Materials Science and Engineering A319– 321 (2001) 788– 791

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Microstructural evolution and change in hardness in type 304H

stainless steel during long-term creep
H. Tanaka *, M. Murata, F. Abe, H. Irie
Frontier Research Center for Structural Materials, National Research Institute for Metals, 1 -2 -1 Sengen, Tsukuba, Ibaraki 305 -0047, Japan

Abstract

The microstructural evolution and the change in hardness have been investigated for 18Cr– 8Ni (type 304H) stainless steel
during long-term creep. Creep and creep-rupture tests were carried out at temperatures between 550 (823) and 750°C (1023 K) for
up to 180 000 h. The hardening behavior during creep depends on the stress level, as well as the precipitation of M23C6 carbides
and s phase. At a high stress of 177 MPa, the hardening during creep is much larger than the age hardening, indicating that the
hardening during creep is mainly caused by the strain hardening due to creep deformation. At a later stage of creep, the softening
occurs due to the recovery of excess dislocations, which becomes more significant with decreasing stress and increasing test
duration. The strain hardening disappears with decreasing stress level and increasing test duration. At a low stress of 61 MPa or
less, the hardening during creep can be approximately given by the age hardening under no stress, except for the final stage of
creep. © 2001 Elsevier Science B.V. All rights reserved.

Keywords: Microstructural evolution; Type 304H; Long-term creep

1. Introduction present, little is known about the microstructure evolu-

Austenitic stainless steels, such as type 304 (l8Cr –
8Ni), 316 (l8Cr – l2Ni – Mo), 321 (18Cr – 10Ni –Ti) and
347 (18Cr –12Ni – Nb) steels, are widely used as high-
temperature components, such as boilers, superheaters
and chemical reactors, which require good mechanical
properties and corrosion resistance at temperatures up
to 650 –700°C. It is well known that long-term exposure
of the steels to stress at these temperatures can cause
microstructure evolution and creep deformation leading
ultimately to creep-rupture. Of the steels, the type 304
steel exhibits the simplest microstructure where only
M23C6 carbides and s phase precipitate at high temper-
atures, while the microstructure of the other steels are
complicated [1]. Several investigations have dealt with
the microstructure evolution in the type 304 steel during
thermal aging and creep [2,3]. But these studies are
limited to specimens tested in periods not exceeding
60 000 h, while high-temperature components are usu-
ally operating for long periods exceeding 100 000 h. At
* Corresponding author. Tel.: + 81-298-592219; fax: +81-298-
592201.
E-mail address: hide@nrim.go.jp (H. Tanaka).
tion during long-term creep for up to 100 000 h or more.
The present authors and co-workers have investigated
comprehensively the microstructure evolution during
creep and its effect on long-term creep strength for type
304H steel, where the term H means high carbon
concentration, using specimens tested in the NRIM
Creep data sheet project [1,4 –6]. A number of micro-
graphs for the type 304H steel were recently published
in ‘Metallographic Atlas of Long-term Crept Materials’
[7]. In the present research, the relationship between the
microstructure evolution and the change in hardness has
been investigated for the type 304H steel during creep
for up to 180 000 h at high temperature. The measure-
ment of hardness is frequently used for estimating
materials degradation and remaining life for high-tem-
perature components.
2. Experimental procedure
The material used was the commercially produced
heat ABE of 18Cr –8Ni steel (304H TB) in the NRIM
Creep Data Sheet No. 4B [8], where the creep rupture
data were presented for nine heats of 18Cr –8Ni steel.

