Austenitic Stainless Steels This process improved the productivity of melt

shops, permitted lower cost raw materials and higher

Austenitic stainless steels are an extraordinary family metallic yields, and resulted in cleaner, lower carbon,
of alloys that have exceptional corrosion resistance lower sulfur stainless steels. Variants on the AOD
and equally impressive mechanical properties. They process using vacuum-assisted decarburization also
have unsurpassed strength, toughness, and formability find occasional use.
among the commercially viable alloys from cryogenic Equally important in the development of austenitic
to elevated temperatures. They are also valued aes- stainless steel was the transfer of continuous casting
thetically and are environmentally benign. Table 1 lists technology from carbon steel. Because of the tendency
the most common austenitic grades and two of the chromium in molten stainless steel to reoxidize,
precipitation hardening grades. Although only about elimination of the ingot teeming step was a major
10.5% chromium is required to render iron alloys improvement in cleanliness. Continuous casting also
stainless, austenitic stainless steels all contain at least eliminated the high cost of slabbing and its poor yield.
15% chromium with which nickel, manganese, Nicodemi (1993) reviews the state of the art.
carbon, and nitrogen are combined to stabilize the f.c.c. Hot rolling of slabs is increasingly performed on hot
structure. reversing mills rather than tandem mills because their
Austenitic stainless steels have been in use since the flexibility in pass schedule and coil box capability
1920s, but advances in processing implemented in the allows the hot rolling to be better tailored to the high
1970s made them much more cost effective for com- hot hardness and narrow rolling temperature range of
mon use in applications where coated or plated steels, austenitics.
aluminum, or copper alloys may otherwise be Austenitics can be used as hot rolled or further
preferred. Other inherent factors contributing to their reduced by cold rolling but they are generally annealed
increased use is long service life with low maintenance and pickled in either case. Cold reductions of 80% are
cost, ability to be recycled, and benign effect on the possible but require cluster mills because of the high
environment and human health. work hardening rates of austenitics. Final annealing is
conducted either in air or in hydrogen\nitrogen
protective atmospheres.
The heat treatment of austenitic stainless steel is
simply annealing, which is done from about 1000 mC to
1. Processing 1100 mC. The function of annealing is to eliminate the
The processing advances that have most benefited effects of cold work by recrystallization, to control
stainless steels are the argon–oxygen decarburization grain size, and to dissolve any precipitated carbides.
(AOD) and the continuous caster processes, but Cooling from annealing temperatures must be
significant advances have been made in hot and cold sufficiently rapid to avoid carbide precipitation. No
rolling mills as well as in the annealing line. martensite can form from quenching. Mechanical
Stainless steel is typically produced from a com- deformation is required to transform these alloys.
bination of recycled scrap and virgin charge materials
melted in an electric arc furnace. After melting it is
2. Structure
transferred to another vessel, an AOD one, for
refining, i.e., to reduce the carbon level from about 1% Austenitic stainless steels are designed as solid solution
to about 0.05%. In the AOD vessel a mixture of alloys. From a structural point of view it is convenient
oxygen and argon is injected into the molten metal at to classify the alloying elements by the degree to which
around 1700 mC. The ratio of argon to oxygen is they replicate the effects of chromium in stabilizing
controlled to keep the partial pressure of carbon ferrite or nickel in stabilizing austenite. Each element
monoxide sufficiently low such that carbon is oxidized plays a separate role in corrosion resistance or
in preference to chromium. At the end of the refining strengthening, so alloy design seeks to simultaneously
cycle, the small chromium losses are recovered from satisfy the objectives of structure, corrosion resistance,
the slag by the addition of silicon. mechanical properties, cost, and fabricability.

Table 1
Principal grades of austenitic stainless steel.
Grade Carbon Nitrogen Manganese Silicon Chromium Nickel Molybdenum Other
S20100 0.15 0.25 5.5–7.5 1.0 16.0–18.0 3.5–5.5
S30100 0.15 2.0 1.0 16.0–18.0 6.0–8.0
S30400 0.08 0.10 2.0 1.0 18.0–20.0 8.0–10.5
S31600 0.08 0.10 2.0 1.0 16.0–18.0 10.0–14.0 2.0–3.0
S17400 0.07 1.0 1.0 15.0–17.5 3.0–5.0 3.0–5.0 Cu;
0.15–0.45 (NbjTa)
S17700 0.09 1.0 1.0 16.0–18.0 6.5–7.75 0.75–1.5 Al
1
Austenitic Stainless Steels

