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Investigation of the Dynamic Strain Aging and Mechanical Properties in

Alloy-625 with Different Microstructures

Article  in  Metallurgical and Materials Transactions A · March 2015

DOI: 10.1007/s11661-014-2717-z

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Investigation of the Dynamic Strain Aging and Mechanical
Properties in Alloy-625 with Different Microstructures
ARNOMITRA CHATTERJEE, GARIMA SHARMA, R. TEWARI,
and J.K. CHAKRAVARTTY

Tensile tests were carried out on service exposed Alloy 625 ammonia cracker tube used at heavy
water production plant to study the effect of microstructure on the serrated yielding and
mechanical properties of the material. Owing to temperature gradient during service exposure,
the microstructure was different in top, middle, and bottom sections of the tube. Variation of
flow stress, ductility, and average work hardening were monitored with temperature. In the
present work, emphasis was given on the study of serrated yielding in the service exposed Alloy
625. Detail investigations were made to study the effect of microstructure on the underlying
mechanism of dynamic strain aging of the material. The study revealed that both the normal
and the inverse Portevin–Le Chatelier effect (PLC) occured in the material at lower and higher
temperature regime, respectively. While the normal PLC dynamics was associated with locking
of dislocations by interstitial carbon atoms, the inverse one was accomplished by the dislocation
pinning by substitutional Mo atoms. Further analyses identified that the basic deformation
mechanism was different in middle and bottom samples as that in the top samples which was
reflected in the difference in their respective activation energy and stress drop magnitude.

DOI: 10.1007/s11661-014-2717-z
 The Minerals, Metals & Materials Society and ASM International 2014

I. INTRODUCTION exposed condition as precipitation of various phases have

THE Alloy-625 is an austenitic alloy which is being used
for a variety of components in the aerospace, marine,
chemical, and nuclear industries.[1–4] It possesses excellent
strength at both ambient and elevated temperatures along
with good oxidation and corrosion resistance.[2–4] More-
over, the alloy has a very good resistance to creep
deformation and hydrogen attack, excellent formability,
and low hydrogen permeability which make this alloy very
suitable for use as the cracker tube material in ammonia
cracker units of heavy water production plants.[2–4]
Cracker tubes are the primary containment of gaseous
mixtures of nitrogen, hydrogen, and deuterium produced
by cracking of enriched ammonia at temperature from
923 K to 973 K (650 C to 700 C) at a pressure of around
14 MPa. The tubes are approximately 12 m long with a
circular cross section of diameter 90 mm and wall thickness
of 8 mm. They are placed inside a rectangular furnace
which heats the tubes from outside. Even though, the Alloy
625 cracker tubes are designed for a lifetime of 105 hours
under service conditions, several tubes fail before the
anticipated lifetime. The microstructure of the solution-
treated virgin material changes considerably in the service
ARNOMITRA CHATTERJEE, Scientific Officer D, GARIMA
SHARMA, Scientific Officer G, and J.K. CHAKRAVARTTY,
Outstanding Scientist, Director Materials Group, are with the
Mechanical Metallurgy Division, Bhabha Atomic Research Centre,
Trombay, Mumbai 400 085, India. Contact e-mail: jayanta@barc.
gov.in R. TEWARI, Scientific Officer H, is with the Materials Science
Division, Bhabha Atomic Research Centre.
Manuscript submitted August 28, 2013.
Article published online December 23, 2014
been identified during service exposure.[1,2,4–7] Precipita-
tion-induced hardening accompanied with reduction in
ductility and toughness during service exposure could be
implicated for the premature failure. Hence, a huge
amount of work has been done on Alloy-625 to study the
mechanical properties of the material after service expo-
sure and to establish the structure property correlation to
predict the life time of the tube from microstructural
changes of the material.[1–3] Raman et al.[5] have studied
mechanical behavior of Alloy 625 cracker tubes which had
undergone 3 9 104 hours of the service life. They noticed
the change in mechanical properties along the length of the
tube because of the process-related temperature gradient
set up during operation. However, no attempt was made to
correlate the changes in mechanical properties with micro-
structure. Vani Shankar et al.[3,7] and Sundararaman
et al.[6] also studied several features of the microstructure
of the material. Chakravartty et al.[2] carried out a detailed
study of the Alloy 625 of cracker tube material after
completion of 105 hours of service exposure to evaluate the
influence of service temperature on the development of
microstructure and mechanical properties. Structure prop-
erty correlation was developed further depending on the
experimental observations. Apart from the aforemen-
tioned studies, the serrated yielding in Alloy 625 has been
a topic of considerable interest among the researchers.
Serrations in the flow curves, commonly known as the PLC
effect[8–11] arise from Dynamic Strain Aging (DSA) pri-
marily due to repeated pinning-unpinning of mobile
dislocations by diffusing solute atoms. Serrated flow has
also been reported due to precipitate formation and their
shearing, formation of shear bands and occurrence of
stacking faults.[12–14] The serrations in stress–strain curves

