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JOURNAL OF IRON AND STEEL RESEARCH, INTERNATIONAL. 2012, 19(7): 55-59
Microstructure Evolution in 9Cr Martensitic Steel During
Long-Term Creep at 650 "c
HU Zheng-fei' , WANG Qi-jiang' , ZHANG Bin'
(1. School of Material Science and Engineering, Tongji University, Shanghai 200092, China;
2. Institute of Baosteel, Shanghai 201900, China)
Abstract: Standardarized creep and rupture strength tests were conducted for commercial T91 martensitic heat-resist-
ant steel at 650 'C and corresponding microstructure was characterized by BSED, TEM and EDS. The martensitic
microstructure degenerated seriously during creep exposure, including martensitic substructure recovering, carbides
coarsening, dissolving and precipitating. EDS analysis shows that the M23 C6 carbides in different morphologies have
dissimilar compositions. The rod/sheet like MZ3 Cs particles within the matrix contain more additions, which might
precipitate in situ while fine MX particles were re-solving. The high content of silicon in these rod/sheet like MZ3Cg
carbides is probably related to self diffusion coefficient increasing for the exposed condition at 650 C close to Curie
temperature T,. For those reasons, martensite substructure becomes unstable, and microstructure evolution is accel-
erated and leads to creep strength deteriorating severely.
Key words: T91 steel; creep strength; microstructure; carbide; coarsening; self-diffusion
Tempered martensitic steels with Cr of 9% are
most popular materials used as components in power
plant due t o their excellent mechanical properties at
high Their prominent creep strength
with suitable toughness is achieved by martensitic mi-
crostructure coupled with dispersive distribution of
fine precipitates. The microstructure consists of
lath, block and packet martensite containing a high
density of dislocations and fine carbonitride parti-
cles. For long-term steady performance in practical
service condition, it is suggested that t he stability of
martensitic microstructure at elevated temperature is
i mp ~ r t a n t ~ ~ - ~ ' . In advanced 9CrlMo steels, high
creep strength has attained by the addition of V, Nb
and N which form fine precipitatesC5]. Furthermore,
in order to achieve anti-oxidation at high tempera-
t ure, the minor additions of silicon and sulphur are
From the past studies, the silicon ad-
dition effects on the long-term stability of martensit-
ic microstructure and creep resistance at high tem-
perature are not well understood. The present paper
describes the creep behavior and microstructure evo-
lution in T91 martensitic steel at 650 "C. More atten-
tion is paid to the fine characteristics of microstructure
evolution as well as precipitation behavior during
creep at temperature close to Curie temperature.
1 Experimental Procedure
A typical commercial T91 martensitic steel was
employed. Its chemical compositions (in mass percent,
%) were analyzed to be Cr 8. 3 , Mo 0. 90, Mn 0. 4 , Si
0. 32, V 0.21, Nb 0. 09, Ni 0. 09, and C 0.11. Creep
tests were carried out at 650 "C ( 923 K) up to about
2 X l o4 h under constant load condition, using speci-
mens of 10 mm in gauge diameter and 25 mm gauge
in length. The microstructure evolution during creep
was observed by BSED (backscatting scanning elec-
tron microscope) and TEM (transmission electron
microscope). To examine the size and composition
of the precipitates, extraction replicas as well as thin
foils were prepared and analyzed using spectroscope
EDS method. The methods of preparing the samples
are described in many references[*'
2 Results and Discussion
Fig. 1 shows t he results of accelerated test at
Foundation 1tem:Item Sponsored by National Natural Science Foundation of China (50871076)
Biography:HU Zheng-fei(l964-), Male, Doctor, Professor; E-mail: huzhengfatongji. edu. cn; Received Date: February 14, 2011
56 - Journal of I r on and Steel Research, International VOl. 19
.-
10 102 103 101 10
Timeih
Fig. 1 Plot of stress with rupture time exposed at 650 C
650 *C. Stress rupture data have been plotted in term of
log stress with rupture time. The curve shows that
stresses are linear with rupture times; t hus, t he
threshold st rengt h of t he examined T91 at 650 C
was determined by extrapolation method as follows :
Thi s result conforms t o t he requirement of
ASTM standard and is identical t o t he values given
by other reportsi3991.
