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Article history: An attempt has been made to predict phase formation using a CALPHAD-based approach for a large num-
Received 22 June 2012 ber of compositions that are known to form FCC, BCC and a mixture of FCC and BCC phases. The stable
Accepted 22 July 2012 phase is assumed to be the rst phase that is formed upon cooling from liquid state with the highest driv-
Available online 7 August 2012
ing force. The driving force for other phases at the transition for various compositions is also presented. A
comparison between the parametric approach of phase prediction by study of thermodynamic and topo-
Keywords: logical parameters on one hand and the CALPHAD approach on the other is also presented. CALPHAD
Multi-component alloys
approach appears to predict BCC phase formation much more accurately than the FCC phase formation.
High entropy alloys
Thermodynamics
The results indicate that solid solution formation in multicomponent alloys is favored when the ratio of
CALPHAD DScong/DSfusion is greater than 1 and 1.2 for equiatomic and non-equiatomic alloys, respectively. The
Phase prediction results also point out that BCC phase is favored when the atomic size difference is larger, which is
reected by a higher value of DSr/k. Formation of FCC phase appears to be governed mainly by DHmix,
while BCC phase governed by DSr/k, which is representative of strain in the structure.
2012 Elsevier B.V. All rights reserved.
1. Introduction with their references [223]. These are in turn divided according to the predomi-
nant phase that is observed (a) FCC, (b) FCC + BCC and (c) BCC. In total, 93 com-
positions were studied that fall into either FCC or BCC or a mixture of FCC and
Multi-component nearly-equiatomic alloys, also known as BCC phase forming compositions. The exact split is given in Table 3.
high-entropy alloys (HEAs) constitute a recent class of alloys rst
developed by Yeh and his co-workers [1] in 2004. The most signif-
icant aspect of this class of alloys is that they yield mostly a simple 3. Background of the CALPHAD-based approach
solid solution or a mixture of solid solutions based on FCC or BCC
phases. The presence of multi-principal elements in nearly equi- The CALPHAD technique makes use of the principle that the
atomic composition gives rise to large entropy of mixing (congu- Gibbs energy of a phase, described as a function of temperature
rational entropy), which increases with the number of elements if and composition, is enough to obtain a complete thermodynamic
the composition remains close to equiatomic. Consequently, alloys description of the system since almost all thermodynamic proper-
can be formed with simple crystal structure by suppressing forma- ties can be derived from the Gibbs energy function. Central to nd-
tion of complex phases and intermetallics. ing the stable/metastable state of the system is the Gibbs energy
Further, alloys with these simple structures also possess several minimization. Equilibrium conditions are described as a set of
promising properties such as high strength, wear resistance, oxida- non-linear equations involving the Gibbs energies of the corre-
tion resistance, etc., which in turn closely depend on the phase(s) sponding phases.
formed. In this regard, to obtain better homogeneity in properties According to the CALPHAD approach, the Gibbs energy of a
and to truly call the resulting alloy a high-entropy alloy, the tar- phase u is expressed as [28]
get is to obtain a single solid solution. In this work, formation of Gu ref Gu id Gu ex Gu 1
FCC and BCC phases, the two most important phases seen in this
The rst term is the contribution of the pure components of the
class of alloy systems is studied using CALPHAD-based and para-
phase, the second is the ideal mixing contribution and the third is
metric thermodynamic and topological analyses.
the excess Gibbs energy of mixing. The second term is given by:
2. List of compositions
id
Gu RT Ri xi ln xi 2
For a liquid phase, the excess Gibbs energy is described as:
For the present work, the systems from literature used for the analysis are listed
in Table 1 (equiatomic systems) and in Table 2 (non-equiatomic systems) along ex
Gu Ri Rj>i xi xj Rv L/ij xi xj v 3
Corresponding author. The L/ij model parameters are the RedlichKister parameters that
E-mail address: murty@iitm.ac.in (B.S. Murty). need to be determined by an assessment procedure that relies on
0925-8388/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2012.07.105
R. Raghavan et al. / Journal of Alloys and Compounds 544 (2012) 152158 153
Table 1 Table 2
Equiatomic compositions studied in literature used for this work. MA stands for Non-equiatomic compositions studied in literature used for this work.
synthesis by Mechanical Alloying.
System Synthesis Route Refs.
System Synthesis route Refs.