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 46A, MARCH 2015—1097

are classified in three generic types: type A, type B and type
C.[1,15] Type A serrations are locking serrations character-
ized by abrupt rise in stress followed by a drop to or below
the general level of the stress–strain curve.[1] Type B
serrations are oscillations about the general level of the
stress–strain curve which occurs due to discontinuous
deformation band propagation arising from DSA.[1]
Finally, for type C serrations, stress drops below the
general level due to the unlocking of dislocations.[1] The
repeated locking-unlocking of dislocations by solutes is
translated into negative strain rate sensitivity (SRS) of the
system.[16,17] In order to understand the nucleation and
propagation steps involved with these serration types and
their relationship with microscopic mechanisms, consider-
able experimental and theoretical efforts have been made.
Zhang et al.[18] investigated the nucleation and propaga-
tion of PLC bands by a novel digital speckle pattern
metrology technique consisting of digital speckle pattern
interferometry (DSPI) and digital speckle correlation
(DSC). P. Zavattieri et al.[19] have reported a detailed
investigation of spatio-temporal characteristics of the PLC
effect in austenitic steel with twinning-induced plasticity
(TWIP). Spatio-temporal pattern of PLC bands has been
investigated by Tong et al.[20] by a technique based on high-
speed digital photography and image correlation. In the
present work, no visual techniques have been adopted to
classify the PLC bands. Instead, band characterization has
been made based on the types of serrations observed in the
stress–strain curves.
Kim and Chaturvedi[21] investigated serrated flow in
Alloy 625 in solution-treated condition and found out
that the Mo atoms play an important role in serrated
yielding behavior of the material. Vani Sankar et al.[1]
carried out a detailed study on the solution-treated
Alloy 625 retrieved from cracker tubes after
60,000 hours service exposure at 873 K (600 C). They
reported serrated yielding behavior in Alloy 625 in a
temperature regime of 523 K to 1023 K (250 C to
750 C). They estimated the activation energy for DSA
to be 98 kJ/mol and conjectured that Mo solute is
responsible for serrated yielding in the solution-treated
material. During the tensile tests, Chakravartty et al.[2]
could observe serrations in the flow curves in a
temperature range of 523 K to 823 K (250 C to
550 C) which was attributed to DSA but no study
was carried out to investigate the DSA phenomenon in
the service exposed Alloy 625. It has already been
established that the temperature gradient along the
length of the tube during service exposure renders
different microstructure development in terms of the
types, size, and distribution of precipitates along the
length of the tube in the top, middle, and bottom
sections of the cracker tube and thus results in different
mechanical properties in these sections.[2] Hence, it
Table I. Nominal Chemical Composition of the Alloy 625 Cracker Tube Material
Element Ni Cr Mo Nb + Ta
Weight percent bal. 20 to 23 8 to 10 3.15 to 4.15
1098—VOLUME 46A, MARCH 2015
would be very fascinating to investigate if this is
reflected in the DSA behavior of the material as well.
In general, DSA has been found to influence plastic
behavior of many engineering materials abnormally and
have a detrimental effect on the ductility and toughness
which may lead to the premature failure of the compo-
nents. Since Alloy-625 is intended for structural appli-
cation, it is very important to investigate to what extent
DSA influences the mechanical properties of the alloy. It
is likely that the partitioning of both substitutional (Nb,
Cr, Mo) and interstitial (such as carbon) elements
between the matrix and precipitates (during service
exposure), and the size, the distribution and the nature
of precipitates may have considerable influence on the
dynamics of serrated flow behavior. In the present work,
the serrated yielding behavior of the service exposed
Alloy 625 has been studied to elucidate the effect of
microstructure and to identify the mechanism of DSA.
The serrated flow behavior has been characterized here
by monitoring the variation of yield stress (YS), ultimate
tensile strength (UTS) and ductility with temperature
and strain rate, evaluating strain rate sensitivity (SRS),
and estimating activation energy for all the three
microstructural conditions corresponding to top, mid-
dle, and bottom sections.
II. EXPERIMENTS
Materials for this study was taken from a used
ammonia cracker tube of Alloy-625 (service exposed for
100,000 hours) obtained from a heavy water plant and
was the same as used in an earlier work.[2] The nominal
composition of the alloy is given in Table I. The outside
skin of the top, middle, and bottom locations of the 8 m
long tube were exposed to a temperature of 932 K,
949 K and 958 K (658 C, 676 C and 685 C), respec-
tively, under operating conditions. Various samples
(tensile, impact and fracture toughness) were machined
from the central portion of top (T), middle (M) and
bottom (B) sections. The details of samples and test
procedure are given elsewhere.[2] Tensile tests were
performed over a temperature regime from room
temperature (RT) to 973 K (700 C) under a constant
strain rate condition. Three different strain rates were
chosen for the study: 8.8 9 105, 4.4 9 104, and
1.8 9 103 s1. The tests were carried out in a screw
driven tensile testing machine using a resistance heating