Fig. 2 illustrates t he transmission electron mi-
crograph of t he examined T91 material in as-received
state. It clearly shows a typical lath martensitic micro-
structure, with carbides distributing along boundaries
and much finer particles in t he matrix.
It is known that t he steels with Cr of 9%-12%
&Q =57. 1 MPa (1)
Fig. 2 Transmission electron micrograph from
as-received microstructure
contain several precipitate types, such as M2,C6, MX
and Laves, which form either during t he final nor-
malizing and tempering heat treatment or during
subsequent creep exposure. These various precipi-
tates have special chemical compositions, which
mean that it is possible t o discriminate between them
by measurements of their chemical composition.
SEM can obtain backscattered electron (SEM-BSE)
images which present t he atomic number contrast t o
discriminate between particles. Fig. 3 gives the SEM-
( a) 140 MPa, 115 h;
Fig. 3
( b) 130 MPa, 386 h; ( c ) 120 MPa, 3685 h ; ( d) 110 MPa, 12353 h.
SEM-BSE images of accelerated test samples ruptured at 650 c under different stresses
Issue 7 Microstructure Evolution in 9Cr Martensitic Steel During Long-Term Creep at 650 C . 57
BSE images of the samples for accelerating rupture
tests under different stresses. It shows that the sizes
of the precipitates distributing along grain bounda-
ries increase obviously, especially the M,, c6 parti-
cles along prior austenitic boundaries have been
coarsened during creep deformation. The fine pre-
cipitates within the matrix do not exhibit obvious
coarsening. However the density of these fine parti-
cles within the matrix decreases with the rupture
time prolonging. It means that the precipitates
coarsen obviously during long-term rupture life. In
Fig. 3 ( d ) , the contour of prior austenite grain
boundaries outlined by M,, C6 become much more
clear but lath boundaries are indistinct or even disap-
peared. These indicate the martensitic lathes have
undergone a degeneration during long-term accelera-
ting at 650 C. The coarsening of laths is processing
by two ways, the recovery of dislocations within
lath boundaries and the recombination of two sub-
grain boundaries which mainly takes place near the
triple point of lath boundaries by moving and causes
0 2 4 6 8 10
the disappearance of lath boundaries. Furthermore,
during moving of lath boundaries to cause progres-
sive local-coalescence, dissolution and re-precipitati-
on of M2,C6 carbides distributing along lath bounda-
ries take place repeatedly.
What observed above is totally coincident with
the results mentioned by others[4391 that the rupture
strength of T/P91 deteriorates obviously over 600 C
and this characteristic is relative to the unstable mi-
crostructure for the much faster coarsening process
of carbides and lath structure.
The composition of the carbides is determined
in TEM via energy dispersive microanalysis (EDS) ,
as shown in Fig. 4. The unlabeled peaks in Fig. 4 are
from copper grids. It is shown that the carbides along
boundaries are Cr rich [Fig. 4 ( a) ] and correspond-
ing electron diffraction pattern inserted in Fig. 4 ( a)
is identified as M,,C, in the [lll] orientation. Other
fine precipitates dispersive within the matrix are
confirmed to be rich in V-rich or Nb-rich [Fig. 4
( a ) , marked as A in Fig. 5 (a)]. The inset electron
2 4 6 8 10 12 14 16 18 20
EncrgykeV
Fig. 4 EDS X-ray spectra of extraction replica from sample ruptured at 650 c under 140 MPa for 115 h
0 2 4 6 8 1 0 0 2 4 6 8 1 0 0 2 4 6 8 1 0
EnergykeV
(a) 140 MPa, 115 h; ( b) 120 MPa, 3386 h ; ( c ) 120 MPa, 12353 h.
Fig. 5 Typical TEM micrographs of extraction replica of accelerated test samples at 650 c under different
stresses and EDS X-ray spectra from particles B (d) , C (e) and D ( f )
58 . Journal of Iron and Steel Research, International VOl. 19
diffraction pattern in Fig. 4 ( b ) is identified as MX
carbonitrides and the zone axis is [112]. Even though
the MX carbonitrides seem highly stable against coarse-
ning for their sizes without obvious variety, their
number density tends to reduce. This implies that
partial MX particles have redissolved during long
term exposure at 650 "C.
