 Alloy 622
corrosion 601)
General Acidic Critical Pitting 300 Series SS 317L Duplex Alloy 25-6 Mo
Attack Alloys Alloy 625

4. EXPERIMENTAL METHOD
The tests samples were prepared from a pipe that was then split and flattened into plates by using Computer
Numerical Control Wire Electrical Discharge Machining (CNC WEDM). A GDS 500A Glow Discharge
Spectrometer was employed to determine the chemical composition. The results of the chemical composition and the
mechanical properties are shown in Table 2 and Table 3, respectively.

Table 2. Result of GDS and Standard Composition of UNS S32205

Result of GDS UNS S32205
Element
(wt. %) (wt. %)
Fe 66.0 Balance
C 0.0136 0.020
Cr 22.2 22.1
Ni 6.27 5.6
Mo 3.07 3.1
N 0.0892 0.18
Mn 1.12 2.0
Si 0.637 1.0

Table 3. Result of Tensile Test

Properties As received sample Standard UNS S32205
Tensile stress (MPa) 489.66 620
Modulus of elasticity (GPA) 220.63 200

A longitudinal section of the specimen was cut and mounted into a standard cylindrical mould by using
Automatic Hydraulic Mounting Machine in order to carry out the grinding and polishing process. The sample was
then ground to 4000 grit, and polished in accordance to the standard procedures. The polished samples were etched
using Kalling’s No. 2 (5g copper chloride, 100ml hydrochloric acid, and 100ml ethanol) to reveal the microstructure
of the duplex stainless steel for examination by optical microscopy.
Immersion test
A total immersion test was carried out to measure the corrosion performance of the specimens. All specimens
were pre-stressed to the standard values and according to the test conditions. The microstructures of the stressed
region of the specimens were analyzed by using an image analyzer. Any possible cracking that formed during the
corrosion test was identified. Eighteen specimens were prepared according to ASTM G48 [13]: Standard Test
Methods for Pitting and Crevice Corrosion Resistance of Stainless Steels and Related Alloys by use of ferric

6 The Arabian Journal for Science and Engineering, Volume 34, Number 2C December 2009
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 

chloride and sodium chloride solutions. The immersion test was done under two different temperatures, 25oC and
50°C for 72 and 144 hours. These temperatures were selected due to their common applications with duplex steels.
Solutions with different percentages varying the chloride concentration and acidity (pH) of the solution were used.
Table 4 shows the immersion test conditions, including test temperatures, the types of solutions, immersion durations,
pH, and chloride concentrations of the solution.

Table 4. Immersion Condition of Specimens

Chloride
Period Corrosion rate
Specimen T(°C) Solution concentratio pH
(Days) (mm/y)
n

