Journal of Materials Science

Experimental investigation on phase equilibria of Cu-Ti-Hf system and performance of

Cu(Ti, Hf)2 phase
--Manuscript Draft--

Manuscript Number: JMSC-D-17-04800

Full Title: Experimental investigation on phase equilibria of Cu-Ti-Hf system and performance of
Cu(Ti, Hf)2 phase

Article Type: Manuscript (Regular Article)

Keywords: Phase equilibria; Cu-Ti-Hf system; Isothermal section; Diffusion triple;

Nanoindentation.

Abstract: Phase relations in Cu-Ti-Hf ternary system have been studied by diffusion triple
technique supplemented with typical alloy sampling method. Based on results from
electron-probe microscopy analysis (EPMA) and X-ray diffraction (XRD), isothermal
sections of the Cu-Ti-Hf system at 800 oC and 700 oC were established, which consist
of 10 and 9 three-phase regions, respectively. It is observed that Ti can completely
substitute Hf in the CuHf2 phase, indicating formation of a continuous solid solution
Cu(Ti,Hf)2. Hf can substitute about 20% Ti in the phase CuTi, while solubility of Ti in
Cu10Hf7 and Cu51Hf14 phases respectively reaches to 13 at% and 10 at% at 800 oC.
The Cu8Hf3 phase of existence at 800 oC was proved to be unstable at 700 oC. In
addition, the elastic modulus and hardness of solid solution Cu(Ti,Hf)2 were
determined using Nano-indentation.

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1 Experimental investigation on phase equilibria of Cu-Ti-Hf system

