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Glass formation in a high entropy alloy system
by design
Article in Intermetallics · April 2012
DOI: 10.1016/j.intermet.2011.12.006

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125. All rights reserved. to describe these systems.25 were produced by vacuum arc melting and investigated as a potential high entropy alloy and glass forming system.3] (HEAs). Iain Todd a a b University of Sheffield. Yeh [2] later introduced the phrase “high entropy alloy”. BMG compositions also tend to occur close to eutectic compositions. which would be expected according to the Gibbs phase rule and the Hume-Rothery rules for alloying.3. doi:10. Keywords: B. Department of Materials Science and Engineering. UNAM. 0. a large negative enthalpy of mixing between atom pairs. *.Intermetallics 23 (2012) 204e207 Contents lists available at SciVerse ScienceDirect Intermetallics journal homepage: www. with models to predict glass forming compositions based on the need for a high density of atomic packing.ac. Tel.12. 0. where R is the universal gas constant.125 and 0. which may result in an observable macrostate by Boltzmann’s equation.2011.006 % and 35 at% and possessing the ability to form simple solid solution phases with face centred cubic (fcc) or body centred cubic (bcc) crystal structures. John Plummer a. These combinations of high strength and ductility are not realized in conventional alloys where high yield strength and ductility are often competing properties and. HEAs were defined by Yeh et al.F. Amorphous or glassy alloys have been extensively studied. Introduction Two metallic materials receiving extensive interest are bulk metallic glasses (BMGs) [1] and the more recently reported high entropy alloys [2.elsevier. Casting C.intermet.8] whilst exhibiting work hardenability [9] and good ductility up to 26% strain to failure [2. All rights reserved. for these reasons. which has sufficiently high configurational entropy to overcome the effects of the heat of mixing of the alloy.cunliffe@sheffield. 0966-9795/$ e see front matter Ó 2011 Elsevier Ltd. In the case of HEAs U is the number of ways of arranging N component species . Sir Robert Hadfield Building. UK Instituto de Investigaciones en Materiales. South Yorkshire S1 3JD. Rapid solidification processing E. Inoue proposed three parameters that promote glass formation by encouraging dense random packing. The alloys x ¼ 0. The unique feature of the high entropy alloys in this study was the high vacancy formation energies compared to other reported high entropy alloys and this is believed to be responsible for their ability to form an amorphous phase and their relative sensitivity to Ni content.: þ44 0 114 2225941. fax: þ44 0 114 2225943. [6] in 2004. The ability of HEAs to form such simple microstructures is the key to their properties. HEAs are attracting interest as potential structural materials. 04510 Mexico D. This behaviour is explained by considering the enthalpy and entropy of mixing of the alloys and decomposition products.uk (A. three or more components and large differences in atomic radii between the constituent species [4]. reducing the critical cooling rate for glass formation [5]. Ignacio Figueroa b. E-mail address: andrew. the large number of component elements results in a solid solution.3. have high strengths comparable to those of BMGs in some instances [2. Sheffield..15 were capable of forming either amorphous or high entropy alloy phases. Tg) is at a minimum. Mutual frustration of several possible competing eutectic phases also aids in shifting the nose of the crystalline phase field on a time-temperature-transformation (TTT) diagram to the right.7e9]. Mappin Street. increasing the Ni content destabilised the high entropy alloy phase. resulting in a good understanding of the essential considerations for obtaining glass formation. Ó 2011 Elsevier Ltd. which states Sconf ¼ RlnU. as a result of heavy alloying solid solution strengthening.7. prediction 1. Phase stability. Alloy design B. Thermodynamic and thermochemical properties C.15.com/locate/intermet Glass formation in a high entropy alloy system by design Andrew Cunliffe a. [2] as alloys comprising 5 or more components in roughly equiatomic proportions between 5 at * Corresponding author. Cunliffe). This phenomenon forms alloys which. with their unique ability to precipitate solid solution phases from the melt in preference to intermetallics.1016/j. Mexico a r t i c l e i n f o a b s t r a c t Article history: Received 3 October 2011 Received in revised form 8 December 2011 Accepted 10 December 2011 Available online 23 January 2012 The alloys (TiZrNbCu)1xNix x ¼ 0. The molar configurational entropy (DSconf) of the alloys is related to the number of equivalent microstates (U). This ability to form simple solid solutions rather than the expected complex mixture of intermetallic phases (which are typically observed on devitrification of BMGs) was first observed by Cantor et al. 0. where the melting point is suppressed and so the temperature difference between it and the point at which the glassy structure is frozen in (termed the glass transition temperature.2.

