Journal of Alloys and Compounds 460 (2008) 253257

Synthesis and characterization of nanocrystalline AlFeTiCrZnCu high entropy solid solution by mechanical alloying
S. Varalakshmi, M. Kamaraj, B.S. Murty
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036, India Received 5 May 2007; received in revised form 28 May 2007; accepted 29 May 2007 Available online 2 June 2007

Abstract Traditional alloys are based on one or two major alloying elements. High entropy alloys are equiatomic multicomponent alloys, wherein congurational entropy is maximized to obtain single phase solid solutions. The present paper reports synthesis of nanostructured equiatomic high entropy solid solutions from binary to hexanary compositions in AlFeTiCrZnCu system by mechanical alloying. These alloys have BCC structure with crystallite size less than 10 nm. The high entropy solid solution in these alloys is stable even after annealing at 800 C for 1 h. The hardness of AlFeTiCrZnCu solid solution is 2 GPa in the sintered condition with a density of 99%. The similar nanostructured solid solutions have also been synthesized in CuNiCoZnAlTi and NiFeCrCoMnW alloys. 2007 Elsevier B.V. All rights reserved.
Keywords: Mechanical alloying; Entropy; Enthalpy; Transmission electron microscopy

1. Introduction High entropy alloys are a new generation alloys and are quite different from traditional alloys, which are based on one or two elements. These multicomponent alloys are solid solutions with equiatomic or near equiatomic compositions [1]. The principle behind the high entropy alloys is that the congurational entropy is maximum at equiatomic composition and it increases with increase in the number of elements in the system, thus making it difcult for the formation of intermetallics. The congurational entropy at equiatomic compositions for binary, ternary, quaternary, quinary and hexanary alloys is i.e. 5.8, 9.2, 11.6, 13.5, 15.0 respectively which is higher than even the entropy of fusion (711 J mol1 K1 ) of most of the common metals. The formation of amorphous phase, which can be another competing phase in these multicomponent systems, can be avoided by choosing elements carefully, which have small size factors. Table 1 gives the size factor and the enthalpy of mixing for the binary equiatomic alloys in the AlFeTiCrZnCu hexanary system [2]. Even if the enthalpy of mixing is higher (either positive or negative) in some binary combinations, due to the high

mixing entropy these multicomponent equiatomic alloys tend to form only solid solutions. Their structure being simple, these alloys were easy to analyze. Yeh and co-workers [36] is the only group that has so far reported the synthesis of these advanced alloys by conventional casting and thin lm deposition techniques. These alloys can be used for various applications that demand high temperature strength, oxidation, corrosion and wear resistance. However, mechanical alloying (MA) has not been reported so far as a processing route for the synthesis of these alloys. MA is a widely used solid state processing route for the synthesis of advanced materials [7,8]. High entropy alloys reported by Yeh and coworkers [36] are microcrystalline and their properties can be signicantly enhanced if they can be synthesized in nanocrystalline form. MA can easily lead to the formation of high entropy alloys in the nanocrystalline and hence the present study was taken up to demonstrate this in AlFeTiCrZnCu hexanary system.
2. Experimental details
Al, Fe, Ti, Cr, Zn, Cu powders with purity higher than 99.5% and particle size of 45 m (325 mesh) were mechanically alloyed from binary AlFe to hexanary AlFeTiCrZnCu systems in equiatomic ratio. The milling was carried out up to 20 h in high energy planetary ball mill (Fritsch Pulverisette P-5) at 300 rpm with a ball to powder weight ratio of 10:1. Tungsten

Corresponding author. Tel.: +91 44 22574754; fax: +91 44 22574752. E-mail address: murty@iitm.ac.in (B.S. Murty).