Austenitic stainless steels are designed to initially All commercially used alloying elements stabilize
contain several percent ferrite after solidification and austenite, even those that promote ferrite during
cooling to ambient temperatures. The amount of this solidification. All austenitic grades have roughly com-
ferrite, which dissolves during normal processing, can parable yield strengths when annealed and abundant
be calculated from (Nicodemi 1993) ductility, but their work hardening rates vary greatly,
because the strain-induced martensite is a much harder
% ferrite l 3(Crj1.5SijMo)k2.8(Nij0.5 Mn) phase than the austenite from which it forms. This
factor is extensively exploited in selecting alloys whose
k84(CjN)k19.8% (1) work hardening rate is optimized for the forming
method preferred.
Suutala (1983) correlated the solidification mode, i.e.,
as primary dendrites of austenite vs. ferrite, as crucial
to hot cracking in welds, and by extension to hot
workability. Suutala’s formula for predicting the 4. Carbide and Nitride Precipitation
solidification mode gives 1.55 as the critical value for
Cr eq\ Ni eq above which solidification occurs in the Austenitic stainless steels can contain up to 0.15%
preferred ferritic mode which results in fewer carbon. Carbon is an impurity more than an alloying
impurities, such as sulfur, phosphorus, selenium, tin, element. It increases yield strength and helps stabilize
lead, etc., being rejected to interdendritic grain bound- austenite, but, if not kept in solid solution, it combines
aries. In this relationship the equivalencies are expres- with chromium as M C , where M is principally
chromium, but also iron. #$ ' This carbide precipitates
sed as
initially at grain boundaries, then at twins, then within
Cr eq l % Crj1.37% Moj1.5% Si austenite grains. The grain boundary precipitation
leaves the surrounding volume significantly depleted
j2% Nbj3% Ti (2) of chromium. This phenomenon is called ‘‘sensitiz-
Ni eq l % Nij0.31% Mnj22% C ation’’ and it is particularly detrimental to corrosion
resistance. The kinetics of this precipitation are such
j14% Nj% Cu (3) that grades with 0.08% carbon sensitize in minutes
while those with less than 0.03% require 100 times
Since the continuous caster puts a premium on hot longer. Increasing nickel and molybdenum and cold
workability, austenitic alloys are designed to solidify work accelerate the precipitation, while nitrogen and
as ferrite retaining a small amount of delta ferrite, manganese retard it. Reducing carbon levels has
which dissolves in subsequent processing. This become the preferred way to avoid sensitization in
approach also makes them weldable without danger service. Some alloys are designed to eliminate the
of weld cracking. precipitation of chromium carbides by preferentially
forming titanium or niobium carbides. In certain high-
temperature applications this can be more appropriate
for austenitics while it is the normal method in ferritic
3. Austenite Stability stainless steels, where no practical refining method can
A critical characteristic of the austenitic phase is its reduce carbon levels sufficiently to prevent sensitiz-
stability. As in carbon steels, stainless steels with ation.
metastable austenite can transform to martensite The carbide precipitation reaction occurs between
either by cooling or by deformation. The martensite 600 mC and 1000 mC. At similar temperatures other
start temperature, Ms, is well below room temperature intermetallic phases, principally sigma, can precipitate
in all commercial alloys, but the strain-induced trans- at much longer times in the more highly alloyed
formation is nearly always present in normal process- industrially used grades. This occurs in alloys where
ing involving cold rolling, deep drawing, wire drawing, the matrix is rich in chromium equivalents, over 18%,
grinding, or polishing. The quantity of martensite and low in dissolved carbon. Such phases are of much
formed depends on the temperature, strain rate, and more practical importance in ferritic grades where
the composition. The influence of composition is their kinetics of formation is about 100 times faster.
described by (Angel 1954)

Md30(C) l 497k462(% Cj% N)k9.2% Si

5. Hardening of Austenite
k8.1% Mnk13.7% Cr
Interstitial alloying elements, carbon, nitrogen, and to
k20% Nik18.5% Mo (4) a limited degree boron, have a pronounced strength-
ening effect on austenite, compared to the more
where Md30 is the temperature at which 50% mar- modest influence of substitutional solid solution
tensite forms at a true strain of 30%. elements and of grain size. Empirical relationships