(a) FCC
(a) FCC CoCrCuFeNiTi0.5 Casting [2]
CoCrCuFeNi Casting [2] CoCrCuFeNiTi0.8 Casting [2]
CoCrCuFeNiTi Casting [2] Cu2.5NiCoZnAlTi MA [4]
FeNiCrCuMo Casting [3] Cu5NiCoZnAlTi MA [4]
CuNi MA [4] Ni2.5FeCrCoMnW MA [5]
CuNiCo MA [4] Ni5FeCrCoMnW MA [5]
CuNiCoZn MA [4] NiCrCuFeMo0.25 MA [14]
CuNiCoZnAl MA [4] NiCoCrFeMo0.25 MA [14]
NiFe MA [5] Al0.5CoCrCuFeNi Casting [15]
NiFeCr MA [5] Al0.375CoCrFeNi Casting [8]
NiFeCrCo MA [5] Al0.5CrFeCoNi Casting [16]
NiFeCrCoMn MA [5] CoCrFeNiAl0.3 Casting [17]
FeNiMn MA [5] CoCrFeNiMo0.3 Casting [17]
NiCoCrCuFe MA [6] CoCrFeNiAl0.3Mo0.1 Casting [17]
(b) FCC + BCC FeCoNiCrCu0.5 Casting [18]
FeNiCrCuAl Casting [3] Ti0.5CrFeCoNiAl0.25Cu0.75 Casting [19]
FeNiCrCuMn Casting [3] Al0.5CoCrCuFeNi Casting [20]
AlCoCrCuFeNi Casting [7] Cu0.5NiAlCoCrFeTiMo MA [21]
AlCoCrFeNi Casting [8] (b) FCC + BCC
AlCrFeCoNiCuMn Casting [9] Ti0.5CrFeCoNiAl0.5Cu0.5 Casting [19]
AlCrFeCoNiCuTi Casting [9] Al0.5CoCrCuFeNiTi0.2 Casting [20]
CrCuMnNi MA [10] Al0.5CoCrCuFeNiTi0.4 Casting [20]
AlCrCuFeNiZn MA [11] Al0.5CoCrCuFeNiTi0.6 Casting [20]
AlCoCrCuNiZn MA [11] Al0.5CoCrCuFeNiTi0.8 Casting [20]
(c) BCC Al0.5CoCrCuFeNiTi Casting [20]
AlFe MA [12] Al0.3CrFe1.5MnNi1.5 Casting [22]
AlFeTi MA [12] Al0.3CoCrFeNi Casting [23]
AlFeTiCr MA [12] Al0.3CoCrFeNiMo0.1 Casting [23]
AlFeTiCrZn MA [12] Cu0.5CoNiCrAl Casting [24]
AlFeTiCrZnCu MA [12] Ti0.5CrFeNiAlCo1.5 Casting [25]
FeTiCrZnCu MA [5] Ti0.5CrFeNiAlCo2 Casting [25]
CuNiCoZnAlTi MA [5] Ti0.5CrFeNiAlCo3 Casting [25]
NiCoZnAlTi MA [5] Al0.45FeNiCrCuCo MA [26]
NiFeCrCoMnW MA [5] (c) BCC
FeCrCoMnW MA [5] Al2.5CoCrFeNi Casting [3]
FeNiMnAl MA [5] Al3CoCrFeNi Casting [3]
FeNiMnAlCr MA [5] Al0.45FeTiCrZnCu MA [5]
FeNiMnAlCrCo MA [5] Al2.5FeTiCrZnCu MA [5]
NiMnAlCrCo MA [5] Al5FeTiCrZnCu MA [5]
AlCoCrCuFe MA [6] AlFe0.45TiCrZnCu MA [5]
AlCuCrFe MA [6] AlFeTi0.45CrZnCu MA [5]
AlCrCoFe MA [6] AlFeTiCr0.45ZnCu MA [5]
TiCrFeCoNiAl Casting [13] AlFeTiCrZn0.45Cu MA [5]
AlFeTiCrZnCu0.45 MA [5]
Cu0.45NiCoZnAlTi MA [5]
Ni0.45FeCrCoMnW MA [5]
statistical techniques to obtain the best t to available experimen- Fe0.45NiMnAlCrCo MA [5]
tal data. The binary excess terms are combined using the Muggianu Fe2.5NiMnAlCrCo MA [5]
Fe5NiMnAlCrCo MA [5]
geometrical extrapolation scheme [29].