Zr)58.) .1 J K1mol1 respectively would make a random solid solution the more stable state.2 124. The melt-spun ribbons were also analysed by XRD.5 35 40 49 55 43. no high entropy alloy system.0 12. the first corresponding to niobium and the second an unknown bcc HEA phase with a ¼ 2. The ingots were flipped and re-melted 4 times to ensure complete melting and then suction cast into a water-cooled copper die of 6 mm diameter.9 45. (a) Nb Ka EDS map A-HEA3 Nb (green) partitions to dendrites the remaining elements form the matrix phase. In this work we investigate the extent to which this alloy system may form an HEA solid solution or amorphous phase depending on chemistry and cooling rate. as the increase in entropy from a segregated alloy to a random solid solution is greater than that for a polysubstituted intermetallic to a random solid solution [16]. save for the inferred requirement for a positive enthalpy of mixing.2 /min. A-HEA3 and A-HEA4 respectively and the reported HEA compositions CoCrNiFeTi [18] and CoCrNiFeAl [19] were prepared from high purity elements by arc melting in the presence of a Ti “getter”. A-HEA1.6 127. Many of the reported HEA compositions have positive heats of mixing when calculated using the Miedema model [13] and the regular melt model [14]. 0. Results and discussion The A-HEA alloys solidified to form the dendritic microstructure seen in Fig. consisting of 5 or more elements and forming a simple fcc or bcc solid solution [2] with the ability to form an amorphous phase on rapid cooling has been reported.14] give negative DHmix in the range 35 to 55 kJ mol1.Zr)58 and Cu10Zr7 signals. with a slow scan rate of 0. A-HEA2.4 43.15. 0. The compositions (TiZrNbCu)1xNix.125. m. The compositions A-HEA3 and A-HEA4 also precipitated niobium dendrites but the HEA peak is suppressed in the XRD trace of A-HEA3 and absent in A-HEA4. and one that is incompatible with glass formation. Fig. Alloy Dr (%) DHmix (kJ mol1) G (GPa) B (GPa) m A-HEA1 A-HEA2 A-HEA3 A-HEA4 12. and by differential scanning calorimetry (DSC) with a Perkin Elmer Diamond DSC.51 nm. This corresponds to increased Ni content causing the enthalpy of mixing of the alloys to become more negative.20.125. The compositions also all fulfil the requirements of an HEA former.5 125. 1b.25 fulfil the main requirements of a glass former discussed above. m (m ¼ 12(B/Gþ0. The compositions CoCrCuFeNiAl (fcc) [8] and WNbMoTaV (bcc) [15] have heats of mixing 18. It may be that compositions with positive heats of mixing and prone to segregation form HEAs most readily. To date.0 42 42 42 42 onto the n non-equivalent lattice points of the crystal unit cell [10. 3. and (2) scanning electron microscopy (SEM) using an FEI Sirion.7 kJ mol1 and 13.67)) [17]. 1.15 12.25. Thus if the formation of random solid solution phases in HEAs depends wholly upon sufficiently high entropy of mixing then a zero or positive value of enthalpy of mixing must be a requirement of the alloy system. x ¼ 0. with energy dispersive spectrometry (EDS) capability. 0.5 % and the kinetic glass index. being replaced by Ni42(Ti.8 130. though at high temperature the configurational entropy of each solid solution of 22. Cunliffe et al. was calculated using the method of Park et al. (For interpretation of the references to colour in this figure legend. 0. / Intermetallics 23 (2012) 204e207 Table 1 Theoretical elastic moduli (calculated from method in Ref. (2) the fcc lattice has the highest entropy for 6e10 component HEAs and (3) for compositions above 10 components an hexagonal close packed (hcp) lattice would have the greatest entropy.11]. 0. the reader is referred to the web version of this article. The high Sconf of the HEA solid solutions must be large enough to overcome the enthalpy of mixing of the metals composing the alloy. 2. This may be the reason why no hcp HEAs have been reported although electronic structure undoubtedly plays an important role in the lattice type [12].0 46. the size mismatch of the alloys 205 varies from 12. DHmix 64 kJ mol1. 1a and EDS analysis found that the dendrites consisted mainly of Nb e see Fig.20.9 kJ mol1 respectively and would normally be expected to segregate. 