2
 Austenitic Stainless Steels

have been developed to quantify these effects (Pick- 7. Formability

ering et al. 1969):
Because of their exceptional ductility, austenitic stain-
less steels have excellent formability. The most com-
Y0.2% (MPa) l 15.4[4.4j23(C) mon cold-forming procedure is drawing and it is
j32(N)j1.3(Si)j0.24(Cr) useful to distinguish two modes. In the first, called
deep drawing, a flat blank is pulled freely into a die by
j0.94( Mo)j1.2( V ) the action of a punch with no added restraint. A
j0.29( W )j2.6( Nb ) second type of drawing restrains the periphery of the
blank and the metal is stretched into the die. This is
j1.7(Ti)j0.82(Al ) drawing by expansion.
j0.16(% ferrite)j0.46dk" ] (5) Carbon steels and ferritic stainless steels both deep
# draw well because the anisotropic nature of flat-rolled
where d is the mean grain diameter and t is the twin b.c.c. structures resists thinning in the thickness
spacing, both in millimeters. Nitrogen is the most direction, giving them a drawability beyond that which
effective agent for increasing the strength of austenite their inherent ductility would suggest. Austenitic
because it has the largest strengthening coefficient and stainless steels are to a first approximation isotropic,
high solubility. Since nitrogen also suppresses carbide so they lack that benefit, but make up for it with their
and other phase precipitation, enhances corrosion exceptional ductility.
resistance, and has negligible cost, it is a crucial Work hardening rate is critical in expansion forming
component of modern austenitic alloy design. because localized thinning which would lead to frac-
One of the most characteristic features of austenitic ture is countered by the increase in strength in the
stainless steels is their pronounced strain hardening, critical location where stretching is the greatest. The
which at a minimum of 0.4 is far above that of ferritic controllably high work hardening rate of austenite is a
steels. The strain-induced transformation of meta- great advantage and permits extraordinary stretch
stable austenite to martensite can increase that coef- formability.
ficient to nearly 1.0. Cold-worked austenitic stainless Among austenitic stainless steels, those with the less
steels are commonly used at tensile strengths stable austenite such as 301, e.g., 17% chromium, 7%
approaching 2000 MPa. nickel, are favored for items such as sinks where part
geometry lends itself to stretch forming. High aspect
ratio cylindrical parts made in multistage dies without
intermediate annealing use richer grades to lessen or
6. Precipitation Hardening Stainless Steels completely eliminate martensite formation. 305 with
up to 19% chromium and 13% nickel represents that
Another class of austenitic stainless steels is the
extreme. Between the two a continuum of levels of
precipitation hardenable stainless steels. There are
chromium and nickel are used depending on the mode
also a related group of martensitic precipitation
of deformation that must be satisfied.
hardenable stainless steels, more familiarly known as
Surface finish is always a key consideration. Grain
maraging steels, which are discussed elsewhere. The
size must be kept sufficiently fine such that the surface
austenitic precipitation hardenable grades rely on the
relief produced within grains during deformation does
precipitation of a coherent intermetallic γh phase
not become visible. This is the ‘‘orange peel’’ defect.
from a stable, supersaturated austenite matrix. The
The defect of Luders bands, stretcher strains, does not
precipitate is composed of nickel, aluminum, and
occur on austenitic stainless steels as it does on mild
titanium and a typical precipitation treatment involves
steels and ferritic stainless steels. Neither does the
aging at 725 mC for 16 h after a 1000 mC solution anneal.
defect known as ‘‘ridging’’ or ‘‘roping’’. As-formed
A286 and Discaloy are two prominent examples of
austenitic parts can have high hardness and high
this alloy family.
residual stresses. This can make them susceptible to
A second, more common, group is the semi-
brittle delayed failure if they have residual hydrogen
austenitic precipitation hardenable stainless steels,
content from previous bright annealing operations.
which have a carefully balanced lean austenite. High-
temperature, e.g., 1065 mC, solution treatment pro-
duces a metastable austenite, which is soft enough to
fabricate. Subsequent ‘‘conditioning’’ at 750 mC desta-
8. Corrosion
bilizes the austenite by precipitating Cr C , which
#$ '
results in an austenite that can thermally transform to Whatever their other attributes, the austenitic stainless
martensite to produce a primary hardening. This steels owe their widespread use to their resistance to
martensite is in turn aged at 500–600 mC to produce a corrosion. This corrosion resistance can be attributed
true precipitation hardening via nickel and aluminum to the tendency of stainless steel to form a passive film.
γh. 17-7PH and 15-7PH are representative of this In environments where passivity cannot be main-
group. tained, the corrosion of stainless steels can proceed

