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Abstract
A generalized phase transformation kinetics model is used to understand the martensite to austenite transformation in a cold-rolled
and annealed metastable AISI 301LN ultrafine-grained austenitic stainless steel. The model shows that the presence of interstitial nitro-
gen and heavy cold-rolling is important to promote fast transformation kinetics, through rapid nitrogen-diffusion and austenite nucle-
ation at austenite/martensite phase boundaries.
Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
1359-6454/$36.00 Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2010.10.012
S. Rajasekhara, P.J. Ferreira / Acta Materialia 59 (2011) 738–748 739
cold-rolled martensite structure is lath-type, the austenite where they assume that the embryos of a new phase nucle-
phase nucleates at the lath boundaries and intersections, ate randomly from the time-dependent parent phase. In the
and grows from these sites into the martensite lath. On the case of the a0 ? c phase transformation, this relationship
other hand, if the parent martensite morphology is disloca- may be expressed as:
tion-cell-type (comprising dislocation forests and ultrafine Z
4p t 3 3
lath martensite), equiaxed ultrafine austenite grains nucleate lnð1 nc ðT ; tÞÞ ¼ v ðT ; tÞJ ðT ; tÞðt sÞ ds ð1Þ
3 0
at martensite grain boundaries. The present authors and
other research groups have consistently observed these find- where nc(T, t) is the time (t) and temperature (T) dependent
ings in several cold-rolled and annealed commercial and spe- austenite phase volume fraction, v(T, t) the austenite grain
cialty SS grades [17–20]. Qualitatively, this time-dependent growth velocity, J(T, t) the austenite phase nucleation rate
“diffusion-type” mechanism is characterized by: (i) a wide and s the incubation time for the formation of the first aus-
annealing temperature range; (ii) the formation of defect- tenite nuclei. For simplicity, we assume the nucleation rate
free equiaxed austenitic grains which grow in size with time; to be independent of annealing duration. Eq. (1) thus re-
(iii) a wide austenite grain size distribution; and (iv) possible duces to:
formation of secondary phase precipitates [18]. Z
4pJ ðT Þ t 3 3
Clearly, there is experimental and phenomenological lnð1 nc ðT ; tÞÞ ¼ v ðT ; tÞðt sÞ ds ð2Þ
3 0
evidence that seem to confirm the diffusion-type phase
transformation mechanism in cold-rolled and annealed While the term J(T) will be discussed later, the integral in
ultrafine-grained austenitic SS. However, despite the avail- Eq. (2) may be solved by using an explicit time and temper-
able work, there is a lack of quantitative understanding ature dependence relationship for v(T, t), which is given by
regarding the kinetics of the a0 ? c phase transformation. [20]:
In addition, several fundamental concepts involved in this 1
phase transformation, such as: (i) the type of the diffusing ðktÞn
vðT ; tÞ ¼ ð3Þ
species driving the phase transformation; and (ii) the nat- nt
ure of austenite/martensite grain boundary junctions where where k is the austenite grain growth parameter, n is the
the transformation occurs are not yet known. An under- austenite grain growth exponent and t is the annealing
standing of these factors is critical for tailoring the compo- time. As has been discussed elsewhere [20,23–26], the grain
sition of metastable austenitic SS grades, as well as for growth parameter k is a measure of the material’s grain
optimizing the cold-rolling procedure and subsequent boundary mobility, which depends on annealing tempera-
annealing to promote an efficient a0 ? c transformation, ture and grain growth activation energy, while the grain
which can lead to the production of ultrafine-grained SS. growth exponent n depends on the annealing temperature,
In this work, we apply the general phase kinetics rela- grain orientation, texture, residual strain and soluble impu-
tionship proposed by Erukhimovitch and Baram [21,22], rities. By combining Eqs. (2) and (3), the generalized phase
and quantitatively address the a0 ? c phase transformation transformation kinetics relationship can be rewritten as:
in a cold-rolled and annealed metastable ultrafine-grained Z 1
!3
austenitic AISI 301LN SS grade, the composition of which 4pJ ðT Þ t ðktÞn 3
lnð1 nc ðt; T ÞÞ ¼ ðt sÞ ds ð4Þ
is shown in Table 1. The AISI 301LN SS is an ideal candi- 3 0 nt
date for this study because: (i) it has a wide commercial use;
(ii) it exhibits a very rapid (1–100 s) diffusion-driven a0 ? c Solving Eq. (4) for nc(T, t), we obtain the expression
transformation within a wide annealing temperature range 3 3
!
