Corrosion of Stainless Steels☆

AJ Sedriks, Office of Naval Research, Arlington, VA, United States

OS Zaroog, Universiti Tenaga Nasional, Selangor, Malaysia
r 2017 Elsevier Inc. All rights reserved.

Introduction

Stainless steels are corrosion-resistant iron-base alloys containing a maximum of 1.2% carbon and a minimum of 10.5% chro-
mium by weight. This is the minimum amount of chromium that prevents the formation of rust in humid unpolluted atmo-
spheres, hence the designation “stainless.” The corrosion resistance of stainless steels is provided by a very thin and protective
surface film, known as the passive film, which is self-healing when damaged in a wide variety of environments. The Fe–Cr–Ni and
Fe–Cr–Ni–Mn–N grades of stainless steels are austenitic and are popularly known by the former AISI type numbers in the 300 and
200 series, respectively. The Fe–Cr grades are martensitic at lower chromium levels and ferritic at higher chromium levels, and are
known by numbers in the 400 series. The most popular austenitic, ferritic, and martensitic grades have been type 304 (containing
19% chromium, 10% nickel and also known by the UNS Number S30400), type 430 (17% chromium, S43000), and type 410
(12% chromium, S41000), respectively. Another popular grade has been the ferritic type 409 (S40900) because of its use in
automobile exhaust systems. Duplex grades (containing about 50% austenite, 50% ferrite) and precipitation hardening grades
(mostly martensitic) are also available for higher strength applications. Stainless steels are used for consumer products, machinery,
architectural and military applications, and for equipment in the petroleum, chemical, aerospace, power, and process industries.
Some 180 different alloys can be recognized as belonging to the stainless steel group, with chemical compositions adjusted to give
improved resistance to pitting and crevice corrosion, intergranular corrosion, stress-corrosion cracking and hydrogen embrittle-
ment, general corrosion, and attack by high-temperature gases (Fig. 1).

Resistance to Pitting and Crevice Corrosion

Resistance to pitting and crevice corrosion is usually improved by further alloying the austenitic and duplex grades with chro-
mium, molybdenum, and nitrogen, and the ferritic grades with chromium and molybdenum. The beneficial effects of these
alloying elements are complex and interactive, and attempts have been made by suppliers of stainless steels to develop a
compositionally derived pitting and crevice corrosion resistance index known as the pitting resistance equivalent number (PREN).
The PREN is given by the compositional parameter %Cr þ 3.3(%Mo) þ 16(%N) þ 1.65(%W). In general, the larger the numerical
value of PREN, the higher the pitting and crevice corrosion resistance. The major drawback in using a parameter based only on
chemical composition is that it ignores the often-found detrimental effects of microstructural constituents such as manganese
sulfide, sigma, chi, chromium-depleted zones, and alloying element segregation due to coring produced by processes such as
welding. However, PREN provides some guidance for alloy selection for service in oxidizing chloride or acidic environments.
Among the proprietary stainless steels with a large numerical value of PREN are the superaustenitics, such as 254SMO (S31254),
6XN (N08367), 925hMo (N08925), and 654SMO (S32654); the superferritics, such as 29-4C (S44735), Sea-Cure (S44660), and
Monit (S44635); and the superduplexes, such as DP-3W (S39274), Zeron 100 (S32760), and Uranus 52N (S39255), Ferralium
SD40 (S39253), SAF2507 (S32750), as an example, the pitting corrosion resistance of SAF2507 (S32750) is determined by the
pitting resistance equivalent number of a weaker phase, which has been proved by both the pit morphologies of specimens
annealed at different temperatures (Fig. 2) and the similarity between the tendencies of critical pitting temperature data and pitting
resistance equivalent number of a weaker phase as the annealing temperature increases (Hua Tan et al., 2009).