0. Calculating Sconf in this way it can be seen that (1) the entropy of the bcc lattice is highest for 5 component HEAs.36 12. The suction cast rods were investigated by: (1) X-ray diffraction (XRD) using a Siemens D500 diffractometer with a Cuka source. Experimental procedures Four alloys in the (TiZrCuNb)1xNix system with x ¼ 0. The chamber was evacuated to a pressure of 103 Pa and backfilled with high purity argon. Identification of an alloy system which forms both an HEA solid solution and a glassy phase would allow novel processing routes for high entropy alloys and create he possibility of HEA reinforced amorphous alloy composites but would also force a re-evaluation of the explanation of HEA formation. [25]) and kinetic fragility index. High concentrations of Ni push the equilibrium between the solid solution and the decomposition products towards formation of Ni-X intermetallic phases. XRD traces in Fig. as calculations using Miedema’s model [2. [17] to be the intermediate value of 42 (based on theoretical elastic moduli) see Table 1.A.0 % to 12. using gold sample pans and a heating rate of 20 Kmin1.15.5 J K1mol1 and 19. Ribbons with a thickness of approximately 20 microns of each alloy were generated by melt spinning. 2 confirm that the cast alloys A-HEA1 and A-HEA2 solidified to form two phases. Heats of mixing calculated using the Miedema model [13] imply that at these compositions Ni would react most favourably with Ti and Zr to form intermetallic phases of the type Ni42(Ti. (b) back scattered electron image of A-HEA3 microstructure.

XRD traces show A-HEA1 & 2 solidify to form a dual phase microstructure consisting Nb and another bcc HEA phase. As a consequence of this. this supports Yeh’s explanation of the HEA phenomenon [2].5 % further lowering of the enthalpy of mixing of the alloys and in A-HEA3 and A-HEA4 competition between intermetallic formation. As Ni content is increased in A-HEA3 and A-HEA4 there is an additional increase in peak 1 area. for the suppression of intermetallics. U ¼ 1000DSmix/DHmix where if U < 1 a HEA will be formed. Should this occur. 3. when the difference in free energy of the solid solution and the intermetallic phase DGIM-SS ¼ 0). with a characteristic broad peak between approximately 20 and 30 2q. XRD traces of the melt-spun A-HEA alloys reported here (Fig. the rule of mixtures (RoM) melting point is shown in Table 2 for comparison. DSC traces of A-HEA alloys.15 and 0. These were taken as the onset values and are shown in Table 2. corresponding to an increase in the volume fraction of the Ni-rich intermetallic phase.206 A. In general both Tg and Tx increase with increasing Ni content. The method of calculation of the enthalpy of mixing and melting points of the alloys is neglect of vibrational entropy. The melting point of each alloy was outside the range of DTA measurements and therefore known to be greater than 1723 K. which does not show signs of ordering in the XRD trace. also confirming glass formation. resulting in ambiguity in the prediction for this alloy.6 Tm to substitute into Zhang’s equation is not available. which both show a clear tendency towards ordering have values of Tc greater than the predicted melting temperature and would therefore be expected to solidify directly to the ordered structure. 3) show amorphous traces. 4. . Tg and Tx respectively. whilst those for A-HEA3 and A-HEA4. For the alloys reported here the melting temperature is not known and so a suitable value of 0. A-HEA 2 and A-HEA3 and three peaks for A-HEA4. and instead precipitated crystals. It is noteworthy that the Tc of A-HEA1. resulting in the Zr and Cu reacting to form the intermetallic Cu10Zr7. The configurational entropy of the 5 component bcc solid solutions was calculated as described above. the alloy would then be depleted in Ti and Ni and the remaining composition has insufficient configurational entropy to form an HEA random solid solution phase. showing Tg and Txs. 2.6 Tm for the alloys reported in [20] below which diffusion would be sluggish and the HEA phase would be metastable. 