(700–1000 °C) [8,18]; and (iii) there is experimental phase 4pJ ðT Þk n tnþ4
nc ðt; T Þ ¼ 1 exp ð5Þ
fraction and grain size data against which our analysis 3n3
may be compared [8,18,20].
Eq. (5) gives the austenite phase fraction nc as a function of
2. Kinetics model grain growth kinetic parameters k, n and the nucleation
rate J(T). Not surprisingly, Eq. (5) has a form similar to
2.1. Basis for the model the kinetics relationships developed by Avrami [27,28]
and Johnson and Mehl [29]. However, Eq. (5) is written
Erukhimovitch and Baram [21,22] proposed a general in terms of experimental parameters, namely the nucleation
kinetics relationship for solid-state phase transformations rate J(T) and the grain growth parameters k and n.
Table 1
Weight percent and mole fractions of the various elements present in AISI 301LN SS.
C N Ni Cr Mn Si Cu Mo Fe
wt.% 0.017 0.15 6.5 17.3 1.29 0.52 0.2 0.15 Balance
Mole fraction 0.0008 0.006 0.063 0.186 0.013 0.005 0.002 0.002 0.744
740 S. Rajasekhara, P.J. Ferreira / Acta Materialia 59 (2011) 738–748
According to classical nucleation theory, the time- grain boundary area of the eliminated a0 /a0 interface and
dependent nucleation rate J(T, t) in solid-state transforma- the volume free energy change DGv(T). Thus, DG(T)
tions is given by [30,31]: may be expressed as [33]:
s
DG 4ðbra0 =c ara0 =a0 Þ
3
J ðT ; tÞ ¼ ZbC 1 exp exp ð6Þ DG ðT Þ ¼ ð10Þ
kBT t 27c2 ðDGv ðT ÞÞ
2
where Z is the Zeldovich non-equilibrium factor that ac- where a is the eliminated martensite grain boundary area
counts for the nuclei that exceed the critical nucleus size, during the a0 ? c phase transformation, b is the new aus-
b is the rate at which atoms are added to the critical nu- tenite/martensite grain boundary area, c is the new austen-
cleus, C1 is the concentration of available nucleation sites, ite nucleus volume [33] and DGv(T) is the volume free
DG is the activation energy for heterogeneous austenite energy change due to the martensite to austenite transfor-
nucleation and s is the incubation time. As mentioned pre- mation. The parameters a, b and c depend on the geometry
viously, we initially assume the nucleation rate to be con- of the nucleating grain (to be discussed later). On the basis
stant within 1–100 s of annealing. Later, in Section 3, we of Eqs. 7, 8a, 8b, 9, 10, Eq. (5) may be rewritten as:
will show that this assumption is justified. Thus, the time- 3 1
0 DG ðT Þ
independent nucleation rate may be written as: 4pZðT ÞbðT ÞC gb exp
3
k n tnþ4
1
@
nc ðt; T Þ ¼ 1 exp
kB T
A
DG 3n3
J ðT Þ ¼ ZbC 1 exp ð7Þ
kBT
ð11Þ
The relationships for Z and b have been developed by
Johnson et al. [31], and modified for the specific case of where all the terms retain their previous definitions. At this
austenite nucleation as shown below: point, to calculate nc(t, T) we still need to determine
DG(T). Therefore, the values for the a0 /c interfacial
2
V a0 Fe ½DGv ðT Þ energy, the a0 /a0 interfacial energy, the volume free energy
ZðT Þ ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð8aÞ
8p k B TK j ra0 =c change DGv(T), the martensite grain boundary width d gb a0 ,
the grain size da0 and the magnitudes of a, b and c for dif-
16pr2a0 =c DðT ÞLj ferent austenite/martensite grain junctions in Eq. (10) must
bðT Þ ¼ 2
ð8bÞ
a4a0 ðDGv ðT ÞÞ be found. We estimate these parameters in the subsequent
sections.
