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Effect of Valence Electron Concentration on Stability of Fcc Or Bcc Phase in High Entropy Alloys Sheng Guo, Chun Ng, Jian Lu, and C

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Effect of Valence Electron Concentration on Stability of Fcc Or Bcc Phase in High Entropy Alloys Sheng Guo, Chun Ng, Jian Lu, and C View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by PolyU Institutional Repository Effect of valence electron concentration on stability of fcc or bcc phase in high entropy alloys Sheng Guo, Chun Ng, Jian Lu, and C. T. Liu Citation: J. Appl. Phys. 109, 103505 (2011); doi: 10.1063/1.3587228 View online: http://dx.doi.org/10.1063/1.3587228 View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v109/i10 Published by the American Institute of Physics. Related Articles Hydrogen quantum effects in hydride LaNi5H7 J. Appl. Phys. 110, 063533 (2011) Accurate determination of the Gibbs energy of Cu–Zr melts using the thermodynamic integration method in Monte Carlo simulations J. Chem. 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Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions JOURNAL OF APPLIED PHYSICS 109, 103505 (2011) Effect of valence electron concentration on stability of fcc or bcc phase in high entropy alloys Sheng Guo,1 Chun Ng,1 Jian Lu,2 and C. T. Liu1,a) 1Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, People’s Republic of China 2College of Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong (Received 8 March 2011; accepted 3 April 2011; published online 16 May 2011) Phase stability is an important topic for high entropy alloys (HEAs), but the understanding to it is very limited. The capability to predict phase stability from fundamental properties of constituent elements would benefit the alloy design greatly. The relationship between phase stability and physicochemical/thermodynamic properties of alloying components in HEAs was studied systematically. The mixing enthalpy is found to be the key factor controlling the formation of solid solutions or compounds. The stability of fcc and bcc solid solutions is well delineated by the valance electron concentration (VEC). The revealing of the effect of the VEC on the phase stability is vitally important for alloy design and for controlling the mechanical behavior of HEAs. VC 2011 American Institute of Physics. [doi:10.1063/1.3587228] I. INTRODUCTION find out the physical parameters that control the stability for the fcc and bcc phases in HEAs. High entropy alloys (HEAs) constitute a new type of metallic alloys for structural and particularly high-tempera- II. ANALYSIS ture applications, due to their high hardness, wear resistance, high-temperature softening resistance and oxidation resist- Wang et al. briefly discussed the reason of addition of 1–3 ance. HEAs are typically composed of more than five me- Al in the AlxCoCrCu1ÀxFeNiTi0.5 system causing the struc- tallic elements in equal or near-equal atomic ratios, and tural transition from fcc to bcc.6 They claimed that the alloy- interestingly they tend to form solid solution structure ing of larger Al atoms introduces the lattice distortion (mainly fcc and/or bcc) rather than multiple intermetallic energy, and the formation of a lower atomic-packing-effi- compounds as expected from general physical metallurgy ciency structure, such as bcc, can decrease this distortion principles. They were termed as HEAs because the entropy energy. This does make sense but is far away from being sat- of mixing is high when the alloying elements are in equia- isfactory; besides, it can not quantitatively predict when the tomic ratio, and it was initially believed that the high entropy bcc structure will form as a function of Al additions. Ke of mixing leads to the formation of the solid solution struc- et al. claimed that, in the AlxCoyCrzCu0.5FevNiw system, Ni ture rather than intermetallic compounds. and Co are fcc stabilizers and Al and Cr are bcc stablizers; The generally used alloying elements in HEAs are fcc- 1.11 Co is equivalent to Ni as the fcc stablizers and 2.23 Cr type Cu, Al, Ni, bcc-type Fe, Cr, Mo, V and hcp-type Ti, Co is equivalent to Al for the bcc stablizers. Furthermore, if the (crystal structure at ambient temperature). When these alloy- equivalent Co % is greater than 45 at. %, the alloy has an fcc ing elements are mixed with different combination, or with structure, and the alloy has a bcc structure if the equivalent same combination but different amount of certain elements, Cr % is greater than 55 at. %.7 This empirical rule is