furnace with temperature control ±1 C. Apart from the
conventional tensile tests, a number of strain rate jump
tests were also carried out under different temperatures
to estimate the SRS of the material. TEM investigations
were done on the tensile-tested samples by slicing
samples at 45 deg to the fractured region in the guage
Ti + Al Fe Co Si C P and S
0.4 each 5 max 1.0 0.5 0.01 0.015 each
METALLURGICAL AND MATERIALS TRANSACTIONS A
portion. Samples for TEM investigation were prepared
by jet polishing 3 mm disks using 20 pct perchloric acid
and 80 pct methanol at 20 V and 228 K (45 C). TEM
analysis was performed on the Jeol 2000 FX operating
at 200 kV.
III. RESULTS
Both optical and electron microscopic examinations
have been carried out to reveal microstructural features
of the undeformed specimens from the three locations.
The solution-annealed virgin tube exhibited precipitates
of different types within the matrix and at grain
boundaries on service exposure. The details of micro-
structural characterization have been reported previ-
ously[2] and Tables II, III summarizes the
microstructural features observed in three sections.
While the grain boundaries in the T specimens showed
a thin and discontinuous layer of carbides, thicker and
continuous precipitates were found in the M (carbides)
and the B (carbides and d) specimens. c¢¢ phase was the
major precipitate within the matrix in all the three
sections. However, the size of c¢¢ phase was largest in the
B specimens followed by the M and the T specimens. In
addition to c¢¢ phase, Ni2(Cr,Mo) and d were observed
within the matrix of the T and the B specimen,
respectively. Electron microscopic investigation con-
firmed the carbides to be of the M23C6 type. It has
been reported that microstructural development in each
section could be matched very well with the temperature
experienced and it was established that the B section
experienced the highest temperature. The complex
microstructural development in the three sections
resulted in distinctly different mechanical properties
which have also been published.[2] When these mechan-
ical properties are compared with the virgin material, it
is seen that there is a significant increase in strength
(both YS and UTS) with corresponding decrease in
ductility and impact toughness of the service-aged
materials.[2] When the service exposed materials were
tensile tested over the temperature range of RT to 973 K
Table II. Average Sizes of c¢¢ and Ni2(Cr, Mo) Particles
Measured at Different Sections of the Cracker Tube
Sample c¢¢ Particles (nm) Ni2(Cr,Mo) Particles
Top 6.7 14.8
Middle 39.7 — rate combination. Figure 2 exhibits a typical variation
Bottom 225 — of serrations with test temperature in the M specimen
Table III. Precipitation of Various Phases Formed During Service in Alloy 625 at Different Locations of the Cracker Tube
Formation Site and Type of Precipitate
Sample Within Matrix
Top fine c¢¢ and Ni2(Cr, Mo)
Middle large c¢¢ particles only
Bottom very large c¢¢ + d particles
METALLURGICAL AND MATERIALS TRANSACTIONS A
(700 C) at a strain rate of 4.2 9 104 s1, following
important observations were made
(i) A decrease in YS was noted in specimens of all
sections with increasing temperature except in the
temperature range 523 K to 673 K (250 C to
400 C). While UTS of the B and the M sections
increased with temperature up to 873 K (600 C),
the T section showed a moderate decreasing trend
of UTS up to about 773 K (500 C) followed by a
rapid drop. At temperatures above 923 K
(650 C) the UTS values of both the B and the M
sections were found to decrease rapidly. The vari-
ation of the strength parameters with temperature
appeared to be related to the prevailing micro-
structure and chemical composition of the matrix
phase.
(ii) The ductility (total elongation at break) showed
an increasing trend with temperature for all the
sections
(iii) The T section exhibited higher strength and duc-
tility in the temperature range RT—773 K
(500 C) compared to that observed for the M
and the B sections.
(iv) A good correlation between microstructure and
mechanical properties could be established.
Although, at ambient temperature, stress–strain
curves were smooth at the strain rates employed in the
previous study, serrations appeared in stress–strain
curve at higher temperature regime of 523 K to 873 K
(250 C to 600 C). In the following, the experimental
results of serrated flow behavior of service exposed
Alloy 625 are presented.
Stress–strain curves were obtained for all the three
conditions in the temperature range of RT—973 K
(700 C) at three different strain rates: 8 9 105,
4.4 9 104, and 1.8 9 103 s1. Serrated yielding was
observed between 523 K and 873 K (250 C and
600 C) in all three sections for all the strain rates
employed. At temperatures up to 473 K (200 C), as
well as at 873 K (600 C) [923 K (650 C) for the T
samples] and above the flow curves did not exhibit
serrations for all the strain rates employed. Typical true
stress–strain curves for the service exposed Alloy 625 M
sample deformed with a strain rate of 8.8 9 105 at
623 K and 873 K (350 C and 600 C) are shown in
Figures 1(a) and (b), respectively. Three types of serra-
tions could be distinguished namely Type A, Type B,
and Type C depending on the temperature and strain
for the strain rate of 8 9 105 s1. It is quite evident
At Grain Boundary
M23C6 type carbides: very few in volume and discrete distribution
large chunky M23C6 type carbides: almost continuous distribution
continuous film of M23C6 carbide + d phase particles
VOLUME 46A, MARCH 2015—1099