where Va 0 Fe is the average volume of an iron atom in the
martensite phase, DGv(T) is the Gibbs free energy change
2.2. Estimation of the interfacial energies ra0 /a 0 and ra/c
per unit volume of martensite to austenite phase transfor-
mation, Kj and Lj are geometric parameters that depend
When an austenite grain nucleates within the martensite
on the a0 -phase and c-phase interfacial energies, D(T) is
matrix, the martensite grain boundary is eliminated and a0 /
the temperature-dependent diffusion coefficient of the spe-
c interface is created. Prior research has shown that
cies that govern the martensite to austenite transformation,
h1 1 0i-type austenite (fcc) boundaries form at h1 1 1i-type
ra 0 /c is the martensite–austenite interfacial energy, and aa 0 is
martensite (bcc) boundaries [34,35]. Keeping this in mind,
the martensite lattice parameter.
and based on theoretical grain boundary calculations per-
To calculate J(T) in Eq. (7), we further need to estimate
formed by Shibuta et al. [36] for a specialty Fe–Cr alloy,
C1, the concentration of nucleation sites available for aus-
the bcc phase h1 1 1i-type grain boundary energy ra0 /a 0 is
tenite nucleation, which depends on the type of nucleation
assumed to be approximately 1.3 J m2 [35]. Furthermore,
sites considered. On the basis of several studies on cold-
because the interfaces are crystallographically related
rolled SS grades and Fe–X alloys [7,8,16,17,32], we have
through the Nishiyama–Wasserman (½110c ==½11 1a0 ) rela-
assumed that the austenite nucleates on martensite grain
tionship [34,35,37], we assume that the energy of the new
boundaries. The concentration of martensite grain bound-
a0 /c interface is equal to the eliminated a0 /a0 interface. This
aries C gb 1 available for austenite nucleation is estimated
is a reasonable assumption, as discussed by Gjostein et al.
according to [26]:
[38], who have experimentally determined the bcc/fcc inter-
dgb facial energy ratio for Fe–C alloys to be approximately 1.
a0
C gb
1 ¼ C 0 ; ð9Þ
da0
2.3. Estimation of the volume free energy change DGv(T)
where C0 is the total equilibrium concentration of nucle-
ation sites available, d gb
a0 is the martensite grain boundary DGv(T) is the free energy change per unit volume
width and da0 is the average martensite grain size. between the product-phase austenite and the parent-phase
Finally, to determine J(T) in Eq. (7), the activation martensite. It can be expressed (in J m3) as:
energy for heterogeneous nucleation DG(T) must be calcu-
0
lated. DG(T) depends on the volume of the austenite Gc ðT Þ Ga ðT Þ
DGv ðT Þ ¼ ð12Þ
nucleus, the grain boundary area of the a0 /c interface, the Vc Va
0
S. Rajasekhara, P.J. Ferreira / Acta Materialia 59 (2011) 738–748 741
0
where Gc(T) and Ga (T) are the free energies per mole of the parameters describing the interaction between the ith and
0
austenite and martensite phases respectively, and Vc, Va the jth element in the respective phases. Miettinen has
the molar volumes of austenite and martensite phases tabulated the first-order interaction parameters Lij, for
respectively. The free energy per mole contribution of an the bcc and the fcc phases in commercial SS, to determine
element j in the martensite and austenite phases can be the excess free energy in the respective phases [40,42].
written as [39,40]: Finally, we ignore the magnetic ordering contribution to
Xn X
n the free energy because, as has been discussed elsewhere
0 0 0 0
Ga ðT Þ ¼ xj Gaj ðT Þ þ xj RT lnðxj Þ þ Gaxs ðT Þ þ Gam ðT Þ [40], their values are close to zero above room temperature.
j¼1 j¼1 Thus Eq. (11) may be rewritten as:
ð13aÞ Pn Pn P Pn
c
j¼1 xj Gj ðT Þ þ lnðxj Þ þ n1
j¼1 xj RT i¼1
c
j¼iþ1 xi xj Lij
DGv ðT Þ ¼
X
n X
n V c
Table 2
Kinetic parameters for grain growth n and k at different annealing
temperatures [22].
Annealing Kinetic parameters
temperature (°C)
n k
Fig. 3. TEM bright-field image of cold-rolled AISI 301LN SS [18]. The 800 2.8 0.1
lath martensite size da0 was determined to be approximately 0.17 lm. 900 2.8 1.6
1000 2.4 3.6
2.7. Determination of the kinetic parameters – k and n Fig. 5. (a) Exponential regression analysis to determine k value at 700 °C;
(b) linear regression analysis to determine n value at 700 °C.