3
Austenitic Stainless Steels

rapidly. Fortunately, stainless steel is passive in more can be a site of attack, but further, when dissolved, it
normally encountered environments, so from a design may introduce ions that prevent formation of a passive
point of view, it is considered inert and with indefinite film at that site. Such is the case with the very common
life. MnS inclusion. Unless removed by pickling at the
Passivity is the formation on the surface of a thin (a producing mill or in the field by ‘‘passivation,’’ i.e.,
few nanometers) layer of tightly adherent and chemi- cleaning the surface with nitric or other acid, sulfides
cally stable oxide or hydroxide with low ionic per- seriously degrade pitting performance.
meability. Because of its low ionic permeability, such a Designers should be especially wary of pipe and
layer cannot grow, so further consumption of the tubing, which often has high sulfur levels to facilitate
underlying metal in the reaction that formed the layer tube welding, but at the expense of corrosion
ceases. Corrosion effectively stops. resistance. 316 tubing with 0.015% sulfur has no better
Chromium is the element whose concentration in pitting resistance than 304 with less than 0.003%
the passive film gives it its stability. In the least sulfur. Titanium will form sulfides in preference to
aggressive aqueous environments about 11% chro- those of manganese and thereby eliminate the harmful
mium in the alloy is necessary for stable passivity, but effect of sulfur.
in more aggressive environments, higher concentra- Any disruption to the surface after pickling runs the
tions are required. The exact nature of the passive film risk of degrading pitting resistance. The most common
is not well understood, but it can be thought of as an problem is that caused by abrasive polishing of the
ordered iron\chromium oxide that undergoes tran- surface to produce a no. 3 or a no. 4 finish. These very
sition to a more hydrated form facing the environment. eye-pleasing finishes diminish pitting resistance by
The film forms spontaneously in air or water and is about the same amount as the effect of sulfides cited
self-healing. Films are not stable in all environments, above. This can be alleviated by pickling after polish-
however. The principle factors that influence film ing or by using an embossed finish of the same
stability are the difference in potential between the appearance.
metal and the solution, the temperature, the acidity, Crevice corrosion is a related phenomenon in which
and the halide concentration. Much empirical data are mechanical restrictions to fluid flow permit crevices to
available to determine which stainless alloy is stable become more acidic than the bulk solution with the
in a given environment. From a design point of view consequent danger of loss of passivity. Avoidance of
the main objective is always to design for stable crevices is thus a design priority while resistance to
passivity. crevice corrosion is similar to resistance to pitting
The more significant consideration in the use of corrosion.
stainless steel is not general corrosion, but localized Stress corrosion cracking is a form of brittle delayed
corrosion, which most commonly takes the form of failure, which generally occurs at 100 mC or above in
pitting. Crevice corrosion is a parallel phenomenon. austenitic stainless steels when a certain threshold
Pitting is insidious because with very little loss of stress is exceeded. A necessary precondition seems to
metal, perforation could cause component failure. be pitting, so again if pitting can be avoided in the
Avoidance of pitting requires knowledge of the initial design, few hazards need be feared from
environment, which permits the appropriate grade corrosion-related phenomena.
selection. A full treatment of the corrosion of stainless steel
The resistance of austenitic stainless steels to pitting, can be found in Lacombe et al. (1990).
and by extension to crevice corrosion, is proportional
to their content of those elements that enhance passive
film stability and the absence of those factors that
9. Oxidation and Creep
diminish it. The resistance to pitting based on alloy
composition is commonly expressed as its pitting The same tendency of chromium to form an adherent,
resistance equivalent number, PREN (Sedriks 1984), stable oxide with low ionic permeability gives aus-
which is given by tenitic stainless steels excellent oxidation resistance.
Increasing chromium and nickel enhance oxidation
PREN l % Crj3.3(% Mo)j16(% N) (6) resistance to a maximum at the 25% chromium\20%
nickel level of the 310 grade. Additions of other
This relationship explains the widely perceived dif- elements that form stable oxides, such as silicon and
ference in corrosion performance between ferritic and aluminum, can also enhance performance. Calcium
austenitic stainless steels. Ferritics contain essentially and rare-earth elements can greatly enhance the
no nitrogen in solution, while austenite dissolves an adherence of Cr O and result in reduced oxidation
amount equivalent in performance to 1–2% of rates, apparently#through
$ their strong effect on sulfur.
chromium. The primary weakness of stainless steels in high-
Corrosion resistance can be degraded by any temperature use is the tendency of the protective oxide
inhomogeneityonthesteelsurfacethatisnotasresistant layer to spall in thermal cycling. In such cases ferritic
to the environment as the steel that surrounds it. So it stainless steels can be preferred.