Fig. 1—A typical true stress–strain curve for the M sample deformed
with a strain rate of 8.8 9 105 s1 at (a) 623 K (350 C) and (b)
873 K (600 C).
from the figure that the nature of the serrations changes
with change in test temperature. At the lowest temper-
ature of 523 K (250 C), the serrations are of type A in
nature which is characterized by an abrupt rise in stress
value over the general trend of stress–strain curve. At a
higher temperature of 623 K (350 C), a combination of
type A and type B serrations are observed. Apart from
sudden rise and drop to the general trend of flow curve
(type A), oscillations about the general trend of stress–
strain curve are also observed, which is identified as type
B serrations. On increasing the temperature further, type
C serrations are found in both 723 K and 773 K (450 C
and 500 C). These types of serrations are characterized
as stress drops below the general trend of flow curve
with much higher drop magnitude compared to the type
A and type B serrations. Serrations appeared only after
a finite amount of plastic strain (critical strain). The
details of serrated flow will be discussed in a section to
follow.
A. Effect of Strain Rate and Temperature on Tensile
Properties
The variations of YS and UTS and their strain rate
dependence on temperature are given in Figure 3. The
trends of the variations are also shown by the dotted line
for all the three conditions. It is seen that in the
temperature range of 498 K to 873 K (225 C to
600 C), while YS of all the sections exhibit a plateau
or small peak, UTS values show a little decreasing trend.
At temperatures higher than this range both YS and
UTS show a rapid decreasing trend indicating operation
1100—VOLUME 46A, MARCH 2015
of recovery mechanisms. These observations are clearly
revealed in Figure 3 where the variations of YS and
UTS with temperature and strain rate are shown for the
three samples with that of the M specimen in the
serrated flow regime given in magnified scale in the inset.
Further it was seen that UTS decreased with strain rate
at the temperature regime 523 K to 873 K (250 C to
600 C). At all strain rates, while the T samples recorded
the highest strength, the B one exhibited the lowest
strength value. The variations of both elongation to
fracture and elongation to UTS with temperature were
also recorded and the latter is depicted for all the three
types of samples deformed at a strain rate of
8.8 9 105 s1 in Figure 4. Unlike the dip in ductility
associated with DSA[22] for example in ferritic steels, the
ductility in service exposed Alloy 625 increased mark-
edly with temperature. Similar observations have been
made by Kim and Chaturvedi[21] in Alloy 625 and
Gopinath et al. in 720Li.[17] The T samples maintained
highest ductility as compared to the B and the M
samples throughout the temperature regime considered
here. Since the ductility is controlled by work hardening
behavior or relative magnitude of the difference (UTS-
YS), the variation of average work hardening with
temperature was monitored for all the samples. A
typical variation of average work hardening with
temperature for the T, M, and B samples are shown in
the inset of Figure 4 to understand the variation of
ductility in the serrated flow regime. Two distinct peaks
were observed in the work hardening behavior at the
start and end of the DSA regime. However, it is seen
that within the DSA regime average work hardening
rate do not vary significantly.
The SRS was also estimated for the material by strain
rate jump tests following the equation:[17]


