Journal of Alloys and Compounds 460 (2008) 253–257

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 configurational 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 Al–Fe–Ti–Cr–Zn–Cu 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 configurational entropy is maximum at equiatomic composition and it increases with increase in the number of elements in the system, thus making it difficult for the formation of intermetallics. The configurational 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 (7–11 J mol−1 K−1 ) 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 Al–Fe–Ti–Cr–Zn–Cu 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 [3–6] is the only group that has so far reported the synthesis of these advanced alloys by conventional casting and thin film 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 [3–6] are microcrystalline and their properties can be significantly 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 Al–Fe–Ti–Cr–Zn–Cu 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 Al–Fe to hexanary Al–Fe–Ti–Cr–Zn–Cu 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

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

89 1. Fig. The density of the samples was measured by Archimedes’s principle.8 GPa and sintered at 800 ◦ C for 1 h in an argon atmosphere. 3. Lattice strain (%) 0. 1(a)–(e). Binary system Size factor A–B 1 2 3 4 5 6 7 8 9 10 11 12 Al–Fe Al–Ti Al–Cr Al–Zn Al–Cu Fe–Ti Fe–Cr Fe–Zn Fe–Cu Ti–Cr Ti–Cu Zn–Cu 11 1 9 3 10 15 3 9 1 10 11 7 B–A 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.94 – Al–Fe–Ti–Cr–Zn–Cu CS (nm) Lattice strain (%) 1. The powder samples were taken at regular intervals of 5 h of milling.254 S. and hexanary Al–Fe–Ti–Cr–Zn–Cu equiatomic elemental blend at different intervals of milling are shown in Fig. no. respectively.42 1. 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 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 Al–Fe–Ti–Cr–Zn–Cu system Milling time (h) Al–Fe CS (nm) 0 5 10 15 20 cs: crystallite size.47 – – Al–Fe–Ti–Cr CS (nm) Lattice strain (%) 0.34 – – Al–Fe–Ti CS (nm) Lattice strain (%) 0. single phase solid solution was observed within 15 and 20 h of milling. 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 Al–Fe to quaternary Al–Fe–Ti–Cr system. The nanocrystalline nature and the crystal structure of the milled powders were analyzed by Philips CM12 transmission electron microscope (TEM).71 1. 3 clearly indicate that the homogeneity and the equiatomic composition is maintained in each particle of the alloy after 20 h. and the quantitative elemental analysis results from the EDX spectrum in Fig.49 0. The milled powders were analyzed by Shimadzu XD-D1 X-ray diffractometer (XRD) with a Cu K␣ radiation. The nanocrystalline nature of the high entropy alloy has been confirmed from the TEM bright field image and the corresponding selected area diffraction (SAD) pattern shown in Fig. Varalakshmi et al. / Journal of Alloys and Compounds 460 (2008) 253–257 Table 1 The size factor and the enthalpy mixing for various binary equiatomic alloys in the Al–Fe–Ti–Cr–Zn–Cu hexanary system calculated using Miedema’s approach [6] S. The crystallite size in most of the cases is below 10 nm after 10 h of milling as shown in Table 2.39 1. The longer milling time needed for the solid solution formation in systems with larger number of elements could be attributed to slower diffusivities. The nominal composition of each element in this alloy is 16.%.63 1. 4 for the multicomponent AlFeTiCrZnCu high entropy alloy. ternary Al–Fe–Ti. The multicomponent high entropy alloy powders were compacted at 1. quaternary Al–Fe–Ti–Cr. In case of quinary Al–Fe–Ti–Cr–Zn and hexanary Al–Fe–Ti–Cr–Zn–Cu compositions. In general. The crystallite size of the alloy has been calculated from the X-ray peak broadening using Viogt peak profile analysis after eliminating the instrumental and strain contributions. 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. The hardness of the sintered samples was measured using Vickers hardness tester at 3 kg load. quinary Al–Fe–Ti–Cr–Zn.50 0. in all the cases. respectively.31 1. Results and discussion The XRD patterns of binary Al–Fe.6 at. This can be attributed to the nanocrystallite formation and the lattice strain.52 14 10 – – 18 9 – – 20 10 – – 25 14 14 – 10 9 9 9 . 2(a) and (b). The homogeneity of the chemical composition of all the high entropy alloys has been confirmed by EDX microanalysis. 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). significant broadening of the XRD peaks and disappearance of all the peaks of the solid solution except the most intense one has been observed.23 – – Al–Fe–Ti–Cr–Zn CS (nm) Lattice strain (%) 0.

ternary AlFeTi. . XRD patterns of equiatomic (a) binary AlFe. which reveals the alloy is a single phase solid solution with BCC structure and is nanocrystalline (crystallite size of 20 nm) even after sintering. (c) quaternary AlFeTiCr. which proves the high stability of the high entropy solid solution. 1. The XRD pattern of AlFeTiCrZnCu high entropy alloy sintered at 800 ◦ C for 1 h is shown in Fig. Varalakshmi et al. The compacted AlFeTiCrZnCu alloy sintered at 800 ◦ C for 1 h in an argon atmosphere has shown 99% density. and (e) hexanary AlFeTiCrZnCu high entropy alloys as a function of milling. 5. calculated from the X-ray peak broadening. / Journal of Alloys and Compounds 460 (2008) 253–257 255 Fig. The analysis of the rings in the SAD pattern of Fig. (b) ternary AlFeTi.S. The hardness of the sintered hexanary high entropy alloy is 2 GPa suggesting that these nanocrystalline multicomponent solid solutions have high strength. quaternary AlFeTiCr and the quinary AlFeTiCrZn nanocrystalline high entropy alloys have also been found to have BCC structure. Similarly equiatomic binary AlFe [9]. 4 has clearly indicated that the phase has BCC structure. (d) quinary AlFeTiCrZn.

Conclusions The binary to hexanary equiatomic high entropy alloys in Al–Fe–Ti–Cr–Zn–Cu system have been successfully synthesized by MA. 5. The similar nanostructured single phase solid solutions have also been obtained in Cu–Ni–Co–Zn–Al–Ti and Ni–Fe–Cr–Co–Mn–W systems. Trans. The XRD patterns of equiatomic hexanary (a) CuNiZnCoAlTi and (b) NiFeCrCoMnW high entropy alloys as a function of milling time. A. Fig. Sci. [2] A. . Curr. The TEM bright field image and SAD pattern of AlFeTiCrZnCu hexanary alloy after 20 h of MA. The formation of nanostructured solid solutions with BCC crystal structure has been observed in all the compositions. 4. [1] S. Ranganathan. References Fig. 3. 2. The high entropy alloys prepared by MA have excellent homogeneity in composition and have a crystallite size of about 10 nm. JIM 41 (2000) 1372–1378. Takeuchi. The nanocrystalline high entropy alloy is stable even after sintering at 800 ◦ C for 1 h and has a high hardness of 2 GPa. Mater. Varalakshmi et al. 85 (2003) 1404–1406. 4. Inoue. The XRD patterns of 20 h milled and 20 h milled + sintered equiatomic hexanary AlFeTiCrZnCu high entropy alloy. / Journal of Alloys and Compounds 460 (2008) 253–257 Fig. The EDX spectrum and quantitative analysis of equiatomic AlFeTiCrZnCu hexanary alloy after 20 h of milling. Fig.256 S.

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