Metallographic Study of

Type 304 Stainless Steel Long-Term

Creep-Rupture Specimen
V. A. BISS AND V. K. SIKKA
Types 304 and 316 austenitic stainless steel are
developed for structural applications between 450 and
700 ~ Prolonged exposure to stress at operating
temperature causes microstructural changes and creep
deformation leading to grain boundary cavitation and
ultimately intergranular failure. Several publications ~-6
deal with the microstructure of stainless steel exposed
to creep or thermal aging. However, these studies are
generally limited to specimens aged or ruptured in
periods not exceeding 10,000 h. Relatively little is
known about the microstructural changes accompanying long-term exposure to creep stress. Previous
microstructural analysis of long-term creep rupture by
Biss e t a l 7 was performed on specimens with rupture
times approaching about 49,000 h at 595 and 650 ~
We extend that work to the microstructural analysis
o f a type 304 stainless steel specimen that exhibited a
59,900 h (6.84 year) rupture life at 595 ~ and 117 MPa.
The test specimen came from a commercially produced heat of type 304 stainless steel having the following chemical analysis (wt pct): C, 0.068; Cr, 18.8;
Ni, 9.43; Mn, 0.83; Si, 0.59; Mo, 0.07; Nb, 0.01; V,
0.025; Ti, 0.002; Ta, <0.0005; W, 0.006; Cu, 0.15;
Co, 0.05; Pb, 0.01; Sn 0.02; N, 0.031; P, 0.018; O,
0.0042; H, 0.0005; S, 0.008; and Fe, balance. Before
testing, the bar stock was annealed at 1065 ~ and
water quenched.
The techniques employed in this study consisted of
examination of microstructures by optical and electron microscopy and identification o f phases by electron diffraction and energy-dispersive X-ray (EDX)
microanalysis. Metallographic specimens were prepared from longitudinal sections o f the gage length
adjacent to the fracture and from the low-stress
region near the end of the test bar. The specimens
were mechanically polished with conventional polishing techniques and electrolytically etched as cathodes
in 50 pct aqueous HNO3 at 20 V.
Carbon extraction replicas were prepared by using a
two-stage carbon extraction technique, involving dualcomponent synthetic resin as a primary dry stripping
medium and carbon substrate as a secondary extraction replica. The phases present on the replicas were
examined in a 100 kV transmission electron microscope
and were identified by selected-area electron diffraction. The compositions of the phases were determined
by EDX analysis by using an energy-dispersive spectrometer interfaced with a scanning electron microscope.
V. A. BISS is Senior Research Associate, Research Laboratory,
Climax Molybdenum Company of Michigan, P.O. Box 1568, Ann
Arbor, MI 48106, and V. K. SIKKAis Research Associate, Metals
and Ceramics Division, Oak Ridge National Laboratory, Oak
Ridge, TN 37830.
Manuscript submitted October 22, 1980.
1360--VOLUME 12A, JULY 1981

The microstructures in the low-stress region and the

gage length of the test bar are illustrated by the optical micrographs in Fig. l(a) and (b), respectively.
Both sections contain fine precipitate particles
throughout the matrix and along the twin and grain
boundaries. The precipitate was identified as M23C 6 by
electron diffraction analysis of extraction replicas.
The lattice size was calculated to be a0 = 1.068 nm,
which correlates reasonably well with that of Cr23C 6
(a0 = 1.064 nm). An EDX analysis of the extracted
carbide particles, which contained chromium as the
only metallic component, substantiated the identity of
the fine matrix precipitate as Cr23C 6. In Fig. l(a), the
Cr23C 6 particles are appreciably concentrated along the
grain boundaries. In the gage section [Fig. l(b)], the
carbide particles are more uniformly distributed. Most
of the Cr23C 6 in both sections of the test bar consisted
of rectangular 50 to 100 nm particles, as illustrated by
the extraction replica electron micrograph in Fig. 2.
In the low-stress region, Cr23C6 appears to be the
only precipitate formed. In the gage length, creeprupture testing at 595 ~ produced sigma phase in
addition to the Cr23C6. Sigma phase precipitated primarily along the austenite grain boundaries, as illus-

Fig. 1--Longitudinal sections through type 304 stainless steel after

59,900 h creep-rupture test at 595 ~ and ll7 MPa. (a) Low-stress
region near end of bar. (b) Gage section near fracture. Regions of
localized grain boundary migration are marked A.