Intergranular Corrosion

Intergranular corrosion results from chromium depletion in the alloy matrix near grain-boundary chromium carbides (and
sometimes nitrides) precipitated during welding or some other high-temperature exposure. This depletion occurs at certain
time–temperature combinations which are sufficient to precipitate chromium carbide but insufficient to rediffuse chromium back
into the austenite near the carbide. For example, heating a type 304 stainless steel containing 0.039% carbide for 10 h at 7001C
will reduce the chromium level from 19% to less than 13% in the region next to the grain-boundary carbide precipitate, resulting
in a loss of corrosion resistance in this region. This depletion is known as sensitization. The metallographic analysis revealed the
presence of intergranular corrosion in the heat-affected zone. This type of corrosion occurs due to steel overheating (referred to as
sensitization). Due to the segregation of chemical elements, corrosion is also associated with pitting corrosion (Fig. 3) that leads
directly to pipeline perforation (Ryl et al., 2014).

☆
Change History: March 2016. O.S. Zaroog added the Abstract, Keywords, Figures, expanded text with additional review materials, and updated the list of
references.

Reference Module in Materials Science and Materials Engineering doi:10.1016/B978-0-12-803581-8.02893-9 1

2 Corrosion of Stainless Steels

Fig. 1 Compositional and property linkages in the stainless steel family of alloys.

Remedial measures for sensitization include lowering the carbon content to 0.03% maximum (see L-grades in Fig. 1), stabi-
lizing with titanium or niobium þ tantalum additions, postweld heat treatments if feasible, or using duplex stainless steels which
do not exhibit sensitization at the austenite–ferrite grain boundaries because of faster chromium diffusion and carbide growth
kinetics in the ferrite phase.

Stress-Corrosion Cracking

Stress-corrosion cracking (SCC) may occur in the presence of a tensile stress and a specific corrosive (eg, chlorides at high
temperatures, caustics, acids, high-temperature (3001C) water containing traces of dissolved oxygen, or aqueous solutions con-
taining sulfur compounds). For SCC caused by sensitization the remedies are the same as for intergranular corrosion. Austenitic
stainless steel has a high SCC resistance, however it was found that SCC occurred in the field as well as in the laboratory (Terachi
et al., 2012; Ilevbare et al., 2010).
In other cases susceptibility to SCC can be minimized by increasing the nickel content of the alloy (for austenitics only), selecting
a suitable ferritic or duplex stainless steel instead of an austenitic one, lowering the service temperature, stress-relief annealing, shot
peening to introduce compressive surface stresses, adding chemical corrosion inhibitors to the service environment, or cathodic
protection. The last option should not be used for high-strength martensitic grades which crack by a hydrogen embrittlement
mechanism. For martensitic stainless steels tempering heat treatments to produce lower strengths may improve cracking resistance.

General Corrosion

General (uniform) corrosion can be encountered in strong acids or alkalis. Surface analysis shows (Fig. 4) that the main corrosion
form of 316L SS is severe general corrosion accompanied by localized pitting. After immersion in the test solution, the surface
 Corrosion of Stainless Steels 3

Fig. 2 The metastable pitting morphologies of UNS S32750 specimens after different solution treatment, characterized by SEM. (a) Annealed at
10501C for 2 h, (b) annealed at 10801C for 2 h, (c) annealed at 11001C for 2 h, and (d) annealed at 12001C for 2 h (Hua Tan et al., 2009).

Fig. 3 SEM micrographs of a join pitting and intergranular corrosion within the heat-affected zone, proving weld decay presence. Picture taken
after Strauss test. Magnification  500 (Ryl et al., 2014).

roughness increased rapidly and severe corrosion was obvious, indicating the significant tendency of localized corrosion (Jina et al.,
2014).
Corrosion resistance in sulfuric and organic acids is promoted by alloying with copper, molybdenum, and nickel; copper-
containing stainless steels such as 904L (N08904), 20Cb-3 (N08020), alloy 825 (N08825), and the cast alloy CN-7M (J95150) are
often used in the chemical industry for sulfuric acid service.
Phosphoric acid is handled by high-molybdenum grades such as alloys 28 (N08028), G-30 (N06030), and 3127hMo
(N08031). Nitric acid can be handled by type 304L (S30403), and higher-chromium alloys, such as type 310S (S31008) and alloy
800 (N08800), have been used for very hot, concentrated nitric acid. The ferritic stainless steel E-Brite (S44627), as well as
unalloyed nickel (N02201), has been used to handle elevated temperature caustic environments.
4 Corrosion of Stainless Steels

Fig. 4 The AFM images (10 mm  10 mm) of type 316L SS surface in the simulated solution after various exposure times (Jina et al., 2014).