ln r1=r2
m¼  ;
ln e_ 1=e_ 2
where the stress level changes from r1 to r2 during a
strain rate jump test from strain rate e_ 1 to e_ 2 for a given
strain and temperature. A typical variation of SRS with
temperature for the M sample is shown in Figure 5.
B. Serrated Flow and Mechanism of DSA
The investigation of the mechanism of DSA in any alloy
system has drawn huge attention since it enables to identify
the solute responsible for serrated yielding at different test
conditions and further prediction of degradation of
mechanical properties can be done by knowing the reaction
of the solute species with other phases present in the alloy.
The examination of the serrated flow curves for Alloy 625
revealed that the height of serrations (amplitude and
frequency) increased with increasing temperature and
decreasing strain rate. The types of serrations were also
observed to be changing with e_ and T combination
(Table IV). At the lowest strain rate of 8.8 9 105 s1, in
the M and the B samples type (A + B) serrations were
observed at 573 K (300 C) and below and type C
serrations were observed above 573 K (300 C). However,
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 2—A typical representation of different types of serrations at different test temperatures for the M sample deformed with a strain rate of
8.8 9 105 s1.
in the T samples, the type (A + B) serrations prevailed up
to a temperature of 623 K (350 C) and above that
temperature was observed to be transformed to type C in
nature. At the intermediate strain rate of 4.4 9 104 s1,
type (A + B) serrations were observed up to 723 K
(450 C) for the T samples, where as, for the M and the B
specimens it was up to 623 K (350 C). Above the
aforementioned temperature limit, the serration type
changed to type C. Finally, for the highest strain rate of
1.8 9 103 s1, type C serration took place of the type
(A + B) serration above the temperature of 823 K
(550 C) for the T samples, whereas the M and the B
samples exhibited type C serrations at and above a
temperature of 823 K (450 C) for this strain rate.
Previous investigations in the field of DSA suggest
that the evaluation of critical strain (ec) and its varia-
tions with strain rate and temperature lead to the
estimation of the activation energy (AE) of the DSA and
hence, carry the signature of the underlying mechanism
of DSA. According to the formulation of McCor-
mick,[10] the much used[23–26] dependence of ec on strain
rate and temperature can be expressed as
emþb
c ¼ K_e expðQ=RTÞ;
where m and b are the respective exponents in the
relations for the variation of vacancy concentration (Cv)
METALLURGICAL AND MATERIALS TRANSACTIONS A
and mobile dislocation density (qm) with plastic strain
(Cv  em and qm  eb), K is a constant, Q is the
activation energy, R is the universal gas constant, and
T is the absolute temperature. It is evident from the
above equation that (m + b) can be estimated from the
slope of the plot ln e_ vs lnec at a constant temperature.
Finally, Q can be evaluated following the equation from
the slope of a plot of ln ec vs 1/T at constant e_ as
Q = slope 9 (m + b) 9 R. AE can also be estimated
by another method, called the stress drop method.[17,26]
It has been found that the stress drop serves as a better
criterion for studying strain aging compared to the
critical strain as critical strain method seems to be
suitable only for very simple alloy systems.[27] Dr is
defined as the difference of stress level for breakaway of
dislocations from their atmosphere and at which they
glide through the lattice. In stress–strain curve, Dr is
simply the height of individual serrations. In this
procedure, Dr at a given strain was calculated for a
range of e_ and T. A constant value of Dr was then
selected and corresponding e_ was determined for each
temperature. Finally, these e_ were plotted as a function
of 1/T and Q was estimated from its slope as
Q ¼ ðln e_ RTÞ.
The critical plastic strain (ec) was estimated from the
load-elongation curves as the minimum value of the true
VOLUME 46A, MARCH 2015—1101
Fig. 3—The variation of YS and UTS with temperature at different strain rate for (a) T, (b) M and (c) B samples. Inset shows variation of YS
and UTS for M sample within serration regime.
plastic strain at which a perceptible load drop of 5 N
occurred. It was observed that within the strain rate
regime of type (A + B) serrations, ec decreased with
increasing temperature suggesting the presence of the
normal PLC effect.[15] At lower strain rate regime where
the serrations were of type C in nature, the scenario was
quite the opposite as ec exhibited an increasing trend
with increasing temperature which is attributed to the
inverse PLC effect.[15,28] In this regime, the serrations are
generally observed as discontinuous load drops below
the general stress–strain curve, in contrast to the locking
type serrations associated with the normal PLC effect at
higher strain rates and lower temperatures. However,
the origin of the inverse PLC dynamics is not well
understood but it is often attributed to the precipitation
before or during tests and depletion of solutes in the
matrix.
The values of (m + b) and subsequently the Q values
were estimated following the method outlined above. A
typical plot for the estimation of (m + b) and corre-
sponding AE for the M samples are shown in
Figures 6(a) and (b), respectively. In all the three
samples, the slope changed from positive to negative
with increasing temperature and a transition tempera-
ture could be identified where PLC dynamics switches
from the normal to the inverse one. The average values
of (m + b) and the corresponding Q values at both the
normal and the inverse regime of PLC dynamics were
represented in Table V. The typical variation of transi-
tion temperature in different samples deformed at a
strain rate of 1.8 9 103 s1 is also listed in Table V. It
is evident that the transition temperature did not differ
much between the M and the B samples, where as it was
markedly higher in the T samples. The average (m + b)
1102—VOLUME 46A, MARCH 2015
values estimated from the test data suggested that the
mean values of the (m + b) for the normal PLC
dynamics were ~1 for all the specimens, whereas those
values in the inverse PLC regime were between 2.0 and
3.0. AE values were found to be much higher in the
inverse PLC regime as compared to the normal PLC
dynamics. The average AE in the normal PLC regime
for the T, M, and B samples were estimated to be 59, 98,
and 72 kJ/mol, respectively. The corresponding AE
values at the inverse regime were 90, 181, and 180 kJ/
mol, respectively. The AE derived from the stress drop
method also yielded similar values and a comparison of
AE values estimated from both the methods for the M
sample is listed in Table VI. Figure 7 exhibits the typical
plots for the estimation of AE by stress drop method for
the M samples. The AE values derived for the normal
and the inverse behavior through stress drop method
were 87 and 140 kJ/mol, respectively.
C. Microstructure Evolution During DSA
Detailed TEM investigations, as already reported in
our previous study,[2] showed presence of c¢¢ and Ni2
(Cr, Mo) precipitates in the T sample with an average
size of 6.7 and 14.8 nm, respectively (Table II). TEM
investigations on the T sample from the PLC regime
showed high density of c¢¢ and Ni2(Cr, Mo) precipitates
and dislocations. As the size of the precipitates is small
and they maintain coherency with the matrix, they are
expected to get sheared by dislocations in the PLC
regime.[13] Figure 8(a) shows the bright field TEM
micrograph showing interaction of dislocations with
precipitates and tangled dislocations. The dislocation
pairs and shearing of precipitates were also observed as
METALLURGICAL AND MATERIALS TRANSACTIONS A
 573 to 873 (300 to 600)
623 to 873 (350 to 600)
673 to 873 (400 to 600)
Type C
B
Identification of Strain Rate and Temperature Domain for Different Types of Serrations in T, M, and B Samples