Fig. 5 displays some rod or sheet like particles
marked as B, C and D, which are presented within
the matrix and some along grain boundaries. They
are much larger than those MX particles and also
recognized as Mz3 Cg by selected area diffraction
(SAD). From their sizes and morphologies, it im-
plies that these carbides within the matrix did not
undergo coarsening, so they are considered to be
precipitated during the accelerating test period.
Fig. 5 also indicates that the much complex composi-
tions of these Mz3Cg carbides and dominant elements
are chromium, iron, molybdenum, vanadium and
silicon. With the density of MX particles decreasing,
it implies that the precipitation of these M'sCg parti-
cles formed subsequently to the dissolving behavior
of MX. In other words, the MX particles in T91 are
not stable while exposing at 650 "C and apt to trans-
form into more stable M'3C6 carbides. These M23C6
particles form in-situ while MX dissolving. The EDS
spectra in Fig. 5 show a special phenomenon in the
rod/sheet like carbides. There is obvious silicon in
their alloying compositions and the Si content (atom
percent) is quite high ( as much as 1 7 %) and vary
strikingly between particles. However no silicon is
found in fine MX particles within the matrix and no
obvious silicon is detected in the Mz3C6 carbides in
different appearances along grain boundaries (Fig. 4).
In ferritic steels with Cr of 9%-12%, the ac-
tions of Si and Mn are contradictory to each other;
Si is a ferrite former, whereas Mn is an austenite
former. It has been claimed that ferritic steel has
better creep rupture when it has low concentration
of Si and Mn["-''' . Reduction of the contents of
both of these elements can lead to a low self-diffu-
sion coefficient in the ferrite matrix and improve
creep strength. Si works to decrease toughness by
promoting the Laves phase, whereas Mn, though
useful for toughness improvement, can impair the
high temperature stability of the ferrite structure by
decreasing the A, transformation temperature in the
same manner as Ni. From another point of view, the
addition of 9-12Cr in combination with appropriate
minor elements, such as silicon and sulphur, is re-
quired from the viewpoint of suitable high-tempera-
ture oxidation resi ~t ance"~' .
The facts of MX dissolving and rod/sheet like
Mz3 c6 carbides precipitating with high silicon con-
tent might be related to the compositions of the ex-
amined steel and high temperature. From the points
of past studies, diffusion coefficient is the most im-
portant parameter in creep, and is required to be as
small as possible in order to retain fine particles for
long duration and to slow down the recovery of the
martensitic substructure. It is known that ferritic
steel transforms from a para- to a ferro-magnetic
state near Curie temperature T, , and its self-diffu-
sion coefficient is reduced by the magnetic transfor-
mation['". Generally, high Cr ferritic steel is used
in this temperature regime just below T,. The diffu-
sion coefficient increases with decreasing T, of the
material. The additions of Si, Mn and Ni increase
diffusion coefficient for their effects to decrease Cu-
rie temperature. In the present study, the examined
samples were exposed at 650 "C which is close t o
Curie temperature, so the self-diffusion coefficient
might increase obviously. All these might promote
MX dissolution and new Mz3c6 precipitation, mean-
while, silicon segregates markedly into these Mz3 c6
particles within the matrix. That means the micro-
structure of T91 steel becomes unstable when expo-
sing at 650 "C under certain stress. With self-diffu-
sion coefficient increasing, the microstructure evolu-
tion is accelerated obviously, including MX precipi-
tates dissolving, rod/sheet like MZ3 C, carbides precipi-
tating and martensitic substructure undergoing re-
covery. These microstructure evolutions lead t o
creep strength deteriorating severely. The silicon
segregating to carbides or boundaries might be a sign
for the deterioration at high temperature for 9Cr
martensitic steels.
3 Conclusions
1) Creep strength of T91 martensitic heat-re-
sistant steel deteriorates severely when it exposed at
650 "C under certain stress and corresponding micro-
structure becomes unstable.
2 ) Martensitic substructure undergoes recovery.
The phenomena of carbonitrides MX re-dissolving
and particles of Mz3Cg forming in-situ, lead to M2,C6
carbides with different morphologies and dissimilar
composition.
3 ) The microstructure evolution is accelerated
obviously which may be related to enhancing self-dif-
fusion coefficient at 650 "C near Curie temperature.
Issue 7 Microstructure Evolution in 9Cr Martensitic Steel During Long-Term Creep at 650 C * 59
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