1 50 FeCl3 1% 6 1% 5.95 0.3461

2 50 FeCl3 5% 6 5% 5.13 1.1458

3 50 FeCl3 10% 6 10% 5.07 1.3389

4 50 NaCl 1% + HCl 5% 6 1% 3.43 2.3848

5 50 NaCl 5% + HCl 5% 6 5% 3.29 3.5686

6 50 NaCl 10% + HCl 5% 6 10% 3.15 6.7230

7 50 FeCl3 1% 3 1% 5.95 0.2273

8 50 FeCl3 5% 3 5% 5.13 0.9402

9 50 FeCl3 10% 3 10% 5.07 1.1922

10 50 NaCl 1% + HCl 5% 3 1% 3.43 2.3371

11 50 NaCl 5% + HCl 5% 3 5% 3.29 3.4530

12 50 NaCl 10% + HCl 5% 3 10% 3.15 6.3182

13 25 FeCl3 1% 6 1% 5.95 0.0868

14 25 FeCl3 5% 6 5% 5.13 0.2181

15 25 FeCl3 10% 6 10% 5.07 0.3419

16 25 NaCl 1% + HCl 5% 6 1% 3.43 1.2552

17 25 NaCl 5% + HCl 5% 6 5% 3.29 1.6199

18 25 NaCl 10% + HCl 5% 6 10% 3.15 2.8866

Metallographic examinations were used to confirm the presence of corrosion, and it is imperative to note that this
usually occurs with no significant loss in mass of the test specimens, inasmuch as the duplex stainless steel has high
resistance to general corrosion. Furthermore, quantitative pitting analysis was also performed using simple software.
5. RESULTS AND DISCUSSIONS
Visual inspection and the corrosion rate
Figure 2 shows the representative of the visual inspection. In general, ferrichloride produces general thinning and
pitting while the combination of the sodium chloride and hydrochloride produces a fibrous-like, feathery appearance
corrosion attack.

December 2009 The Arabian Journal for Science and Engineering, Volume 34, Number 2C 7
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 
 

Figure 2. Appearance of representative samples after immersion

Graphical representation of the effect of the pH is shown in Figure 3. As the pH is decreasing (acidity increase),
the corrosion rate is increasing. This is because low pH solutions accelerate corrosion by providing hydrogen ions.
Hydrogen attacks and damages the surface of steel and increases the weight loss. The temperature plays an important
role in accelerating the corrosion rate of metals. The higher the temperature is, the higher the corrosion rate is. The
chloride concentration also increases the corrosion rate (Figure 4). The addition of chloride ions has a noticeable
effect on the corrosion behavior of stainless steel in acidic solutions, since in the presence of this ion, a passivity
breakdown process takes place above a certain potential that decreases with the chloride concentration. Chloride ions
slowly penetrate into the surface, at which the protective film is destroyed and the steel begins to corrode. Chloride
corrosion tends to evenly pit the entire surface area of the specimens with shallow, flat-bottomed, irregular shaped
pits. Chloride penetration in metal is due to the presence of different mechanisms, mainly diffusion and capillary
absorption. Temperature also influences the corrosion rate, as shown in Figure 5. This is due to temperature
dependant on the chemical reactivity.

Figure 3. Effect of the pH on the corrosion rate

8 The Arabian Journal for Science and Engineering, Volume 34, Number 2C December 2009
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 

Figure 4. Effect of the chloride concentration on the corrosion rate

Figure 5. Effect of the temperature on the corrosion rate

Microstructure and pitting morphology
Many pittings are visible using the naked eye (as indicated by the arrows in Figure 6), but using cross section and
optical micrograph, the diameter and depth of the pits can be determined accurately. An example is shown in Figure
7, which shows the photomicrograph of a typical pitting on one of the specimens. Table 5 shows the average of the
pitting depth. Clearly the effect of the pH and the chloride concentration is strong. The pitting density was also
evaluated. To do so, a random (2 x 2) cm2 area was selected on each specimen, and the amounts of small, medium,
and large pits in the area were counted. Table 6 shows the pitting density for representative specimens.

Figure 6. Surface appearance showing the pitting existence

December 2009 The Arabian Journal for Science and Engineering, Volume 34, Number 2C 9
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 
 

Figure 7. Typical morphology of the pits

Table 5. Pitting Depth

Acidity pH 5.13 pH 5.07

83.53 µm 238.8 µm
Depth of 94.51 µm 221.2 µm
pitting 98.17 µm 148.2 µm
15.64 µm 136.5 µm

Average 72.96 µm 186.18 µm

Table 6. Pitting Density Average Per 4 cm2 Area

Size of pitting pH 5.13 pH 5.07

Small 19 9

Medium 9 11

Large 1 7

Total 29 27

A specimen immersed in a solution with higher pH (low acidity) has more pits but shallower pitting. A specimen
immersed in a solution with lower pH (high acidity) has fewer pits but with a greater depth. Although there are more
pits on specimens with a higher pH, the greater depth of narrower pits makes it lose less weight than specimens
exposed in lower pH. This explains why the corrosion rate of the specimen immersed in solution with lower pH is
higher than the specimen immersed in solution with higher pH.