2
3
4 and performance of Cu(Ti, Hf)2 phase
5
6 J.L. Liu 1, X.M. Huang 1, G.H. Li 1, G.M. Cai 1, * H.S. Liu 1, Z.P. Jin 1
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8 1
School of Materials Science and Engineering, Central South University, Changsha,
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Hunan410083, PR China
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13 Corresponding author’s E-mail: caigemei@csu.edu.cn
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15
16 Abstract
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Phase relations in Cu-Ti-Hf ternary system have been studied by diffusion triple
20
21 technique supplemented with typical alloy sampling method. Based on results from
22
23 electron-probe microscopy analysis (EPMA) and X-ray diffraction (XRD), isothermal
24
25 sections of the Cu-Ti-Hf system at 800 oC and 700 oC were established, which consist
26
27 of 10 and 9 three-phase regions, respectively. It is observed that Ti can completely
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29 substitute Hf in the CuHf2 phase, indicating formation of a continuous solid solution
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31 Cu(Ti,Hf)2. Hf can substitute about 20% Ti in the phase CuTi, while solubility of Ti
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33 in Cu10Hf7 and Cu51Hf14 phases respectively reaches to 13 at% and 10 at% at 800 oC.
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35 The Cu8Hf3 phase of existence at 800 oC was proved to be unstable at 700 oC. In
36
37 addition, the elastic modulus and hardness of solid solution Cu(Ti,Hf)2 were
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39 determined using Nano-indentation.
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42 Key words: Phase equilibria; Cu-Ti-Hf system; Isothermal section; Diffusion triple;
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44 Nanoindentation.
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48
1. Introduction
49 Cu-based bulk metallic glasses have displayed good strength, high conductivity
50
51 and outstanding corrosion resistance caused by amorphous structure [1-3]. Especially,
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53 Cu-Hf based alloys can be cast with amorphous structure and are very attractive for
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55 industry applications [4, 5]. However, only a few micro-scale amorphous ribbons can
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be made in Cu-Hf binary alloys. Previous works show that glass forming ability of
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Cu-Hf alloys can be improved significantly through alloying, e.g. addition of Ti [6, 7].
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 It is known that phase diagrams of the Cu-Hf related systems are important to obtain
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3
related thermodynamic parameters of Cu-based ternary systems for predicting
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solidification behavior, which are beneficial to rapid design of Cu-based bulk metallic
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7 glasses.
8
9 Up to now, phase relations in the constituent binary subsystems Cu-Hf [8-11],
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11 Cu-Ti [11-13] and Ti-Hf [11] have been comprehensively evaluated in terms of both
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13 experimental study and thermodynamic assessment. According to Massalski’s
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15 compilation [11], there are no intermetallic compounds in Ti-Hf binary system, due to
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17 similar crystal structure of Ti and Hf. In Cu-Hf binary system, there are five
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19 intermetallic compounds Cu5Hf [14], Cu51Hf14, Cu8Hf3, Cu10Hf7, and CuHf2. As for
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21 the Cu-Ti system, six intermetallic compounds i.e. Cu4Ti, Cu2Ti, Cu3Ti2, Cu4Ti3,
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23 CuTi and CuTi2 were reported by Massalski’s compilation [11]. However,
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25 information about phase relation in the Cu-Ti-Hf ternary system has not been
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27 published. Also, it is not clear if any ternary phase exists in this ternary system. This
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29 paper aims to measuring phase relations in the Cu-Ti-Hf ternary system.
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31 The crystal structures and stability range of all stable phases in the Cu-Ti-Hf
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ternary system are summarized in Table1.
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Table 1 Crystallographic data and stability range of solid phases of Cu-Ti-Hf system.
37 Phase Person symbol Space group Prototype Stability range(℃) References
38 Cu cF4 Fm3m Cu <1085 [11]
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40 αHf hP2 P63/mmc Mg <1743 [11]
41 βHf Cl2 Im3m W 1743~2231 [11]
42
Cu5Hf cF24  AuBe5 <1055 [14]
43
44 F4 3 m
45 Cu51Hf14 hP68 P6/m Ag51Gd14 <1115 [11, 15]
46
47 Cu8Hf3 oP44 Pnma Cu8Hf3 <990 [11, 15]
48 Cu10Hf7 oS68 Aba2 Zr7Ni10 <1025 [11, 15]
49 CuHf2 tI6 I4/mmm CuZr2 <1310 [11, 16]
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51 αTi hp2 P63/mmc Mg <882 [11]
52 βTi Cl2 Im3m W 882~1670 [11]
53
αCu4Ti oC12 Amm2 Au2V ~ [11, 17]
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55 βCu4Ti oP20 I4/m Au4Zr <882 [11, 17]
56 Cu2Ti oC12 Amm2 Au2V 870~890 [11]
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58 Cu3Ti2 tP10 P4/nmm Cu3Ti2 <875 [11, 18]
59 Cu4Ti3 tI14 I4/mmm Cu4Ti3 <925 [11, 19]
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 CuTi tP4 P4/nmm CuTi <982 [11, 20]
1 CuTi2 tI6 I4/mmm MoSi2 <1005 [11, 20]
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4
5 2. Experimental procedures
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7 Diffusion-triple approach and equilibrated alloy method [21-25] were employed
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9 to determine phase equilibria in the Cu-Ti-Hf system. Pure copper (99.99% Cu),
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11 titanium (99.99% Ti) and hafnium (99.99% Hf) were used as starting materials for