AlCrCuFeMo0.25 MA [14]
The entire thermodynamic description of phases, which pre- AlCoCrCuFeMo0.25 MA [14]
dominantly includes the Gibbs energy functions as a function of AlCoCrCuFeMo0.5 MA [14]
temperature and composition using a suitable model is contained Al2CoCrCuFeNi Casting [15]
in a TDB le. Thermo-Calc is the software used here, which reads Al2CoCrFeNi Casting [8]
Ti2CrFeCoNiAl Casting [13]
the thermodynamic description from the TDB le and performs Ti3CrFeCoNiAl Casting [13]
the equilibrium calculations. The TDB le contains the unary, bin- CrFeCoNiAlCu0.25 Casting [16]
ary and many ternary interaction parameters of liquid, FCC, BCC Ti0.5CrFeCoNiAl0.75Cu0.25 Casting [19]
and HCP phases for all the elements that are listed in the various Al0.5CoCrCuFeNiTi1.2 Casting [20]
Al0.5CoCrCuFeNiTi1.4 Casting [20]
compositions under study (as outlined in Tables 1 and 2). These
Al0.5CoCrCuFeNiTi1.6 Casting [20]
elements are Al, Co, Cr, Cu, Fe, Mn, Mo, Ni, Ti, W and Zn. Al0.5CoCrCuFeNiTi1.8 Casting [20]
Al0.5CoCrCuFeNiTi2 Casting [20]
4. Implementation and results: driving force calculations using Al0.5CrFe1.5MnNi1.5 Casting [22]
Ti0.5CrFeNiAlCo Casting [25]
Thermo-Calc Al2.5FeNiCrCuCo MA [26]
Al5FeNiCrCuCo MA [26]
Using Thermo-Calc, calculations were performed to nd the AlCoCrFe0.6Mo0.5Ni Casting [27]
rst phase that would crystallize from the liquid state, after incor- AlCoCrFeMo0.5Ni Casting [27]
AlCoCrFe1.5Mo0.5Ni Casting [27]
porating all the required interaction parameters in the TDB le. The
AlCoCrFe2Mo0.5Ni Casting [27]
most stable phase is assumed to be the rst phase to nucleate out
154 R. Raghavan et al. / Journal of Alloys and Compounds 544 (2012) 152158
Table 4
Driving force calculations for equiatomic compositions using CALPHAD approach.
Table 5
Driving force calculations for non-equiatomic compositions using CALPHAD approach.
show formation of FCC + BCC, BCC is the predominant where xi is the mole fraction of atom i. Another parameter, used
phase predicted. widely for analysis of bulk metallic glasses and used here, is the
These results also indicate that most of the multicompo- mismatch entropy (DSr/k) formulated by Mansoori et al. [32]. Their
nent equiatomic alloys prefer to form more open BCC empirical relation for the mismatch entropy, which is a measure of
phase rather than the close packed FCC or HCP phases. the difference in sizes of the constituent atoms, is calculated by mis-
t term DSr from the solution of the PerkusYevik integral equation
5. Coupling the approaches of thermodynamic and topological and is given as:
parametric analyses and CALPHAD
DSr 3 3 1
f2 1y1 f 1y2 f 1f 3 lnf 1 y3
k 2 2 2
Traditionally, thermodynamic analysis of phase formation in al-
loys has involved parameters like enthalpy of mixing, congura- 6
tional entropy, d parameter, etc. This approach has been where,
extended to multi-component alloys here. Enthalpy of mixing is
calculated based on the regular melt model using Miedemas ap- 1
f 7
proach [30,31] as shown below. 1f
DHmix Rni1;ij Xij ci cj 4 n is the packing fraction (equal to 0.64 for a dense random pack-
ing).The dimensionless parameters y1, y2 and y3 are calculated
Xij 4DHmix; AB is the regular melt-interaction parameter between according to following equation:
ith and jth elements, and DHmix; AB is the mixing enthalpy of binary
1
liquid alloy AB. DHmix values for binaries are obtained from y1 RnjPi1 di dj di dj 2 ci cj 8
[31].The molar congurational entropy (DScong) of a phase is an
r3
important parameter for phase formation, given by: r2 n
y2 RjPi1 di dj di dj 2 ci cj 9
DSconfig RRni1 xi ln xi 5 r3 2
r2 3
y3 10
r3 2
and,
the radius of atom i and R is the average atomic radius of the alloy
in
system and DSfusion(=Ri1 DSf ;i ) for all the compositions were esti-
mated with a view to study the range of values exhibited them. The
DSf ;i values are the entropy of fusion values for individual elements
of the alloy and are obtained from the Smithells Metals Handbook.