Attack by High-Temperature Gases

Attack by high-temperature gases is usually identified as oxidation, sulfidation, carburization, nitriding, or halogen-gas corrosion.
In oxidizing, sulfidizing, and carburizing gases high chromium contents, as in type 310 (S31000) or its cast variant HK, improve
resistance to attack. In addition, alloying with aluminum and silicon can be beneficial to oxidation resistance, as in type 406 (3.5%
aluminum) and type 302B (S30215, 2.5% silicon), respectively. Resistance to nitriding is improved by alloying with nickel, as in
RA-330 (N08330). For stainless steels the upper temperature limit for operation in dry chlorine is about 3201C, with the presence
of water vapor accelerating corrosion.

Conclusion

Stainless steel is widely used as a rust resistant material, however many types of corrosion attack stainless steel such as pitting and
crevice corrosion, intergranular corrosion, stress-corrosion cracking and hydrogen embrittlement, general corrosion, and attack by
high-temperature gases.
 Corrosion of Stainless Steels 5

Many methods have been used to improve stainless steel corrosion resistance. Ferritic resistance to pitting and crevice corrosion
can be improved by alloying with chromium and molybdenum. The austenitic duplex resistance to pitting and crevice corrosion
can be improved by alloying with molybdenum, chromium and nitrogen. In general, the larger the numerical value of PREN, the
higher the pitting and crevice corrosion resistance.
Lowering the carbon content to a 0.03% maximum improved the resistance of intergranular corrosion. Intergranular corrosion
can be avoided by using duplex stainless steels which do not exhibit sensitization at the austenite–ferrite grain boundaries because
of faster chromium diffusion.
SCC can be minimized in many ways such as selecting suitable ferritic or duplex stainless steel, nickel content of the alloy can
be increased, use of annealing, introducing compressive residual stress by shot peening and adding chemical corrosion inhibitors
to service the environment.
Alloying with copper, molybdenum, and nickel increased the resistance of General (uniform) corrosion resistance in sulfuric
and organic acids. Phosphoric acid is handled by high-molybdenum grades. Very hot, concentrated nitric acid can be handled with
higher-chromium alloys. Elevated temperature caustic environments can be handled with ferritic stainless steel.
High chromium content improves resistance to attack by high-temperature gases, also additional alloying with aluminum and
silicon can help to improve resistance to attack by high-temperature gases.

References

Hua Tan, Yiming Jiang, Bo Deng, Tao Sun, Juliang Xu, Jin Li, 2009. Effect of annealing temperature on the pitting corrosion resistance of super duplex stainless steel UNS
S32750. Materials Characterization 60 (9), 1049–1054.
Ilevbare, G.O., Cattant, F., Peat, N.K., 2010. SCC of stainless steels under PWR primary circuit service conditions. EPRI MRP Conference and Exhibit Show-Materials Reliability
in PWR Nuclear Power Plants. Colorado Springs.
Jina, Z.H., Gea, H.H., Lina, W.W., et al., 2014. Corrosion behaviour of 316L stainless steel and anti-corrosion materials in a high acidified chloride solution. Applied Surface
Science 322, 47–56.
Ryl, J., Wysocka, J., Darowicki, K., 2014. Determination of causes of accelerated local corrosion of austenitic steels in water supply systems. Construction and Building
Materials 64, 246–252.
Terachi, T., Yamada, T., Miyamoto, T., Arioka, K., 2012. SCC growth behaviors of austenitic stainless steels in simulated PWR primary water. Journal of Nuclear Materials 426,
59–70.