523 to 573 (250 to 300)

523 to 623 (250 to 350)
523 to 673 (250 to 400)
Type (A + B)
Fig. 4—A typical variation of total elongation with temperature for
the samples deformed at a strain rate of 8.8 9 105 s1. The inset

Temperature Regime of Different Serrations [K (C)]

shows the variation of work hardening with temperature for the

573 to 873 (300 to 600)

623 to 873 (350 to 600)
673 to 873 (400 to 600)
three types of sample.

Type C
M

523 to 573 (250 to 300)

523 to 623 (250 to 350)
523 to 673 (250 to 400)
Type (A + B)
Fig. 5—A typical variation of strain rate sensitivity with temperature

723 to 873 (450 to 600)

823 to 873 (550 to 600)
623 to 873(350 to 600)
for the M sample. SRS acquires a negative value over the tempera-
ture regime of DSA.
Type C

shown by arrows in Figure 8(b). TEM investigations of

the T sample from the inverse PLC regime, however,
showed presence of high density of shear bands and
interaction between shear bands (Figure 8(c)). In the
present study, in addition to shear bands, twins–band
interactions were also found to take place as shown in
T

523 to 623 (250 to 350)

523 to 723 (250 to 450)
523 to 823 (250 to 550)

Figure 8(d) with inset showing SAD from twinned

region. It is well known that formation of twin is
Type (A + B)

accompanied by shear strain and this will increase the

Table IV.

plasticity of material if plenty of twins have been formed

during DSA. The twin and shear bands were found to be
almost perpendicular to each other which indicate that
the orientation with respect to loading direction influ-
ence the formation of twin.
TEM investigation of normal PLC regime in the M
and the B sample showed similar microstructure. As
Strain Rate (s )
1

already reported in,[2] there was a dissolution of Ni2(Cr,

Mo) precipitates and growth in c¢¢ precipitate, due to
8.8 9 105
4.4 9 104
1.8 9 103

high exposure temperature in the M and the B sample.

Detailed microstructural investigations in PLC regime
in the M and the B samples showed the presence of shear

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 46A, MARCH 2015—1103

Fig. 6—Typical plot for the (a) estimation of the (m+b) values from the ln e_ vs ln ec plots and (b) evaluation of the activation energies from the
ln ec vs I/T plot for M samples.

Table V. Average Value of (m + b) and Activation Energy Derived for T, M, and B Samples

Activation Energy
Average (m + b) (range) (kJ/mol)
Transition
Sample Normal Inverse Normal Inverse Temperature (C)
T 1.01 (0.92 to 1.11) 2.58 (1.95 to 2.95) 59 90 550
M 1.07 (0.85 to 1.36) 2.62 (2.36 to 2.81) 98 181 371
B 0.90 (0.81 to 0.96) 2.23 (1.97 to 2.47) 72 180 394
Typical variation of transition temperature for normal to inverse PLC dynamics for the samples deformed at 1.8 9 103 s1 is also shown.

Table VI. Comparison of Activation Energies Derived from Critical Strain Criterion and Stress Drop Method for the ‘Middle’
Sample

Activation Energy (kJ/mol)

Types of Serration From ln ec vs 1:T Plots Using Average m + b Values Stress Drop Method
Type A and B 98 87
Type C 181 140

bands in addition to a high density of dislocations in the IV. DISCUSSION

vicinity of these shear bands (Figure 8(e)). However,
TEM investigations in the inverse PLC regime of the M
and the B samples showed high density of deformation
twins and twin–twin interactions. Figure 8(f) shows
cross twinning in the B samples with inset showing SAD
from twins. The high density of deformation twins
appeared both in the M and the B sample despite the
high temperature of inverse PLC regime and this could
be due to the instant higher local stress peaks caused by
the DSA process. The sample from the T portion in the
inverse PLC regime predominantly showed formation
and propagation of shear bands. Whereas the B and the
M samples showed formation of deformation twins and
twin–twin interactions as the dominant mechanism in
the inverse PLC regime. These results indicated that
deformation in the T, M, and B sample is dependent on
temperature—strain rate combination along with the
prehistory of these samples.
The distinct differences in several aspects of DSA, like
transition temperature and activation energy which
could be readily identified among the T, M, and B
samples appeared to be a reflection of the differences in
their initial microstructures and alloy chemistry. Cha-
kravartty et al.[2] carried out detail investigation on the
microstructures of service exposed Alloy 625 along the
length of the cracker tube and their findings are
summarized in Table II and III. The value of (m + b)
is supposed to carry the signature of the mechanism of
DSA. It is well established in literature that serrated flow
resulting from the strain aging is attributed to the
interstitial solutes when the value of (m + b) lies
between 0.5 and 1.0 and to substitutional solutes when
it lies in the range of 2.0 to 3.0.[26] The observed low
values of activation energy for type (A + B) serration in
the normal PLC regime along with small value of