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9 1981 AMERICAN SOCIETY FOR METALS AND
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Fig. 2--Morphology of Cr23C 6 particles extracted from the gage

length of the creep-rupture bar (transmission electron micrograph
of carbon extraction replica).

trated in Figs. l(b) and 3, and was frequently associated with localized grain boundary migration [regions
marked A in Fig. l(b)], leaving behind a matrix free
of carbide precipitate. Sigma phase was identified by
electron-diffraction analysis of several particles present
on extraction replicas. Its composition from EDX
analysis was approximately Fe0 6Cr0.4 . The Cr23C 6 particles in the gage section were oriented preferentially
along crystallographic planes of the austenite matrix,
as shown in Figs. l(b), 3, and 4(a).
Several locations of the gage length showed islands
containing elongated precipitate particles, as illustrated
in Fig. 4. By EDX analysis these islands contained
over 22 pct Cr and less than 1 pct Ni. This composition suggests that during exposure austenite transformed locally to ferrite in the high-stress region. The

Fig. 4--1slands of 6-ferrite containing fine sigma phase particles in

the gage length of the creep rupture specimen (scanning electron
micrographs).
~ ' " f~-n'~ t o i d o n t i f v nositively. The
Vqidmanstatten-type microstructural features in the
lower left-hand corner of Fig. 4(a) and lower righthand corner of Fig. 4(b) are martensite formed during
polishing.
The general microstructural features, such as the
presence of M23C 6 plus sigma phase and the stressinduced grain boundary migration, are consistent with
earlier results7 on long-term creep-rupture specimens
of type 304 stainless steel with rupture lives up to
49,000 h. The present results, however, differ in two
ways: the absence of M 6 C and the presence of ferrite
in the microstructure.
The M 6 C w a s present as a grain boundary carbide
in the specimens studied earlier. Since the growth of
the sigma phase is associated with a simultaneous dissolution of carbide particles, 8,9 we may presume that,
if M 6 C formed at any stage during the creep exposure,
the subsequent growth of the sigma phase along the
grain boundaries caused dissolution of both M 6 C and
M23C 6. Since the present specimen sustained longer
rupture life than earlier ones, we expect that the carbide particles dissolved until M 6 C completely disappeared.

~r~ . . . . . . . .

islands are presumed to be fine sigma phase. The

Fig. 3--Massive sigma phase and fine Cr23C 6 particles precipitated

during creep exposure in the gage length (scanning electron micrograph).
METALLURGICAL TRANSACTIONS A

VOLUME 12A, JULY 1981--1361

Ferrite in austenitic stainless steel is recognized as a

metastable transition phase, which subsequently transforms to s i g m a : Such transformation is clearly evident from the scanning electron micrographs in Fig. 4,
where sigma phase particles appear at the austeniteferrite interfaces and within the ferrite grains.
In summary, long-term exposure of type 304 austenitic stainless steel to creep-rupture testing at 595 ~
causes 1) precipitation of Cr23C6, 2) stress-induced
grain boundary migration associated with simultaneous dissolution of Cr23C6 particles and formation of
iron-chromium sigma phase, and 3) localized formation of ferrite as a metastable transition phase, which
subsequently transforms to sigma.
This research was sponsored by the Division of
Reactor Research and Technology, U.S. Department
of Energy, under contract W-7405-eng-26 with the
Union Carbide Corporation.

1. V. K. Sikka, R. W. Swindeman, ~nd C. R. Brinkman: Metall.

Trans. A , 1977, vol. 8A, pp. 1117-29.
2. V. K. Sikka, C. R. Brinkman, and H. E. McCoy: Structural
Materials f o r Service at Elevated Temperatures in Nuclear
Power Generating Systems, MPC-1, pp. 316-50, American

Society of Mechanical Engineers, New York, 1975.