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13 diffusion triples and alloying samples. The fabrication procedure schematic of the
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15 diffusion triple is shown in Fig. 1. The surfaces of copper, titanium, hafnium bricks
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(3*5*15 mm) and titanium out cases were ground and polished to get a flat surface
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20 finish. Then, the different metal pieces underwent a hot pressing at 800 oC to achieve
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22 good interfacial contact with each other. The 6*10*15 mm diffusion couple was
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24 forced into the titanium out-case with 5.5*9.5*15 mm inner dimension to ensure close
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26 contact among the metallic bulks during annealing. Subsequently, the diffusion triples
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28 were encapsulated individually into evacuated quartz tubes back-filled with pure
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30 argon for annealing at 800 °C and 700 °C, respectively. It is worth mentioning, a few
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32 pieces of Ta foils were placed inside each quartz tube to act as oxygen getter for
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34 preventing oxidation of the sample. After diffusion annealing, the quartz tubes
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36 containing the diffusion triples were quickly taken out of the furnaces and quenched
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38 in ice water by breaking the tubes. Finally, phase relations of Cu-Ti-Hf ternary system
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40 were determined using EPMA.
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43 Based on the preliminary experimental results from the diffusion triples, a set of
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45 button alloys of different compositions were further fabricated in order to accomplish
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47 phase equilibria obtained with diffusion triple. In this work, alloy samples with a total
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49 mass of 5 g were prepared from copper, hafnium and titanium rods. Analytical
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51 balance with an error of about ±0.001 g was used for weighting. The weighted raw
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53 materials were mixed and followed by arc melting on a water-cooled copper crucible
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55 under argon atmosphere with titanium as getter material placed in the arc-chamber.
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To ensure a good homogeneity, all samples were re-melted at least 4 times. The
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weight losses of obtained button alloys were less than 1% of the total mass.
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 Subsequently, the samples were sealed in an evacuated quartz tubes back-filled with
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pure argon for annealed at 800 °C for 20 days and 700 °C for 40 days, respectively.
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After that, the tubes with the alloys were taken out of furnace and broken immediately
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7 to make the alloys quench into ice water.
8
9 After standard metallographic preparation, the annealed diffusion triples and
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11 equilibrated alloys were investigated by optical microscope (OM), scanning electron
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13 microscope (SEM), and EPMA. Quantitative EPMA was performed on both a JEOL
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15 JXA-8530F and a JEOL JXA-8800R electron microprobe with an accelerating voltage
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17 of 15 kV and a probe current of 20 nA. X-ray diffraction (XRD)of some typical alloys
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19 were also performed to identify the phases with different structures using a Cu Kα
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21 radiation on an Rigaku D-max/2550 VB+ X-ray diffractometer operated at 40 kV and
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23 250 mA. Nano-indentation test can be performed to determinate elastic modulus and
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25 hardness of Cu(Ti,Hf)2 phase at room temperature using a Nano Indenter UNHT
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27 (CSM Instruments, Peseux, Switzerland) with a Berkovich diamond indenter. In this
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29 study, the applied load was 20 mN with a peak hold time of 10 s.
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Fig.1. Schematic procedure for fabrication of Cu-Ti-Hf diffusion triple.
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51 3. Results and discussion
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3.1 Phase relationship at 800 °C
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54 The BSE images of the tri-junction region in the Cu-Ti-Hf diffusion triple
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56 annealed at 800 °C for 20 days are shown in Figs. 2(a-d). It can be seen from Fig. 2(a)
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58 that β(Ti,Hf) phase was formed in α(Ti)-α(Hf) part, but the β(Ti,Hf) phase
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 disappeared with dilute solid solutions of Cu. As seen in Fig. 2(b), there are four
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layers formed along with the interface between α(Hf) and Cu bulks. In light of results
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of EPMA and by combining the Cu-Hf binary phase diagram [11], these layers can be
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7 identified to be CuHf2, Cu10Hf7, Cu51Hf14, and Cu5Hf, respectively. The Cu8Hf3 phase
8
9 was not detected although it is reported stable at 800 °C [11]. It could not be formed
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11 or it was too thin to be observed. Similar phenomenon was discovered in previous