Finally, to solve Eq. (11), the magnitudes of the grain
growth kinetic parameters k and n are also required. For information and solving the grain growth law for samples
the present work, the grain growth parameters have been annealed at 800, 900 and 1000 °C (Table 2) [20]. The grain
determined by using experimentally known grain size growth law was applied to only these samples because they
744 S. Rajasekhara, P.J. Ferreira / Acta Materialia 59 (2011) 738–748
are assumed to comprise of only austenite phase [20]. determine its values at 700 °C (Fig. 5a). Determining n val-
According to Table 2, k1000 °C > k900 °C > k800 °C, which is ues is less trivial because of challenges associated with
expected because k is directly proportional to the probabil- modeling grain growth parameter as a function of temper-
ity of atoms moving from one grain to the next [26]. We ature and material system. Burke and Turnbull [46], who
also note that n800 °C n900 °C > n1000 °C. The higher n have evaluated grain growth in various metallic systems
value at 800 and 900 °C is likely due to residual strains (microalloyed carbon steels, aluminum, brass), have sug-
and the high texture from the parent martensite phase. gested that n values increase with decreasing temperature.
Additionally, these samples contain chromium nitride pre- Atkinson [47] reviewed that n values depend on the grain
cipitates [18], which inhibit grain growth and contribute to growth mechanism; specifically n-values for grain growth
a higher n value. On the other hand, annealing at higher in an impure system by lattice or grain boundary diffusion
temperatures relieves the residual strains, dissolves the pre- were 3 or 4, respectively. Vandemeer and Hu [48] tabulated
cipitates and increases the atomic migration along the grain that grain growth exponents in zone-refined Fe alloys to
boundaries, which promote the loss of grain curvature and range between 2 and 4. Gavard et al. [49] experimentally
texture; all of which lead to a decreased n value. Indeed, determined n values in ultra-pure stainless steels to range
samples annealed at 1000 °C exhibit a lower n value. between 2 and 6. In the present context, we have obtained
The samples annealed at 700 °C contain significant n-values from linear regression (Fig. 5b). This is a reason-
amounts of martensite, and therefore reliable k and n val- able first assumption because it empirically takes into
ues cannot be obtained by applying the grain growth law. account experimental observations of increasing n-values
Therefore, k and n values for samples annealed at 700 °C with decreasing annealing temperatures. Under these con-
have been obtained by applying regression analysis to the ditions, n and k values at 700 °C are found to be approxi-
k and n kinetic parameters at 800, 900 and 1000 °C. k is mately 3.1 and 0.007 respectively.
shown to have an exponential dependence on temperature Naturally, a possible error in calculating the austenite
[26], and thus an exponential regression is employed to phase fraction is introduced by using k and n values for
Fig. 6. Calculated (curves) and experimental (scatter points) austenite phase percentage as a function of annealing time and temperature. (a–c) show the
phase percentage when nitrogen-diffusion is assumed to be the rate-limiting step, whereas (d–f) show the phase percentage when chromium diffusion is
assumed to be the rate-limiting step.
S. Rajasekhara, P.J. Ferreira / Acta Materialia 59 (2011) 738–748 745
where Di and xi are the diffusivity and the mole fraction of Appendix A
the diffusing species, and all the terms retain their previous
definitions. The incubation times for the rate-limiting cases The free energy of pure elements that are used in this
of nitrogen and chromium diffusion as a function of work have been obtained from the work of Dinsdale [41]
annealing temperatures (700–1000°C) were calculated and Miettinen [42], and are shown below. Gibbs free ener-
(Fig. 7a). The incubation time with nitrogen-diffusion as gies of pure elements in the bcc phase:
the rate-limiting factor is approximately 5–6 ls, while it is
Gbcc o
C ðT Þ GC ¼ 107; 350 þ 35:76T
much higher (several hundred milliseconds) with chromium
diffusion as the rate-limiting factor. This should not be sur- 1 o
Gbcc
N ðT Þ GN 2 ¼ 31; 187 þ 59:8T
prising because of the inverse dependence of the incubation 2
time on the diffusivities (Eq. (20)). bcc
Gnickel ðT Þ ¼ 3535 þ 114T 22 lnðT Þ
Based on the incubation times for the above-mentioned
annealing conditions, the nucleation rates for austenite Gbcc
chromium ðT Þ ¼ 8856 þ 157T 27 lnðT Þ
Lbcc
CrNi ¼ 17; 170 11:82T þ ð34; 418 11:858T ÞðxCr xNi Þ Lfcc
FeN ¼ 92; 779 56:509T þ ð28; 554 þ 24:734T ÞðxFe xN Þ
2
þ ð3805 5:203T ÞðxFe xN Þ
Lbcc
CrSi ¼ 102; 085 þ 9:543T þ ð49; 125 þ 14:11T ÞðxCr xSi Þ
Lbcc
CrCu ¼ 77; 107 Appendix B
Lbcc
NiMn ¼ 51; 785 þ 3:5T þ ð6600ÞðxNi xMn Þ
The geometric parameters a, b and c for different types of
Lbcc
NiMo ¼ 46; 422 martensite grain junctions as a function of the dihedral angle
Lbcc
NiSi ¼ 100; 000
between the surface bounding the austenite nucleus [33].