3. E. F. Etienne, W. Dorrland, and H. B. Zeedijk: Int. Conf.
Creep and Fatigue in Elevated Temperature Applications, vol.
I. pp. 225.1-225.9, Mechanical Engineering Publications, Ltd.,
London, 1975.
4. J. E. Spruiell, J. A. Scott, C. S. Ary, and R. L. Hardin:
Metall. Trans., 1973, vol. 4, pp. 1533-44.
5. B. Weiss and R. Strickler: Metall. Trans., 1972, vol. 3, pp.
851-66.
6. C. J. Bolton et al: Mechanical Behavior o f Materials, vol. 2,
pp. 183-92, Pergamon, Oxford and New York, 1979.
7. V. A. Biss, D. L. Sponseller, and M. Semchyshen:J. Mater.,
1972, vol. 7, pp. 88-94.
8. W. E. White and I. LeMay: Metallography, 1972, vol. 5, pp.
333-45.
9. L. K. Singhal and J. W. Martin: Acta Metall., 1968, vol. 16,
pp. 1441-51.

Time Dependent Stress-Strain

Curves of Nonlinear Anelastic Solids

intentional when automodulation is studied. Another

observation peculiar to a large deformation in the
vicinity of the martensitic transformation is the stressstrain curve, recent examples of which can be found in
the work of Otsuka, Shimizu, W a y m a n and Coil) These
stress-strain curves are strongly nonlinear at large
strains where martensite is induced. In addition, they
display a pronounced hysteresis at large strains. In this
letter, it will be shown that b o t h of these characteristics
also constitute essential features of a nonlinear anelastic
solid. It is thus possible to interpret the stress-strain
curve when martensite is strain induced in terms of the
properties of this solid.
The fact that martensite can be strain induced means
that the austenitic phase possesses a metastable state.
The free energy of this metastable state can be lowered
by the application of an external stress. If this stress is
sufficiently high, the martensitic phase becomes stable.
The free energy, F, of austenite may thus be described
by the polynomial
F(?Q =

1 / 2 C 2 h 2 + l/4C4~k4 + 1/6C6 ~6.

[1]

The quantity ~ is a deformation parameter suitable to

describe a tensile test, 2~ = (1 - lo)/lo. Here, l o is the
original sample length and l - l o denotes the travel of
the crosshead. The constants C, are macroscopic mechanical constants characteristic of the material under
test. It is noted that F(~) has a secondary minimum, i.e.,
a metastable state if ( C 4 / 2 C 6 ) 2 ~ C : / C 6.
The formation of martensite takes time. This aspect is
not reflected in Eq. [1]. It m a y be introduced by treating
the free energy as a time-dependent quantity. Such an
approach, if carried out rigorously, renders the problem
very complex. A simple way of introducing the element
of time consists of defining two free energies--an
unrealaxed free energy, F , , and a relaxed free energy,
Fr. The former refers to very fast deformations and
introduces the nonequilibrium aspect. The latter refers
to very slow deformations and describes the equilibrium
relationship of the phases involved. Unrelaxed and
relaxed free energies have been introduced successfully
before to describe the properties of a linear anelastic
solid: The present approach thus constitutes an extension of a proven concept to large deformations, i.e. to a

.1

MANFRED WUTTIG AND TETSURO SUZUKI

The concept of nonlinear anelasticity has previously
been introduced to interpret two interesting phenom e n a - s t r e a m i n g ~and automodulation. ~ Both are observed in the vicinity of a martensitic transformation.
According to this interpretation, both phenomena have
in c o m m o n that they result from large periodic or
better, finite, mechanical deformations. This deformation is almost incidental in the case of streaming but

~v/," "X

/.- ~, vl I
.05

MANFRED WUTTIG is Professorof Metallurgical Engineering

at the Universityof Missouri-Rolla, Rolla, MO 65401. TETSURO
SUZUKI is Professorof Applied Physicsat the University of
Tsukuba, Sakura, Ibaraki 305 Japan.
Manuscript submitted January 7, 1980.
1362--VOLUME 12A, JULY 1981

Fig. 1--Qualitative plot of the unrelaxed and relaxed free energies as

a function of the deformationin the vicinity of a martensitic
transformation. The quantity F is plotted in units C,2.

ISSN 0360-2133/81/0713-1362500.75/0
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METALLURGICALTRANSACTIONSA