4. Alloy Tg (K)  5 K Tx (K)  5 K DTx (K) RoM Tm (K) Tc (K) A-HEA1 A-HEA2 A-HEA3 A-HEA4 648 651 662 678 721 717 731 743 73 66 69 65 2000 1992 1977 1961 1781 2130 2582 2880 Fig. whether an alloy can remain in the HEA solid solution phase on cooling. at some value of x between 0. These alloys are unable to form a high entropy phase when the critical temperature for HEA formability is higher than the solidus temperature of the alloy. However. Cunliffe et al. This is indeed what was observed. The CoCrFeNiTi and CoCrFeNiAl melt-spun ribbons did not form an amorphous phase during solidification. with enthalpy of mixing of the alloys used to estimate the critical temperature. This appears to be the mechanism at work here. Table 2 Transition temperatures of the alloys.e.2 the enthalpy of formation of the intermetallic phase is such that the entropy of a random solid solution is insufficient to suppress ordering. The increasing area of the first crystallisation peak with Ni content indicates an increase in volume fraction of the intermetallic phase. This is due to the effect of increasing Ni content on the glass formation parameters of Inoue [4] as a result of the increasing atomic misfit from 12. being as it is on the cusp of HEA formability. 1000 K is approximately 0. / Intermetallics 23 (2012) 204e207 Fig. Yeh [2] states the ability of an HEA to form a simple solid solution results from the high configurational entropy of the system. is significantly lower than the RoM melting temperature of the alloy. The Tc of each alloy is shown with Hmix in Table 2.0 % to 12. The devitrificaton products in A-HEA1 and A-HEA2 are the bcc HEA phase and Nb solid solution and these crystallisation events correspond to peaks 1 and 2 respectively in the DSC traces of these alloys in Fig. (i. Tc ¼ Hmix/Sconf. thus Zhang’s model predicts Fig. In a similar calculation Zhang [20] discussed a HEA formability parameter. The DSC data shows the glass transition and crystallisation start temperatures of the alloys. For A-HEA2 the melting and critical temperatures are very similar but XRD data shows no sign of ordering. DSC traces show two crystallisation peaks for AHEA1. XRD traces of the A-HEA alloys showing amorphous halo.

Similar reasoning would also account for the disruption of HEA formability with increasing Ni in this series of alloys. [23] Xuilin J. Science in China Series 2008. Materials Science and Engineering A. 1997:1493e513. on slow cooling from the melt the HEA phase is observed because the nose of the HEA phase field on a TTT type diagram occludes any intermetallic phases but when crystallisation occurs from the metastable amorphous phase. Chen SK. [14] Li A.G 51:427e37. where the formation of vacancies permits selfdiffusion. [19] Li C. 1988. 1995. Johnson WL. Applied Physics Letters 2001. Jiang Q. A possible mechanism. the FeCoCrNiAlCu [22] alloy is known to precipitate intermetallic phases after heat treatment. Chen SK. Journal of Alloys and Compounds 2009. promoting crystallisation. Physical metallurgy and processing of intermetallic compounds. It was suggested that this link is due to the relationship between vacancy formation energy and crystallisation temperature. [11] Stoloff NS. which are unable to form glassy phases by rapid solidification. Materials Science Forum 2010. Journal of Alloys and Compounds 2009. suggesting that they are also capable of accommodating some variation in chemistry whilst still maintaining their structure. MRS Bulletin 2007. [20] Zhang Y. enabling them to form amorphous alloys on rapid cooling. This suggests that there is more determining the formation of HEA phases than simply the entropy of mixing. Vacancy formation energies of the alloys in this study were calculated in Table 3 using the method in [23]. Wilkes GB. along with those of reported CoCrFeNiTi and CoCrFeNiAl HEAs. Kim DH. Methfessel M. This would allow the formation of glassy and high entropy phases in a single system. Shun TT. References [1] Greer AL. Intermetallics 2003.32:611e5. Sikka VK. Ni and Co which are all able to substitute onto the face centred positions of the L12 g0 phase when the two other common HEA components Ti and Al are present [12]. Ni42Ti58 and Cu10Zr7 indicates there is a cooling rate effect in the formation of the HEA phase. Na JH. as Ni promotes the Ni-Ti/Zr intermetallics and the whole system then decomposes to binary and ternary intermetallics. Li BS. Schroers J. Chen YL. Proceedings of the Royal Society London A. Kamaraj M. where they devised the figure of merit DHhDHmixSconf and discovered that there was a strong trend between the magnitude of this value and the critical diameter of an amorphous alloy. [13] Boer FR. It is interesting that the HEAs thus far reported have lower vacancy formation energies. / Intermetallics 23 (2012) 204e207 207 Table 3 Vacancy formation energies of various alloy types. et al. Zhang X. Acta Materialia 2000.478: 321e4. Zhao M. Mattens WCM. These properties separate them from many of the reported HEA compositions.375e377:213e8.508:214e9.11:529e40.654e656:1058e61. Zhao M. Materials Science and Engineering A 2009. [17] Park ES. Vincent AJB. Hand RJ. Here the (TiZrNbCu)1xNix system has been shown to be capable of doing both. Cohesion in metals transition metal alloys. 