4
 Austenitic Stainless Steels

Austenitic stainless steels have superior creep The high strength of cold-worked austenitic stain-
resistance to go with their oxidation resistance. The less steel makes it the predominant material for use in
austenite structure is stable and its deformation less transit cars, but also in springs, seatbelt anchors, and
temperature dependent than that of ferrite. Numerous knife blades.
factors can enhance creep resistance. Interstitial Since austenitics are tough even to liquid helium
solutes, such as carbon, boron, and nitrogen, help. temperatures they are widely used in all cryogenic
Substitutional solutes, such as titanium, niobium, and applications. Uniquely, they are equally useful for uses
molybdenum, have a strong effect. Elements such as up to 800 mC, where they find wide use in heat
vanadium and zirconium, which form stable carbides, exchangers, boilers, turbines, furnaces, and auto-
have a predictably good influence. As in other alloys, motive exhaust systems, where the formability of
large grain size improves creep. ferritics or their creep resistance is insufficient.
Nordberg and Bjorklund (1992) contains numerous
papers on the many industrial uses of stainless steel.
But, like the noble metals, stainless steel can also be
10. Applications
used simply for its aesthetic appeal. The numerous
Austenitic stainless steels are used for domestic, surface finishes that can be applied to stainless steel,
industrial, transport, and architectural products based from mirror to matte, do not degrade over time and
primarily on their corrosion resistance but also for keep their appearance as well as their functionality.
their formability, their strength, and their properties at
extreme temperatures. Because their initial cost is See also: Stainless Steels : Martensitic; Stainless Steels:
often higher than that of alternative materials, their Duplex; Ferritic Stainless Steels; Stainless Steels:
popularity is based on their minimization of cost over Cast
the entire life cycle of their use.
The food, pharmaceutical, chemical, pulp and
paper, and petrochemical industries depend heavily on
austenitic stainless steels because their corrosion Bibliography
resistance yields low maintenance, lack of product
contamination, high cleanability, and long life. Ease of Angel T 1954 J. Iron Steel Inst. London 177, 165
Blank J 1988 Stainless Steels ’87. Institute of Metals, London
welding and fabrication are important in these appli- Boyer H, Gall T 1985 Metals Handbook Desk Edition. American
cations, but stainless is used simply because it is the Society For Metals, Metals Park, OH
most economical material that can do the job. Initial Lacombe P, Baroux B, Beranger G 1990 Les Aciers Inoxydables.
cost is often a poor measure of a material, such as in Les Editions de Physique, Paris
the case of concrete reinforcing bars, where the entire Nicodemi W 1993 InnoŠation in Stainless Steel. Associazone
structure is jeopardized by corrosion of a minor Italiana di Metallurgia, Milan
component. Specifying stainless steel can eliminate Nordberg H, Bjorklund J 1992 Applications of Stainless Steel.
such problems at a small premium to the overall Kristianstads Boktryceri, Stockholm
cost. Peckner D, Bernstein I 1977 Handbook of Stainless Steel.
Sometimes formability becomes an equally import- McGraw-Hill, New York
Pickering F, Irvine K, Gladman T 1969 J. Iron Steel Inst. London
ant a requirement as corrosion resistance. Stretch- 1017
formed parts, such as sinks, are an example of the use Sedriks A 1979 Corrosion of Stainless Steel. Wiley-Interscience,
of the more unstable austenitic grades, while the highly New York
stable grades are used for deeply drawn parts or for Sedriks A 1984 Stainless Steels ’84. Institute of Metals, Go$ te-
components where low magnetic permeability is borg, Sweden
sought. Automotive filter bodies, pen cartridges, Suutala N 1983 Metall. Trans. 191–7
cooking pots, and disk drive parts are examples of the
latter. M. F. McGuire

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Encyclopedia of Materials : Science and Technology
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