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 H. Tanaka et al. / Materials Science and Engineering A319–321 (2001) 788–791
The chemical compositions of the steel used were
0.07C, 0.55Si, l.46Mn, 0.3P, 0.006S, 9.57Ni, 18.95Cr,
0.04Mo, 0.07Cu, 0.062Ti, 0.014Al, 0.0018B, 0.0278
(mass percentage) N and Fe, balance. The creep speci-
mens, having a geometry of 6 mm in diameter and 30
mm in gauge length, were taken longitudinally from the
middle of the wall thickness of the as-received boiler
tube. The tube had a size of 50.8 mm in outer diameter
and 8 mm in wall thickness and was already solution
annealed. Creep and creep rupture tests were carried
out for up to about 180 000 h at temperatures between
550 (823) and 750°C (1023 K). The longitudinal cross-
section of the gauge and head (or grip) portions of the
specimens was observed using optical, scanning and
transmission electron microscopes (SEM and TEM).
The head portion can be regarded as an unstressed
portion. The Vickers hardness was measured at a load
of 49 N (5 kgf mm − 2). The indentation size at this load
Fig. 1. Stress versus time to rupture for the heat ABE of type 304H
steel.
Fig. 2. Vickers hardness of (a) head and (b) gauge portions of
creep-ruptured specimens, as a function of duration of creep rupture
testing.
789
was 200–240 mm which corresponds to two or three
times the average grain size.
3. Results and discussion
3.1. Creep rupture strength
Fig. 1 shows the stress versus time to rupture data.
The solid curves are drawn on the based of the time-
temperature parameter method of Manson-Haferd [8].
The creep fracture modes for the 304H steel are divided
into regimes of transgranular fracture (denoted by T)
and three types of intergranular fracture; the wedge-
type cracking (W), the creep cavitation associated with
M23C6 carbides at grain boundaries (C) and the s/
matrix interface cracking along grain boundaries (s)
[4,5]. The present results suggest that the creep fracture
modes at long times above about 10 000 h are closely
connected with the precipitation behavior of M23C6
carbides and s phase.
3.2. Change in hardness during aging and creep
Fig. 2 shows the Vickers hardness for both the head
and gauge portions of creep-ruptured specimens as a
function of duration of creep rupture testing. The Vick-
ers hardness in the as-received condition was 160. The
specimen head portion under no stress exhibits the two
step age hardening, short-term age hardening at times
less than 1000 h and long-term age hardening at times
above 10 000 h. The short-term age hardening occurs
substantially at short times less than 100 h and the
hardening DH = H−H0, where H and H0 are the hard-
ness at time t and in the as-received condition, respec-
tively, is relatively small 10–15. The long-term age
hardening becomes more significant with time above
10 000 h at around 600°C and is much larger than the
short-term age hardening. Fig. 3 shows the microstruc-
ture evolution with time in the specimen head portion
at 650°C. The TEM observations show that the precip-
itation of M23C6 carbides started to occur from short
times less than 1 h but that of the s phase needed long
times above about 10 000 h at around 600–650°C.
Therefore, the short-term and long-term age hardening
in Fig. 2a results from the precipitation of M23C6
carbides and s phase, respectively.
In the gauge portion of creep-ruptured specimens,
the hardness decreases with time at temperatures except
for 600°C where there is a tendency to increase again at
long times above 10 000 h. The change in hardness with
time for the gauge portion results from the change in
dislocation density produced by creep deformation as
well as the precipitation hardening due to the M23C6
carbides and s phase described above. It should be
noted that the solid lines in Fig. 2b are connecting the
790 H. Tanaka et al. / Materials Science and Engineering A319–321 (2001) 788–791
Fig. 3. Change in TEM microstructure during thermal aging at
650°C. (a) As-received, (b) 71.9 h, (c) 13 718.5 h and (d) 100 491.4 h.
Fig. 4. Creep curves of type 304h steel at 177, 118 and 61 MPa at
650°C.
data points for the creep-ruptured specimens which were
tested at different stress levels as shown in Fig. 1. In
general, resultant dislocation density and resultant dislo-
cation arrangements in the specimens are strongly influ-
enced by stress level in creep rupture testing. This
suggests that the solid lines in Fig. 2b cannot represent
the test duration dependence alone but that they also
involve the effect of stress level.
In order to exclude a possible influence of stress level,
the change in hardness was measured as a function of
time during creep at a constant load condition. The creep
tests were carried out at 650°C and at three different
stress levels, 177, 118 and 61 MPa at which the time to
rupture tr was 71.9, 2621.3 and 100 491.4 h, respectively.
Fig. 4 shows the respective creep curves. The creep tests
were interrupted at times shown by the arrows in Fig. 4
and then the hardness was measured. Fig. 5 shows the
change in hardness during creep as functions of time (Fig.
5a) and normalized time t/tr (Fig. 5b). In this figure, the
hardness in the specimen head portion under no stress
is also shown by the dotted line for comparison. At a high