1104—VOLUME 46A, MARCH 2015 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 7—Plots for the determination of the activation energy by stress
drop method: (a) Variation of average stress drop Dr with strain
rate e_ , (b) ln e_ vs I/T plot using intercepts from (a).
(m + b) (<1.0) suggested that the interstitial carbon
atom might be playing the crucial role in dislocation
locking here. The average value of activation energy was
found to be quite low for normal PLC effect. These
values were close to 69 kJ/mol, the activation energy for
diffusion of C in Ni.[29] Keh and Nakada[30] also found
similar value of AE (62 kJ/mol) for normal PLC
dynamics in Ni-C Alloys which they attributed to the
core diffusion of carbon atoms. Thus, interstitial carbon
atoms could be responsible for the normal PLC behav-
ior in the T sample. TEM investigations for the normal
PLC regime showed dislocation–dislocation interaction
and shearing of precipitates in the T samples. In case of
the inverse PLC dynamics, where the serration was of
type C in nature, the corresponding (m + b) values
(which lies between 2.0 and 3.0) suggested the role of
substitutional solutes in locking the dislocations. The
composition of Alloy 625 showed that the major
substitutional elements present were Cr, Mo, Fe, and
Nb. Since, Cr and Fe are similar in atomic size to Ni;
they were not expected to cause serrated flow. The
activation energy of Cr and Fe or self diffusion of Ni is
~250 kJ/mol or higher.[26] Hence, the possible solute
forming the Cottrell atmosphere around the dislocations
should be Mo or Nb. Since Nb is known to be a slow
diffusing solute in Ni (diffusivity ~1.04 9 106 m2/s, AE
~202 kJ/mol),[31] the substitutional element responsible
for the DSA in this alloy might be Mo.[1] Microstruc-
tural investigations of the T sample from the inverse
METALLURGICAL AND MATERIALS TRANSACTIONS A
PLC regime showed presence of high density of shear
bands and interaction between shear bands (see Fig-
ure 8(c)). Interaction of these multidirectional shear
bands is the signature of localized plastic deformation.
At the inverse PLC regime, the dissolution of Ni2(Cr,
Mo) precipitates take place and Cr and Mo atoms go
into the solution. The observed AE (~90 kJ/mol) value
of the inverse PLC dynamics in the T samples is found
to be in close agreement with the AE for Mo atom
migration (~100 kJ/mol) in Ni matrix. Kim et al.[21] and
Vani Shankar et al.[1] have also reported the AE for Mo
migration in Ni matrix to be ~100 kJ/mol which
matched very well with the results obtained for the
inverse PLC dynamics in T samples in the present study.
Thus, the presence of Mo atoms in the solution is
responsible for the serrated behavior in the inverse PLC
regime. Though Ni has a high stacking fault energy
(SFE) ~150 mJ/m2, presence of solutes like Cr, Mo etc.
brings down the SFE of c¢¢ (25 mJ/m2)[32] considerably.
Singh et al.[33] have reported that low SFE promote
planar slip and thereby promoting shear band forma-
tion. The presence of Mo atoms within shear band acts
as pinning agent for dislocations and thereby increases
local stress concentration. When the stress concentra-
tion reaches a critical value, propagation of shear bands
and initiation of formation of shear bands in adjacent
region take place. Thus, deformation in the inverse PLC
regime in the T sample proceeds by the initiation and
propagation of shear bands. It is worth pointing out
that the dislocation density in these shear bands were
found to be very high. Sundararaman et al.[13] have also
reported the presence of shear bands along with twins in
alloy 718 which is deformed to ~19 pct strains. The
deformation strains reported in the present study is,
however, much higher (~70 pct) and could be the reason
for higher density of shear bands observed. An atomistic
analysis by Qu et al.[34] have reported that shear band
formation and the dislocation structure within these
bands is rather complex, containing twinning partial
dislocations, full dislocations, and even stair-rod dislo-
cations. It has also been reported that as the deforma-
tion proceeds, the dislocation density in these shear
bands increases to a critical value and as a result, further
deformation occurs by movement of these bands.
The microstructural study in the inverse PLC regime
for the M and the B samples showed high density of
deformation twins. In this regard, it is worth mentioning
the work reported by Sundararaman et al.[13] where they
identified a critical size (~10 nm) of the c¢¢ precipitate in
Ni-based super alloys below which deformation would
be enabled by the progress of dislocations while with
larger precipitate size it would be governed by shearing
of precipitates through the passage of deformation
twins. This effect can be assumed to be similar to the
twin induced plasticity (TWIP) and probably be related
to the improved effect of ductility. Singh et al.[33] have
also pointed out the role of deformation twins in service
exposed Ni-based super alloys. In this work, it has been
observed that the Q values for both the normal and the
inverse PLC dynamics in the M and the B samples were
much higher compared to the AE in the T samples. This
difference in deformation mechanism is possibly due to
VOLUME 46A, MARCH 2015—1105