This parametric study was also done with a view to segregate
FCC and BCC phase forming compositions based on the range of
values of these parameters. Some observations of this study are
as follows:
1. It is clear from Fig. 1(a) that most of the equiatomic solid solu-
tions have DScong/DSfusion > 1, conrming the fact that high
value of DScong aids in the solid solution formation. A few equi-
atomic alloys that have their DScong/DSfusion less than 1 are
actually binary and ternary alloys (Fig. 1(a)). All non-equiatomic
solid solutions studied in this work have (DScong/DSfusion) > 1.2,
indicating that equiatomic alloys have greater tendency to form
solid solutions than the non-equiatomic alloys (Fig. 1(b)).
2. Lattice strain in multi-component alloys is inherent due to the
presence of many atoms with varying sizes. The parameters
DSr/k and d are the two topological parameters that describe
this property. Fig. 1(a) and (b) show that d parameter cannot
be used to demarcate the phases that can form in these alloys.
However, DSr/k, on the other hand, is much more sensitive to
the size difference and is much higher for BCC phase forming
compositions in both equiatomic and non-equiatomic alloys
(Fig. 2(a) and (b), respectively). Due to greater strain, which is
reected by a higher value of DSr/k, a more open structure,
Fig. 1. DScong/DSfusion vs. d plot for (a) equiatomic and (b) non-equiatomic systems. i.e., BCC is preferred than FCC. Fig. 2(a) and (b) clearly show that
R. Raghavan et al. / Journal of Alloys and Compounds 544 (2012) 152158 157
Fig. 2. DScong/DSfusion vs. mismatch entropy (DSr/k) plot for (a) equiatomic and (b)
non-equiatomic systems.
Fig. 3. Comparison of DHMiedema and DHCALPHAD for (a) equiatomic systems and (b)
non-equiatomic systems.
we can delineate a window of DSr/k values that can lead to the
formation of BCC phase in most of the alloys under consider- 4. Since DHmix is the predominant thermodynamic parameter and
ation. Fig. 2(a) and (b) also indicate that the window of DSr/k DSr/k the predominant topological/strain parameter governing
over which BCC solid solution forms is wider in equiatomic phase formation, these are plotted for equiatomic compositions
alloys in comparison to non-equiatomic alloys. in Fig. 4. In Fig. 4(a), DHMiedema is considered and in 4(b),
3. Since multicomponent systems quite often show some devia- DHCALPHAD is considered. Interestingly, these graphs show that
tion from ideality, it would be interesting to study how DHmix, DH and DSr/k have an approximately inverse relationship with
calculated using Miedemas approach (Eq. (4)), and the one esti- each other. It is seen that FCC phases are preferred for systems
mated using the CALPHAD approach (Eq. (3)) differ from each having a high DHmix value (and correspondingly low DSr/k) and
other. This is brought out in Fig. 3(a) and (b) for equiatomic BCC phases preferred for systems with high DSr/k and relatively
and non-equiatomic compositions, respectively. The values cal- low DHmix. This clearly shows that strain is the predominant
culated using the Miedemas approach (Eq. (4)) are denoted as parameter for BCC-forming compositions and enthalpy of mix-
DHMiedema and those found using the CALPHAD approach are ing is the one for FCC-forming compositions. Interestingly, sys-
denoted as DHCALPHAD. Linear ts for each type of phase formed tems that show a mixture of FCC and BCC phases have
are plotted. It is seen that for FCC and FCC + BCC phase forming intermediate values of DH and DSr/k, as expected.
compositions, DHMiedema and DHCALPHAD have better linear rela-
tionship than for BCC forming compositions. This is possibly 6. Conclusions
due to large strain energy in BCC forming compositions. The lin-
ear t for (FCC + BCC) has R2 value of 0.92 and 0.97 and slope of 1. The CALPHAD approach has been used to study the formation of
1.22 and 1.24 for equiatomic and non-equiatomic compositions, FCC and BCC phases in multicomponent alloys. It predicts BCC
respectively. The linear t for BCC phase is poor (R2 = 0.64 for forming compositions with a very good accuracy.
equiatomic and 0.68 for non-equiatomic compositions) 2. Prediction of FCC phases using CALPHAD is poor. It is believed
whereas the t for FCC phase is much better (R2 = 0.83 and that this may be because of a greater presence of kinetic effects
0.91 for equiatomic and non-equiatomic cases, respectively). than in BCC, which is a more open structure.