stress of 177 MPa, the hardness increases for up to 50
h, corresponding to t/tr= 0.7, then decreases slightly and
again increases just before creep-rupture. The hardness
in the specimen gauge portion is much larger than that
in the specimen head portion under no stress over a
whole range of test duration, indicating that the harden-
ing during creep is mainly caused by the strain hardening.
The precipitation of M23C6 carbides occurs during
creep but the precipitation hardening DH due to M23C6
carbides is relatively small as described above. The TEM
observations showed that the dislocation density in-
creased for up to 50 h (t/tr= 0.7) at which the accumu-
lated creep strain is 0.16 as can be seen from
Fig. 5. Vickers hardness during creep as functions of (a) time and (b)
normalized time t/tr at 650°C.
 H. Tanaka et al. / Materials Science and Engineering A319–321 (2001) 788–791
Fig. 4. At 65 h (t/tr =0.9), the matrix having low
density of dislocations was surrounded by walls of high
dislocation density, indicating that rearrangement of
excess dislocations had occurred during creep. In the
final stage of creep above 65 h, an increase in disloca-
tion density was observed again in the matrix. At 118
MPa, there is not a large difference in hardness between
the specimen gauge and head portions for up to about
1000 h but the hardness in the specimen gauge portion
increases rapidly with time above 1000 h followed by
softening after reaching a maximum at about t/tr= 0.8.
At short times less than 1000 h, the hardening during
creep is determined mainly by the precipitation harden-
ing due to the M23C6 carbides but the strain hardening
is not large, because the creep strain is relatively small
0.04 or less as can be seen in Fig. 4. The rapid increase
in hardness above about 1000 h correlates with the
rapid increase in creep strain, indicating strain harden-
ing. The softening in the final stage of creep is consid-
ered to result from the recovery or rearrangement of
excess dislocations and the coarsening of precipitates.
At a low stress of 61 MPa, the hardening during creep
is approximately the same as the age hardening for
almost whole range of test duration, except for the final
stage of creep where the softening occurs as at 118
MPa. This suggests that the hardening during creep is
determined substantially by the precipitation hardening
due to the M23C6 carbides at short times and due to the
s phase at long times above 10 000 h. The strain
hardening is much smaller at 61 MPa than at 177 and
118 MPa. The effects of recovery or rearrangement of
excess dislocations and of coarsening of precipitates
become more significant with decreasing stress, because
the test duration becomes longer and the creep defor-
mation rate becomes lower with decreasing stress. The
present results indicate that the difference in hardness
between the specimen gauge and head portions disap-
pears with decreasing stress level and that the harden-
ing during creep under stresses less than 61 MPa can be
approximately given by the age hardening under no
stress, except for the final stage of creep.
In Fig. 2b, the hardness in the creep-ruptured speci-
mens decreases with increasing temperature except for
600°C. This is also correlated with an increased effect
of recovery of excess dislocations with increasing tem-
perature, depending on self-diffusion rates. The increase
in hardness at long times above 10 000 h at 600°C is
caused by the large precipitation hardening due to the
s phase.
3.3. Application to e6aluation of long-term operating
components
Most of high-temperature plants using type 304
austenitic steel are being operated for long times greater
791
than 100 000 h, indicating a low stress condition pre-
sumably much less than 61 MPa at 650°C. Therefore,
for estimating materials degradation or remaining life
for type 304 austenitic steel components, the hardness
can be approximated by the age hardening under no
stress and the results shown in Fig. 2a can be used as
reference or standard data. By comparing the hardness
of the components with the data shown in Fig. 2a and
by observing microstructure, we can also estimate the
operating conditions, such as operating temperature
and time, for the components.
4. Conclusions
During thermal aging under no stress, the precipita-
tion of M23C6 carbides and s phase causes the age
hardening at short times below 1000 h and at long
times above about 10 000 h, respectively, at around
650°C.
The hardening behavior during creep at 650°C de-
pends on stress levels as well as the precipitation of
M23C6 carbides and s phase. At a high stress of 177
MPa, the hardness increases for up to t/tr=0.7, then
decreases slightly and again increases just before creep-
rupture. The hardening during creep is much larger
than the age hardening, indicating that the hardening
during creep is mainly caused by the strain hardening.
The strain hardening disappears with decreasing stress
level and increasing test duration.
For estimating materials degradation or remaining
life for type 304 austenitic steel components, which are
usually operated under stresses presumably less than 61
MPa, the hardness can be approximated by the age
hardening under no stress, except for the final stage just
before creep-rupture.
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