50 nm 50 nm
(a) (b)
100 nm 200 nm
(c) (d)
200 nm 200 nm
(e) (f)
Fig. 8—BF TEM image showing (a) dislocation precipitate interac-
tion in normal PLC regime in the T sample; (b) dislocation pairs and
precipitate shearing in normal PLC regime in the T sample; (c) shear
band interactions in inverse PLC regime in the T sample; (d) shear
band twin interaction in inverse PLC regime in the T sample with
inset showing SADP for twin; (e) dislocation-shear band interaction
in normal PLC regime in the B sample; (f) twin–twin interaction in
inverse PLC regime in the B sample.
variation in the microstructure of the samples. The high
AE in the B and the M samples could be due to
requirement of high local stress concentration for the
formation and propagation of deformation twins at high
temperature. Cui et al.[35] related the inverse PLC effect
in Ni-Co super alloy with the occurrence of continuous
stacking faults within the c¢ precipitates. However, such
stacking faults could not be observed in the present
study.
The study of the microstructures of Alloy 625 after
service exposure suggested that the T samples contained
Ni2(Cr, Mo) phases in the matrix which might have
dissolved at high temperature releasing Mo atoms in the
solution. Vani Shankar et al.[3] reported dissolution of
the Ni2(Cr, Mo) phase at 923 K (650 C). However, in
the present case, the T samples were deformed with
simultaneous exposure to elevated temperature which
1106—VOLUME 46A, MARCH 2015
might have induced the dissolution of Ni2(Cr, Mo) at a
lower temperature. Hence, for the T samples, the
depletion of Mo atoms was delayed further in compar-
ison to the M and the B specimens. As a consequence,
the transition from the normal to the inverse PLC
dynamics in the T samples shifted to a relatively higher
temperature than those of the M and B ones. Apart
from DSA, the difference in mechanical properties in the
T, M, and B samples also were related to their different
microstructure. The finely dispersed c¢¢ and Ni2(Cr, Mo)
particles rendered the high strength to the T samples, as
compared to the M and B ones where only c¢¢ particles
of larger size were present. The usual dip in ductility
during DSA was not observed here. Kim and Chaturv-
edi[21] and Gopinath et al.[17] also reported the absence
of dip in ductility during serrated yielding in nickel-
based super alloys. Kim et al.[21] associated the phe-
nomenon with the longer traveling distance of defor-
mation fronts. In the present work, the plateau observed
in work hardening rate during DSA suggested that the
rate of recovery was quite strong even in the DSA
regime. The lowest ductility and UTS observed in the B
samples can be explained in terms of the presence of
needle-shaped d particles, as reported in our previous
study.[2] These precipitates acted as internal notches at
the grain boundaries which along with the continuous
carbide layer prohibited the slip propagation through
grain boundaries. These conditions led to cracking
locally and thus hindered the attainment of ultimate
strength, resulting in lower UTS and ductility.
V. CONCLUSIONS
The investigation of the Dynamic Strain Aging in
service exposed Alloy 625 revealed that serrated yielding
in the material was confined in a temperature domain of
523 K to 873 K (250 C to 600 C) for the strain rates
considered here. For the T, M, and B samples, the PLC
dynamics exhibited both normal and inverse behavior at
low and high temperature regime, respectively. The
normal behavior was associated with type (A + B)
serrations and interstitial carbon atoms could be
responsible for the normal PLC behavior in the T
sample. TEM investigations for the normal PLC regime
showed dislocation–dislocation interaction and shearing
of precipitates in the T samples. On the contrary, the
serrations were of type C in nature in the inverse PLC
regime and were attributed to the locking of dislocations
by substitutional Mo atoms and nucleation and prop-
agation of twins and shear bands. The differences in AE
in the M and the B samples with that of the T samples
revealed basic difference in the deformation mechanism
owing to different microstructure. The transition tem-
perature from normal to the inverse PLC dynamics also
varied appreciably in the T samples than that of the M
and the B ones which could be explained in terms of the
delayed depletion of Mo solutes in solution for the T
samples. The tensile properties were also investigated in
the DSA regime. The SRS took a negative value in the
DSA regime. Even though YS and UTS showed
marginal peak in this regime, the ductility did not show
METALLURGICAL AND MATERIALS TRANSACTIONS A
 the usual dip in serrated yielding in this material, rather
it followed an increasing trend with temperature.
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