4. Li JC. [12] Paxton AT. Chuang CP. The ability to form vacancies also improves the structural stability of ordered compounds with respect to chemistry. Materials Science and Engineering A 2008. Acknowledgements A Cunliffe and J Plummer would like to acknowledge the financial support of the EPSRC in funding their studentships. [16] Stoloff NS.36:881e93. Zhang JY. Miedema AR. [18] Zhang KB. Journal of Non Crystalline Solids 2009. Zhou YJ. is suggested. Wiley. leading to decomposition of the solid solution and the formation of binary intermetallics [21]. regardless of mechanism. [21] Li C. Yeh JW. 1998.485:154e9. depending upon cooling rate. Applied Physics Letters 2007. [6] Cantor B. Li JC. Fu ZY. Figueroa IA. Conclusions If HEA formability depends only on the entropy of mixing overcoming the enthalpy of mixing to suppress precipitation of intermetallics it would be difficult to produce a system capable of forming both HEA and amorphous phases. Niessen AK. However. Knight P. Tsau HC.355:335e9. 2008. Acta Metallurgica Sinica (English Letters) 2009. Hui XD.34:153e83.11:641e4. [3] Zhang Y. Jiang Q. intermetallic alloys and glass forming alloys.48:279. The observation that there is a kinetic contribution to the formation of HEAs suggests that they are not the most thermodynamically stable phase of the system. Ni and Ti) to greater than a 3:2 ratio disrupts this arrangement. If the entropy of mixing were solely responsible for the formation of a random solid solution then the microstructure would be more stable at elevated temperatures and elements would be expected to remain in solid solution. the alloy decomposes to form binary intermetallics. [4] Inoue A. et al.104. [9] Varalakshmi S. [7] Wang FJ. causing a broadening and eventual splitting of the second peak. North Holland Physics Publishing. . Chang ITH. conversely. Advanced Engineering Materials 2009. Pan Y.22:219e24. [15] Senkov ON. Chen YL. This strongly suggests that the ability of some alloys to form apparent high entropy phases results from their constituent metals’ abilities to substitute for one another in ordered cubic structures. negative enthalpy of mixing and multiple components. Alloy Vitralloy1 A-HEA1 A-HEA2 A-HEA3 A-HEA4 CoCrFeNiTi CoCrFeNiAl NiTi DHh/kJ mol1 283 281 280 274 266 225 212 133 The remaining material then crystallises to form a mixture of Nb solid solution and the Cu10Zr7 phase. [5] Waniuk TA.475:752e7. The low vacancy formation energy of the intermetallic alloys allows the structure to be maintained despite variations in stoichiometry. Statistical physics. Murty BS. Chen GL. Increasing the ratio of Al to all other elemental constituents (Fe. The vast majority of reported HEA compositions contain Fe. Intermetallics 2010. Journal of Applied Physics 2008. [2] Yeh JW. [10] Mandle F. Co.78:1213e5.91:031907. Pettifor DG. Indeed. Zhang Y. [25] Plummer J. [22] Wang YP. Todd I. Boom R. Liaw PK. Davies HA. Springer. Ma E. Chen GL. [24] Loffler JF. Fu HZ. [8] Tong CJ. not at odds with the requirements of a good glass former. Materials Science Forum 2007. Wang YC. That devitrification of these alloys results in the formation of Nb. an alloy system with the capacity to form both a high entropy solid solution and an amorphous phase opens up the possibility of novel processing routes for producing HEAs with nanocrystalline microstructures and metallic glassy alloys toughened with HEA crystallites. Which suggests the HEA phase does not replace intermetallics as the most stable phase but that it is the most readily formed when cooling from the randomly distributed melt phase. Wang H. the A-HEAs in this study have high vacancy energies similar to that of the good glass former Vitreloy 1 [24] The high vacancy binding energy of the A-HEAs compliments the atomic size variation. International Materials Reviews 1989.A. Wang WM. Cunliffe et al. This allows for the large number of degrees of freedom when the Gibbs phase rule is applied to HEA compositions [6] while. Recent work by Pan [23] showed a link between vacancy formation energy of an alloy.560:1e9. Wang ML. 18:1756e8. Lin SJ. Materials Science and Engineering A 2004. Metallurguical and Materials Transactions A 2005. Miracle DB.