Sandeep Vura et al.

/ International Journal of Engineering Science and Technology (IJEST)

SYNTHESIS AND CHARECTERIZATION OF AlFeCrNi FOUR COMPONENT HIGH ENTROPY ALLOY BY MECHANICAL ALLOYING
SANDEEP VURAa, D.S.D.RAMYAb, P V PRAMOD SUKUMARc
Dept of Metallurgical Engineering, Andhra University, Visakhapatnam 530003, Andhra Pradesh, India

P.B.C RAOd
Dept of Metallurgical Engineering, Andhra University Visakhapatnam 530003, Andhra Pradesh, India Abstract: The elemental powders of Al,Fe,Ni and Cr are taken with high purity and are mechanically alloyed(MA) to produce the High-Entropy Alloy. The samples are taken at regular intervals of 5,10,15,20 hr. These samples are characterized by X-Ray Diffraction (XRD) technique. The further analysis of X-Ray Diffraction (XRD) patterns for crystallite size and strain is done. The series of transformations were studied by plotting intensity versus 2.The high entropy alloy was synthesized successfully having a single-phase solid solution. The alloy has a Body Centered Cubic (BCC) crystal structure and a lattice parameter of 2.8952Ao with a residual strain of 0.772%. Keywords: High-entropy alloy, XRD, Mechanical Alloying, Crystallite size 1. Introduction: Since the inception of the concept of the strengthening of the material by forming a solid solution a numerous alloys have been developed. The solid solution formation takes place only when the Hume Rothery [1] rules are satisfied in a binary system. But increase in the number of components leads to the formation of intermetallic compounds which are brittle. So the concept of higher number of components in an alloy designs are discarded. The dispersion hardening was done for a pure metal or an alloy. The reinforcements may be an oxide, intermetallic, nitrides, borides which have no or limited solubility in the parent phase. These materials have good high temperature mechanical properties. The main drawback is that the dispersoids lack coherency with the matrix. The next generation focused on the intermetallics for superior creep resistance as youngs modulus. Surprisingly it has been found that increasing the number of components in systems did not yield a number of intermetallics, but resulted in a single phase or a dual phase solid solution made up of the components. The thermodynamics were investigated, this peculiar behavior was found to be due to the high entropy of mixing during the alloy formation. Hence these were named as High Entropy Alloys [2-3] (HEA). So far in the world the HEA were produced by Vacuum Arc Melting (VAR) by many researchers (Yeh et al[2]). But these alloys can also be produced by Mechanical Alloying [4,13] (MA) in a high-energy ball mill (HEBM). The Mechanical Alloying process is helpful in achieving nanocrystalline state, uniformity of composition through out the alloy. The high entropy alloys have some enhanced properties like high compressive strength [5], wear, oxidation and creep resistance and hence find applications in tools, molds, dies, mechanical parts and furnace parts. Their applications extend to wear resistant coatings, corrosion resistant coatings [6-7], hard facing of golf heads and soft magnetic films. Elemental composition is a critical factor in alloy design and influences the physical and mechanical properties of the High Entropy Alloys. Most alloys are found to contain Al as the one of the principal alloying element [8]. So far, it is not clarified however whether there is a relationship between the structure of the alloying
a,b,c d

student final year

Associate Professor, Department of Metallurgical Engineering, Andhra University.

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elements and that of the HE alloys. This question is especially true when Al as an alloying element is added into the HE alloys. This is partly induced by the dualism of metal and nonmetal characteristics of Al due to its special electronic structure. Many high entropy alloys have been exploited in the past decade and most of the reported systems are high-entropy multi element alloys having elements more than five. The ternary component systems are usually neglected due to the reason that they have low mixing entropy of 1.1R but the four component systems also have an intermediate mixing entropy [14] of 1.39R(11.5565 J/Mol/K) .The present study is taken to synthesis and characterize quaternary component High Entropy Alloys (a) FeCrNiCo (b) AlFeCrNi. The alloying elements are selected based on the factors like Cumulative Atomic-Size Difference, Mixing Enthalpy of Solid Solution. 2. Experimental Procedure: Elemental powders of Fe, Al, Ni, Cr, Co with high purities (>99% assay) and initial particle size less than 149micrometers (-100 mesh) with equiatomic compositions are taken as starting materials. The elemental powders were milled in a planetary ball mill (Retsch PM100) in a hardened steel vial with tungsten carbide grinding media in toluene. The ball-to-powder weight ratio of 10:1 and 300rpm speed was used. The toluene was used as a process-controlling agent in order to avoid excessive cold welding and also act as medium to avoid oxidation of the alloy. In order to confirm the alloy formation during milling, powder samples were taken out in every 5 hr intervals (5, 10, 15 and 20 hr). After 20 h of milling the powders were completely taken out for further characterization. The milled samples were studied by X-ray diffraction (XRD) using Rigaku Ultima IV X-ray diffractometer with CuK (1.5492A0) radiation for monitoring phase formation and to estimate the crystallite size and mean lattice strain in milled powders.

3. Results and Discussion: 3.1 FeCrCoNi system: The x-ray diffraction pattern Fig.1 confirms that there is no formation of the alloy even after the 20 hours of milling. The above pattern indicates that there is a decrease in the crystallite size, this can be inferred from the peak broadening. The graphs (Fig.2, Fig.3) are plotted for the crystallite size and lattice strain versus progressive time of milling respectively. From the crystallite size calculations using the Scherrer formula [9] it was observed to be 21.1nm and the strain calculated using tangent formula[10] was found to be 0.534%.