0925-8388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2007.05.104

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Table 1 The size factor and the enthalpy mixing for various binary equiatomic alloys in the AlFeTiCrZnCu hexanary system calculated using Miedemas approach [6] S. no. Binary system Size factor AB 1 2 3 4 5 6 7 8 9 10 11 12 AlFe AlTi AlCr AlZn AlCu FeTi FeCr FeZn FeCu TiCr TiCu ZnCu 11 1 9 3 10 15 3 9 1 10 11 7 BA 13 1 10 3 11 13 3 8 1 11 13 8 11 30 10 1 1 17 1 4 13 31 9 1 Hchem (kJ/mol)

carbide vials and balls were used as a milling media and toluene was used as a process controlling agent. The powder samples were taken at regular intervals of 5 h of milling. The milled powders were analyzed by Shimadzu XD-D1 X-ray diffractometer (XRD) with a Cu K radiation. The chemical composition of the milled powders was determined by energy dispersive X-ray (EDX) microanalysis system equipped with FEI-Quanta 200 scanning electron microscope (SEM). The nanocrystalline nature and the crystal structure of the milled powders were analyzed by Philips CM12 transmission electron microscope (TEM). The multicomponent high entropy alloy powders were compacted at 1.8 GPa and sintered at 800 C for 1 h in an argon atmosphere. The density of the samples was measured by Archimedess principle. The hardness of the sintered samples was measured using Vickers hardness tester at 3 kg load.

3. Results and discussion The XRD patterns of binary AlFe, ternary AlFeTi, quaternary AlFeTiCr, quinary AlFeTiCrZn, and hexanary AlFeTiCrZnCu equiatomic elemental blend at different intervals of milling are shown in Fig. 1(a)(e). The complete disappearance of all the elemental peaks and the formation of single phase solid solution are evident within 10 h of milling in the case of binary AlFe to quaternary AlFeTiCr system. In case of quinary AlFeTiCrZn and hexanary AlFeTiCrZnCu compositions, single phase solid solution was observed within 15 and 20 h of milling, respectively. The longer milling time needed for the solid solution formation in systems with larger number of elements could be attributed to slower diffusivities. In

general, in all the cases, signicant broadening of the XRD peaks and disappearance of all the peaks of the solid solution except the most intense one has been observed. This can be attributed to the nanocrystallite formation and the lattice strain. The crystallite size of the alloy has been calculated from the X-ray peak broadening using Viogt peak prole analysis after eliminating the instrumental and strain contributions. The crystallite size in most of the cases is below 10 nm after 10 h of milling as shown in Table 2. Similar multicomponent equiatomic nanostructured high entropy solid solutions have also been synthesized in the present work in CuNiCoZnAlTi and NiFeCrCoMnW alloys as shown in Fig. 2(a) and (b), respectively. The homogeneity of the chemical composition of all the high entropy alloys has been conrmed by EDX microanalysis. Fig. 3 shows the EDX spectrum [9] obtained from one of the powder particle in the hexanary AlFeTiCrZnCu high entropy alloy milled for 10 h. The nominal composition of each element in this alloy is 16.6 at.%, and the quantitative elemental analysis results from the EDX spectrum in Fig. 3 clearly indicate that the homogeneity and the equiatomic composition is maintained in each particle of the alloy after 20 h. The nanocrystalline nature of the high entropy alloy has been conrmed from the TEM bright eld image and the corresponding selected area diffraction (SAD) pattern shown in Fig. 4 for the multicomponent AlFeTiCrZnCu high entropy alloy. The particle size obtained from the TEM study (10 nm) is very close to the crystallite size

Table 2 The crystallite size and lattice strain of binary to hexanary equiatomic alloys in AlFeTiCrZnCu system Milling time (h) AlFe CS (nm) 0 5 10 15 20 cs: crystallite size. Lattice strain (%) 0.89 1.34 AlFeTi CS (nm) Lattice strain (%) 0.71 1.47 AlFeTiCr CS (nm) Lattice strain (%) 0.63 1.23 AlFeTiCrZn CS (nm) Lattice strain (%) 0.49 0.50 0.94 AlFeTiCrZnCu CS (nm) Lattice strain (%) 1.31 1.42 1.39 1.52