158 R. Raghavan et al. / Journal of Alloys and Compounds 544 (2012) 152158
References
[1] J.W. Yeh, S.K. Chen, S.J. Lin, Adv. Eng. Mater. 6 (2004) 299.
[2] X.F. Wang, Y. Zhang, Y. Qiao, G.L. Chen, Intermetallics 15 (2007) 357.
[3] C. Li, J.C. Li, M. Zhao, Q. Jiang, J. Alloys Compd. 475 (2009) 752.
[4] S. Varalakshmi, M. Kamaraj, B.S. Murty, Metall, Mater. Trans. 41A (2010) 2703.
[5] S. Varalakshmi, Ph.D. Thesis, IIT Madras (2008).
[6] S. Praveen, B.S. Murty, Ravi S. Kottada, Mater. Sci. Eng., A 534 (2012) 83.
[7] S. Singh, N. Wanderka, B.S. Murty, U. Glatzel, J. Banhart, Acta Mater. 59 (2011)
182.
[8] H.P. Chou, Y.S. Chang, S.K. Chen, J.W. Yeh, Mater. Sci. Eng., B 163 (2009) 184.
[9] B.S. Li, Y.P. Wang, M.X. Ren, C. Yang, H.Z. Fu, Mater. Sci. Eng., A 498 (2008) 482.
[10] A. Durga, K.C. Hari Kumar, B.S. Murty, Trans Ind. Inst. Metals 65 (2012) 375.
[11] K.G. Pradeep, M.Tech.Thesis, IIT Madras (2010).
[12] S. Varalakshmi, M. Kamaraj, B.S. Murty, J. Alloys Compd. 460 (2008) 253.
[13] Z. Yong, Z.Y. Jun, H.X. Dong, W.M. Ling, C.G. Liang, Sci. China, Ser. G 51 (2008)
427.
[14] S. Praveen, Private Communication.
[15] J.M. Wu, S.J. Lin, J.W. Yeh, S.K. Chen, Y.S. Huang, H.C. Chen, Wear 261 (2006)
513.
[16] Y.J. Zhang, J.P. Zhou, Lin, G.L. Chen, P.K. Liaw, Adv. Eng. Mater. 10 (2008) 534.
[17] T.T. Shun, C.H. Hung, C.F. Lee, J. Alloys Compd. 493 (2010) 105.
[18] C.M. Lin, H.L. Tsai, J. Alloys Compd. 489 (2010) 30.
[19] F.J. Wang, Y. Zhang, G.L. Chen, J. Alloys Compd. 478 (2009) 321.
[20] M.R. Chen, S.J. Lin, J.W. Yeh, S.K. Chen, Y.S. Huang, C.P. Tu, Mater. Trans. 47
(2006) 1395.
[21] Y.L. Chen, Y.H. Hu, C.A. Hsieh, J.W. Yeh, S.K. Chen, J. Alloys Compd. 481 (2009)
768.
[22] S.T. Chen, Y.F. Kuo, S.Y. Chen, C.H. Tsau, T.T. Shun, J.W. Yeh, Mater. Sci. Eng., A
527 (2010) 5818.
[23] T.T. Shun, C.H. Hung, C.F. Lee, J. Alloys Compd. 495 (2010) 55.
[24] J.W. Yeh, S.K. Chen, J.Y. Gan, S.J. Lin, Metall. Mater. Trans. A 35 (2004) 2533.
[25] F.J. Wang, Y. Zhang, Mater. Sci. Eng., A 496 (2008) 214.
[26] R. Sriharitha, B.S. Murty and Ravi Sankar Kottada, Intermetallics, Under review.
[27] C.Y. Hsu, T.S. Sheu, J.W. Yeh, S.K. Chen, Wear 268 (2010) 653.
[28] M. Palumbo, L. Battezzati, CALPHAD 32 (2008) 295.
[29] Y.M. Muggianu, M. Gambino, J.P. Bros, J. Chem. Phys. 72 (1975) 83.
[30] A.R. Miedema, P.F. de Chatel, F.R. de Boer, Physica B 100 (1980) 1.
[31] A. Takeuchi, A. Inoue, Mater. Sci. Eng., A 304306 (2001) 446.
Fig. 4. Comparison of DSr/k with (a) DHMiedema and (b) DHCALPHAD for equiatomic [32] G.A. Mansoori, N.F. Carnahan, K.E. Starling, T.W. Leland Jr., J. Chem. Phys. 54
systems. (1971) 1523.