Fig.1 The XRD patterns for FeCrCoNi system at the start and end of 20hr milling

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Sandeep Vura et al. / International Journal of Engineering Science and Technology (IJEST)

Fig.2 Crystallite size (nm) vs milling time (hr) of FeCrCoNi

Fig.3 Strain (%) vs milling time(hr) of FeCrCoNi

3.2 AlFeCrNi Alloy system: The x-ray diffraction patterns Fig.4 confirms that there is formation of high-entropy alloy at the end of 20 hours of milling. The peaks are symmetric. The pattern also indicates that there is a decrease in the crystallite size and increase in mean lattice strain. The graphs (Fig.5, Fig.6) are plotted for the crystallite size and lattice strain versus progressive time of milling respectively.

Fig.4 The XRD patterns for AlFeCrNi system at the start and end of 20hr of milling

Fig.5 Crystallite size (nm) vs milling time (hr) of AlFeCrNi

Fig.6 Strain (%) vs milling time(hr) of AlFeCrNi

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Table-1: Thermo-physical properties of the elements present in the nanocrystalline equiatomic High Entropy Alloy
S. no. 1. 2. 3. 4. 5. Elements Aluminium (Al) Iron (Fe) Chromium(Cr) Nickel (Ni) Cobalt (Co) Structure FCC BCC BCC FCC HCP Atomic radius (nm) 0.143 0.127 0.128 0.124 0.125 Enthalpy of fusion (kJ/mol) 10.7 13.81 21.0 17.5 16.06

[7,9,11,12,14,15]

Entropy of fusion (J/mol K) 11.5 7.63 9.63 10.1 9.08

Plotting intensity versus 2 of 5,10,15,20 hr samples in Fig.7 helps in studying the series of transformations. During the initial stage i.e. at 5hrs of milling the Al and Ni started disappearing. This is inferred from the decrease in intensity of the peak corresponding to Al and Ni. The crystallite size was 43.6nm. The size reduction is taking place simultaneously which can be inferred from the increase in the peak width. After 10hrs of milling the Al peak disappeared completely and also the size reduced below 20nm, which is a prerequisite for mechanical alloying. It can be inferred that the Al and Ni are entering into the Fe and Cr lattices. This can be supported by the fact that Fe and Cr are BCC lattices (Table-1), which have an open structure with an atomic packing fraction of 0.68[15] only.

Fig.7 Series of transformations into HEA of AlFeCrNi system

After 15hrs of mechanical alloying a single phase structure with a small amount of Ni (retained) was observed. The peaks of 20hrs XRD corresponds to a BCC phase high entropy alloy with minor proportion of retained Ni. The BCC phase was confirmed from the values of d1/d2 and d2/d3 calculated and theoretical from the Table2(a), 2(b). The precise lattice parameter [9] calculated for the BCC high entropy alloy using the value of highest (40.945) from the diffractogram is ao = 2.8952Ao. From the crystallite size calculations using the Scherrer formula it was observed to be 13.7nm and the strain calculated using tangent formula was found to be 0.772%.

S. No. 1. 2. 3.

2 44.438 64.7 81.89

22.219 32.35 40.945

Sin 0.37815 0.5351 0.6553

/2sin 2.0484(d1) 1.4476(d2) 1.1819(d3)

Table-2(a): Determination of crystal structure of the AlFeCrNi S. no. 1. 2. Calculated 1.145 1.2248 Theoretical 1.414 1.2247

Table-2(b): Comparison of theoretical and calculated d1/d2 and d2/d3

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4. Conclusions Four-component high entropy AlFeCrNi alloy has been synthesized successfully. A single-phase solid solution of BCC crystal structure has been formed with a small amount of retained Ni with a lattice parameter of ao=2.5982A0. Aluminium is confirmed to be a BCC stabilizer in the High Entropy Alloys. 5. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] Sidney H Avner Introduction to physical metallurgy, 2nd edn, Tata-Mc Graw-Hill Publishing Company Limited, New Delhi. J.W. Yeh, S.K. Chen, S.J. Lin, J.Y. Gan, T.S. Chin, T.T. Shun, C.H. Tsau and S.Y. Chang, Adv Eng Mater 6 (2004) 299 J.W. Yeh, S.K. Chen, J.Y. Gan , S.J. Lin, T.S. Chin, T.T. Shun, C.H. Tsau and S.Y. Chang, Metall Mater Trans A 35 (2004) 2533. S.Varalakshmi,M.Kamraj,B.S.Murthy ,Materials Science and Engineering A 527 (2010) 1027-1030 Y.J. Zhou et al. / Materials Science and Engineering A 454455 (2007) 260265 Y.S. Huang, L. Chen, H.W. Lui, M.H. Cai, J.W. Yeh, Mater. Sci. Eng. A 457 (2007) C. Li, J.C. Li, M. Zhao, Q. Jianga, Journal of Alloys and Compounds 475 (2009) 752757 T.K. Chen, T.T. Shun, J.W. Yeh, M.S. Wong, Surf. Coat Technology 188189 (2004) 193. B.D.Cullity, Elements of X-Ray diffraction, 2nd Edn, Addision-Wilely Publishing Company Inc,Massachusetts. Particle Size and strain analysis by X-ray Diffraction by H & M Analytical Services Anmin LI, Xiyan Zhang. Acta Metallurgica Sinica (Englett) Vol 22.No.3, pp 219-224, June 2009 Greenwood, Norman N.; Earnshaw, Alan. (1997), Chemistry of the Elements (2nd ed.), Oxford: Butterworth-Heinemann. C. Suryanarayana, Mechanical Alloying And Milling, CRC Press 2004 David R. Gaskell, An introduction to thermodynamics of materials (4th Edn), Taylor and Francis, New York. William D. Callister, Jr., Materials Science And Engineering An Introduction(4th Edn), John Whiley &Sons,Inc ,NewYork.

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