14 10

18 9

20 10

25 14 14

10 9 9 9

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Fig. 1. XRD patterns of equiatomic (a) binary AlFe, (b) ternary AlFeTi, (c) quaternary AlFeTiCr, (d) quinary AlFeTiCrZn, and (e) hexanary AlFeTiCrZnCu high entropy alloys as a function of milling.

calculated from the X-ray peak broadening. The analysis of the rings in the SAD pattern of Fig. 4 has clearly indicated that the phase has BCC structure. Similarly equiatomic binary AlFe [9], ternary AlFeTi, quaternary AlFeTiCr and the quinary AlFeTiCrZn nanocrystalline high entropy alloys have also been found to have BCC structure. The compacted AlFeTiCrZnCu alloy sintered at 800 C for 1 h in an argon atmosphere has shown 99% density. The XRD

pattern of AlFeTiCrZnCu high entropy alloy sintered at 800 C for 1 h is shown in Fig. 5, which reveals the alloy is a single phase solid solution with BCC structure and is nanocrystalline (crystallite size of 20 nm) even after sintering, which proves the high stability of the high entropy solid solution. The hardness of the sintered hexanary high entropy alloy is 2 GPa suggesting that these nanocrystalline multicomponent solid solutions have high strength.

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Fig. 4. The TEM bright eld image and SAD pattern of AlFeTiCrZnCu hexanary alloy after 20 h of MA.

Fig. 2. The XRD patterns of equiatomic hexanary (a) CuNiZnCoAlTi and (b) NiFeCrCoMnW high entropy alloys as a function of milling time.

Fig. 5. The XRD patterns of 20 h milled and 20 h milled + sintered equiatomic hexanary AlFeTiCrZnCu high entropy alloy.

4. Conclusions The binary to hexanary equiatomic high entropy alloys in AlFeTiCrZnCu system have been successfully synthesized by MA. The formation of nanostructured solid solutions with BCC crystal structure has been observed in all the compositions. The high entropy alloys prepared by MA have excellent homogeneity in composition and have a crystallite size of about 10 nm. The nanocrystalline high entropy alloy is stable even after sintering at 800 C for 1 h and has a high hardness of 2 GPa. The similar nanostructured single phase solid solutions have also been obtained in CuNiCoZnAlTi and NiFeCrCoMnW systems. References
Fig. 3. The EDX spectrum and quantitative analysis of equiatomic AlFeTiCrZnCu hexanary alloy after 20 h of milling. [1] S. Ranganathan, Curr. Sci. 85 (2003) 14041406. [2] A. Takeuchi, A. Inoue, Mater. Trans. JIM 41 (2000) 13721378.

S. Varalakshmi et al. / Journal of Alloys and Compounds 460 (2008) 253257 [3] C.J. Tong, Y.L. Chen, S.K. Chen, J.W. Yeh, T.T. Shun, C.H. Tsau, S.J. Lin, S.Y. Chang, Metall. Mater. Trans. A 36 (2005) 881893. [4] C.J. Tong, M.R. Chen, S.K. Chen, J.W. Yeh, T.T. Shun, S.J. Lin, S.Y. Chang, Metall. Mater. Trans. A 36 (2005) 12631271. [5] Y.J. Hsu, W.C. Chiang, J.K. Wu, Mater. Chem. Phys. 92 (2005) 112117.

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[6] T.K. Chen, T.T. Shun, J.W. Yeh, M.S. Wong, Surf. Coat. Technol. 199 (2004) 193200. [7] B.S. Murty, S. Ranganathan, Int. Mater. Rev. 43 (1998) 101141. [8] C. Suryanarayana, Prog. Mater. Sci. 46 (2001) 1184. [9] S. Varalakshmi, M. Kamaraj, B.S. Murty, Trans. Ind. Inst. Metals., in press.