useful fcc, bcc or mixed fcc and bcc structures may form. For but it has no scientific merits and is valid only for the specific example, cast CoCrCuFeNi (in atomic ratio, same after- alloy systems. The establishment of scientific principles to wards) has the fcc structure while AlCoCrCuFeNi has the control the crystal structures in HEAs can also contribute to 4 fccþbcc structure; and the amount of Al in the AlxCoCrCu- the alloy design of HEAs with desirable properties. For FeNi system can tune the crystal structure from fcc to example, we can use less expensive Ni to partially or com- fccþbcc and to fully bcc4. The structure directly affects the pletely replace more expensive Co; or we can reduce the mechanical properties, and to take again the AlxCoCrCuFeNi amount of Cu which is known to cause segregation issue system as an example: with increasing x, the structure because the mainly positive enthalpy of mixing between Cu changes from fcc to fccþbcc and finally to bcc; the hardness and other alloying elements.4 and strength increase with the increasing amount of bcc As a test to the equivalency of Ni and Co as fcc stabil- 4,5 phases but the alloys get brittle. Although the embrittle- izers, we prepared a series of AlxCrCuFeNi2 (0.2 x 1.2) ment mechanism by bcc phases still needs further explora- alloys to study the effect of Al amount on the phase stability tion, it is certainly important to be able to control the in this alloy system, in comparison to the well studied formation of bcc phases. The target of this work is hence to AlxCoCrCuFeNi system. The alloys were prepared by arc- melting a mixture of the constituent elements with purity a)Author to whom correspondence should be addressed. Electronic mail: better than 99.9% in a Ti-gettered high-purity argon atmos- [email protected]. phere. Repeated melting was carried out at least five times to 0021-8979/2011/109(10)/103505/5/$30.00 109, 103505-1 VC 2011 American Institute of Physics Downloaded 10 Nov 2011 to 158.132.161.9. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions 103505-2 Guo et al. J. Appl. Phys. 109, 103505 (2011) improve the chemical homogeneity of the alloy. The molten including the d-electrons accommodated in the valence alloy was drop-cast into a 10 mm diameter copper mold. The band, valence electron concentration or VEC.11,12 e/a or phase constitution of the alloy was examined by X-ray dif- VEC for a multi-component alloy can be defined as the fractometer using Co radiation (Bruker AXS D8 Discover). weighted averageP from e/a or VEC of theP constituent compo- n n The X-ray diffraction patterns are shown in Fig. 1 where it is nents: e/a ¼ i¼1 ciðe=aÞi or VEC ¼ i¼1 ciðVECÞi, where clear that at x 0.8, the alloys have a single fcc structure and (e/a)i and (VEC)i are the e/a and VEC for the individual ele- the bcc phase starts to appear at x ¼ 1.0. In the AlxCoCrCu- ment. Hume-Rothery rule works with the e/a definition and FeNi system, fully fcc structure is obtained at x 0.5 and e/a has clear effect on the crystal structure for the so-called bcc phase starts to appear at x > 0.8.4 The experimental electron compounds or Hume-Rothery compounds.9 How- results indicate that Co is not necessarily required in obtain- ever, the HEAs comprise mainly transition metals (TMs) and ing the solid solution structure in HEAs, which is good for e/a for TMs are very controversial.11 Very recently, Mizutani alloy design from economy concerns. This new alloy system reviewed the various definitions of e/a for TMs and con- also provides more data to study the phase stability in HEAs, cluded that e/a for TMs are small positive numbers.11 ideally from the consideration of the fundamental properties Unfortunately, not all e/a for TMs have been determined and of constituent alloying elements. e/a for a TM element even varies in different environment. Zhang et al. studied the relationship between the phase For convenience, VEC was used here to study the electron stability and the atomic size difference, d (¼ 100 concentration effect on the phase stability in HEAs. qPffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi P N 2 n i¼1 cið1 À ri=rÞ , r ¼ i¼1 ciri, where ci and ri are III. RESULTS atomic percentage and atomic radius of the iPth component), n 8 and also the mixing enthalpy, DHmix (¼ i¼1;i6¼j Xijcicj, Following Zhang et al.’s method, the atomic size dif- AB AB Xij ¼ 4Dmix, where Dmix is the mixing enthalpy of binary ference, d, and the mixing enthalpy, DHmix for the AlxCoCr- 8 4 liquid AB alloys) for multi-component alloys.
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