10 The Arabian Journal for Science and Engineering, Volume 34, Number 2C December 2009
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 

Area fraction analysis

To determine which phase is mostly attacked by the pitting corrosion, the area fraction method is used. This
method was applied to the photomicrograph of the specimens using Omninet ™. Figure 8 shows the
photomicrograph of specimen 2 before and after using the software. The area fraction for austenite phase fell from
50.9% to 23.4%. This proves that the mixture of sodium chloride and hydrochloric acid creates a pitting corrosion
attack mostly on the austenite phase. Similar area fraction reductions were also witnessed on samples tested with
other solutions. The site of preferential pitting nucleation is confirmed by using this method. This can be explained
by the fact that austenite with a crystal structure of face-centered cubic (FCC) has a solid solubility of carbon, while
ferrite with a crystal structure of body-centered cubic (BCC) has much less solid solubility of carbon. Carbon is a
weak element with very low corrosion resistance. The galvanic effect created by two cells of austenite and ferrite
also synergizes phase dependency of the corrosion pitting nucleation.

Figure 8. Area fraction analysis

Pitting resistance equivalent number (PREN)
Another method to rank the pitting resistance of stainless steel is using Pitting Resistance Equivalent Number
(PREN). The higher the PREN, the better the pitting resistance is. This parameter is strongly dependent on Cr, Mo,
and N, each of them weighted according to its influence on pitting:
PREN = %Cr + 3.3%Mo + 16%N (1)
Since there are two phases in duplex stainless steel, with the three key elements unevenly partitioned between
them, it is clear that PREN for each phase should be calculated, as the actual pitting resistance is governed by
whichever phase gives the lower value. The phase with the lower value of PREN will corrode easier than the other
phase. The chemical composition (wt%) and PREN of the two phases in UNS S32205 is shown in Table 7. From the
table, it is seen that austenite has a lower PREN than ferrite. Therefore, pitting corrosion will easily attack the
austenite phase.

Table 7. PREN for Each Phase

Phase % Cr % Mo %N PREN
Austenite 20.86 2.43 0.38 34.96
Ferrite 23.86 3.51 0.05 36.24

December 2009 The Arabian Journal for Science and Engineering, Volume 34, Number 2C 11
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 
 