ra0 =a0
Lbcc
NiCu ¼ 8366 þ 2:802T k ¼ cosðhÞ ¼
2ra0 =c
Lbcc
MnMo ¼ 7500
2-grain junction:
Lbcc
MnSi ¼ 89; 621 þ 2:941T þ ð7500ÞðxMn xSi Þ
a ¼ pð1 k 2 Þ
Lbcc
MoSi ¼ 70; 900
b ¼ 4pð1 kÞ
Lbcc
FeC ¼ 119:04T þ ð43:89T ÞðxFe xC Þ þ ð7:89T ÞðxFe xC Þ2 2p
c¼ ð2 3k þ k 3 Þ
Lbcc 2 3
FeN ¼ 19:12T þ ð6:22T ÞðxFe xN Þ þ ð1:02ÞðxFe xN Þ
3-grain junction:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
First-order interaction parameters in the fcc phase:
a ¼ 3dð1 k 2 Þ k 3 4k 2
p
Lfcc
FeCr ¼ 10; 833 7:477T þ ð1410ÞðxFe xCr Þ
b ¼ 12 v kd
12
Lfcc qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
4-grain junction:
Lfcc
CrMn ¼ 19; 088 þ 17:542T 8 20sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi1 39
< 2 2 =
Lfcc
CrMo ¼ 28; 890 7:962T þ ð5974 2:428T ÞðxCr xMo Þ
K K
a ¼ 3 2/ð1 k 2 Þ K 4@ 1 k 2 A pffiffiffi5
Lfcc : 4 8 ;
CrNi ¼ 8090 12:88T þ ð33; 080 16:036T ÞðxCr xNi Þ
p
Lfcc
CrSi ¼ 102; 085 þ 9:543T þ ð49; 125 þ 14:11T ÞðxCr xSi Þ b ¼ 24 k/ u
3
8 20sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi1 3
Lfcc
CrCu ¼ 53; 196 3:312T < p 2 2
K K
Lbcc c ¼ 2 4 u þ kK 4@ 1 k 2 A pffiffiffi5
NiMn ¼ 51; 785 þ 3:5T þ ð6600ÞðxNi xMn Þ : 3 4 8
Lfcc
NiMo ¼ 4804 5:96T þ ð10; 800ÞðxNi xMo Þ )
Lfcc
NiSi ¼ 161; 150 þ 43:799T þ ð118; 251 þ 43:33T ÞðxNi xSi Þ
2k/ð3 k 2 Þ
Lfcc
NiCu ¼ 8366 þ 2:802T þ ð4360 1:812T ÞðxFe xCu Þ where
Lfcc ¼ 22; 300 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
MnMo
4 3 2
Lfcc K¼ 2k 2 k
MnSi ¼ 95; 600 þ 2:941T þ ð7500ÞðxMn xSi Þ 3 2 3
Lfcc
MoSi ¼ 70; 900 K
/ ¼ sin1 pffiffiffiffiffiffiffiffiffiffiffiffi2ffi
Lfcc
FeC ¼ 162; 316 43:512T þ ð60; 803 þ 17:24T ÞðxFe xC Þ 2 1k
pffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffi
þ ð10; 957 3:306T ÞðxFe xC Þ2 1 2 k 3 K2
u ¼ cos pffiffiffiffiffiffiffiffiffiffiffiffiffi
K 1 k2
748 S. Rajasekhara, P.J. Ferreira / Acta Materialia 59 (2011) 738–748