Microstructure and pitting morphology
Pittings are visible to the naked eye (as indicated the arrows in Figure 6). However, using cross section and
optical micrograph, the diameter and depth of the pits can be determined accurately. An example is shown in Figure
7 of a typical pitting on one of the tested specimens. Table 5 shows the average of the pitting depths. Clearly, the
effect of the pH is evident.
The pitting density was also evaluated by using a random (2 x 2) cm² area on each specimen, and the amounts of
small, medium, and large pits in the area were counted. Table 6 shows the pitting density for representative
specimens.
A specimen immersed in a solution with a higher pH (low acidity) has more pits but shallower pitting. A
specimen immersed in a solution with a lower pH (high acidity) has fewer pits but with greater depth. Although there
are more pits on specimens with a higher pH, the greater depth of narrower pits makes it lose less weight than
specimens exposed in lower pH. This explains why the corrosion rate of the specimen immersed in solution with
lower pH is higher than the specimen immersed in solution with higher pH.
Area fraction analysis
To determine which phase is mostly attacked by the pitting corrosion, the area fraction method is used. This
method was applied to the photomicrograph of the specimens using Omninet ™. Figure 8 shows the
photomicrograph of specimen 2 before and after using the software. The area fraction for austenite phase fell from
50.9% to 23.4%. This confirms that the mixture of sodium chloride and hydrochloric acid mainly attacked the
austenite phase. Similar area fraction reductions were also observed on samples tested with other solutions. The site
of preferential pitting nucleation can, fairly, be confirmed by using this method. This can be explained by the fact
that austenite with a crystal structure of face-centered cubic (FCC) has solid solubility of carbon, while ferrite with a
crystal structure of body-centered cubic (BCC) has much solid solubility of carbon. Carbon is a weak element with
very low corrosion resistance. The galvanic effect created by two cells of austenite and ferrite also synergizes phase
dependency of the corrosion pitting nucleation.
Pitting resistance equivalent number (PREN)
Another method to rank the pitting resistance of stainless steel is using Pitting Resistance Equivalent Number
(PREN). The higher the PREN, the better the pitting resistance is. This parameter is strongly dependent on Cr, Mo,
and N, each of them weighted according to its influence on pitting:
PREN = %Cr + 3.3%Mo + 16%N (1)
Since there are two phases in duplex stainless steel, with the three key elements unevenly partitioned between
them, it is clear that PREN for each phase should be calculated, as the actual pitting resistance is governed by
whichever phase gives the lower value. The phase with the lower value of PREN will corrode easier than the other
phase. The chemical composition (wt%) and PREN of the two phases in UNS S32205 is shown in Table 7. From the
table, it is known that austenite has a lower PREN than ferrite. Therefore, pitting corrosion will easily attack the
austenite phase.
6. CONCLUSIONS
The effect of pH and chloride concentration on corrosion behavior of duplex stainless steel, represented by UNS
S32205, has been determined. Decreasing pH increases the corrosion rate. Similarly, increasing temperature
increases corrosion rate. This can be achieved well using different solutions with different temperatures and periods
of immersion, according to the ASTM G48 standard. Similarly, increasing chloride concentration increases corrosion
rate.
Pitting corrosion preferentially attacks the austenite phase. This can be quantified easily using simple
metallography and software analysis, as well as PREN (Pitting Resistance Equivalent Number).
The effect of pH and chloride concentration on the corrosion behavior of duplex stainless steel, represented by
UNS S32205, has been determined. Decreasing pH (increasing acidity) increases the corrosion rate. This can be
achieved well using different solutions with different temperatures and periods of immersion, according to the
ASTM G48 standard. Similarly, increasing chloride concentration increases corrosion rate.
Pitting corrosion preferentially attacks the austenite phase. This can be quantified easily using simple
metallography and software analysis, as well as PREN (Pitting Resistance Equivalent Number).

12 The Arabian Journal for Science and Engineering, Volume 34, Number 2C December 2009
 Yunan Prawoto, K. Ibrahim, and W.B. Wan Nik
 

REFERENCES
[1] J. Charles, “Super Duplex Stainless Steels: Structure and Properties”, In: Proceedings of the Conference of Duplex
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Molybdenum Association, London, 2001.
[3] Iris Alvarez-Armas, “Duplex Stainless Steels: Brief History and Some Recent Alloys”, Recent Patents on
Mechanical Engineering, 1( 2008), pp. 51–57.
[4] R. N. Gunn, Duplex Stainless Steels: Microstructure, Properties and Applications.,Abington Publishing,
Cambridge, England. 1997.
[5] D. S. Bergstrom, J. J. Dunn, J. F. Grubb, and W. A. Pratt, US20036551420B1 (2003).
[6] Marcelo Martinsa and Luiz Carlos Casteletti, “Microstructural Characteristics and Corrosion Behavior of a Super
Duplex Stainless Steel Casting”, Materials Characterization, 60(2009), pp. 150–155.
[7] A. D. Mercer, Corrosion in Seawater Systems,. New York: Ellis Horwood Publishing, New York, 11990.
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Joints”., Mater Charac, 56(4–5)( 2006), pp. 436–441.
[9] A. Miyasaka, K. Denpo, and H. Ogawa, “Prediction of Application Limits of Stainless Steels in Oilfield
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[10] M. B. Rockel, Duplex Stainless Steels for the Chemical Petroleum and Process Industry,. Texas: VDM
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[11] E. N. Simons and E. Gregory, Stainless and Heat-Resisting Steel,. New York: Pergamon Press, New York, 1986.
[12] ASTM Standard: G48 – 07, “Standard Test Methods for Pitting and Crevice Corrosion Resistance of Stainless
Steels and Related Alloys by Use of Ferric Chloride Solution”, ASTM Annual Book of Standards, 01–02(2007).

December 2009 The Arabian Journal for Science and Engineering, Volume 34, Number 2C 13

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