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13 work [26-28]. Whether Cu8Hf3 is stable or not will be clarified by alloy sampling in
14
15 the next step. Along the interface between α(Ti) and Cu blocks, five layers, i.e. CuTi2,
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17 CuTi, Cu3Ti2, Cu4Ti3, and Cu4Ti can be observed as presented in Fig. 2(c). As
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19 illustrated in Fig. 2(d), there is not obvious phase boundary between CuTi2 phase and
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21 CuHf2 phase. EPMA results across the interface between CuTi2 and CuHf2
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23 demonstrates a continuous solid solution of these binary intermediate compounds.
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52 Fig. 2. BSE images of Cu-Ti-Hf diffusion triple annealed at 800 °C for 20 days: (a) BSE image of the tri-junction
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54 region; (b) the enlarged view of part A marked in Fig. 2(a); (c) the enlarged view of part B marked in Fig.
55 2(a); (d) the enlarged view of part C marked in Fig. 2(a).
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57 Based on EPMA results, the schematic diagram of phase distribution in the
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59 diffusion triple annealed at 800 °C can be presented in Fig. 3, where each curve
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 represents an interface between two adjacent phases, and each tri-junction point
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stands for a three-phased equilibrium. The tie-line information was obtained from
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composition profiles of the EPMA scans across phase interfaces based on the
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7 assumption of local equilibrium [29, 30].
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22 Fig. 3. Schematic diagram of phase distribution in the 800 °C diffusion triple. The numbered tri-junction
23 points (1-10) represent ternary equilibria in the Cu-Ti-Hf system.
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25 To complement phase equilibrium information derived from the diffusion triple,
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27 13 alloys of typical compositions were fabricated and annealed at 800 °C for 60 days
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29 to be equilibrated. Microstructures and constituent phases of these equilibrated alloys
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31 were further analyzed, and the constituent phases and compositions of these alloys are
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summarized in Table 2.
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Table 2 Constituent phases and their compositions in the Cu-Ti-Hf alloys equilibrated at 800 °C.
37 Composition(at.%)
38 Alloys’ Phase equilibria
Phase1 Phase2 Phase3
39 number Phase1/ Phase2/Phase3
40 Cu Ti Hf Cu Ti Hf Cu Ti Hf
41 A1 Cu/Cu5Hf/Cu51Hf14 96.3 3.4 0.3 81.8 2.5 15.7 78.8 7.8 13.4
42
43 A2 Cu/Cu51Hf14/ Cu4Ti 95.1 4.5 0.4 78.6 8.9 12.5 79.0 18.7 2.3
44 A3 Cu5Hf /Cu51Hf14 81.9 1.3 16.8 78.6 3.4 18.0 / / /
45
A4 Cu51Hf14/Cu4Ti /Cu3Ti2 77.9 10.5 11.6 77.8 20.1 2.1 59.6 39.3 1.1
46
47 A5 Cu51Hf14/Cu10Hf7/CuTi 77.0 1.9 21.1 59.6 13.8 26.7 50.1 37.8 12.2
48 A6 Cu51Hf14/Cu4Ti3/CuTi 78.2 5.3 16.5 56.7 40.4 2.9 49.2 49.4 1.4
49
A7 Cu51Hf14/Cu10Hf7 77.6 1.2 21.2 60.0 9.8 30.2 / / /
50
51 A8 Cu51Hf14/Cu10Hf7/Cu8Hf3 78.2 / 21.8 60.8 / 39.2 73.4 / 26.6
52 A9 Cu51Hf14/Cu10Hf7/Cu8Hf3 77.4 0.2 22.4 59.8 0.8 39.4 73.4 0.3 26.3
53
54 A10 Cu10Hf7/CuTi /Cu(Ti,Hf)2 59.2 11.9 28.9 49.9 30.0 20.1 34.4 40.4 25.2
55 A11 αHf/β(Ti,Hf)/Cu(Ti,Hf)2 0.6 54.0 45.4 2.7 60.3 37.0 33.9 12.8 53.4
56
A12 αTi/β(Ti,Hf)/Cu(Ti,Hf)2 1.4 98.5 0.1 5.5 94.3 0.2 32.0 67.8 0.2
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58 A13 Cu10Hf7/Cu(Ti,Hf)2 59.1 31.8 9.1 34.5 39.1 26.4 / / /
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 Microstructure of alloy A4 was illustrated in Fig. 4(a), which consists of black
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Cu3Ti2 phase, gray Cu4Ti phase, and white Cu51Hf14 phase. Fig. 4(b) presents the BSE
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image of alloy A10, in which three phases, white Cu10Hf7, gray Cu(Ti,Hf)2, and dark
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7 CuTi can be discriminated. Further, three-phased regions α(Ti)+α(Hf)+β(Ti,Hf) and
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9 α(Ti) +β(Ti,Hf)+CuTi2 respectively exist in alloys A11 and A12, as demonstrated in
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11 Figs. 4(c) and 4(d).
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13 To further clarify the phase assemblages, XRD patterns of relative alloys were
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15 collected. Fig. 5 presents the XRD patterns of representative alloys A4, A10, A11 and
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17 A12, which are in a good agreement with the results of EPMA.
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Fig. 4. Backscattered electron images of the alloys annealed at 800 °C for 60 days: (a) alloy A4; (b) alloy A10;
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51 (c) alloy A11; (d) alloy A12.
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24 Fig. 5. XRD patterns of the alloys annealed at 800 °C for 60 days: (a) alloy A4; (b) alloy A10; (c) alloy A11; (d)
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alloy A12.
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29 To make sure the Cu8Hf3 phase is stable at 800 °C, an alloy with the same
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31 nominal composition of Cu75Hf25 as A8 was employed and analyzed carefully. Fig.
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6(a) shows the as-cast microstructure of the alloy which contained Cu51Hf14 and
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Cu10Hf7. After annealed at 800 °C for 60 days, three phases can be observed as seen
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38 in Fig. 6(b), which contains gray Cu8Hf3, white Cu10Hf7 and dark Cu51Hf14 matrix
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40 phase, and the white Cu10Hf7 phase is surrounded by gray Cu8Hf3. According to
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42 Gibbs phase rule, there are at most two phases coexisting in an equilibrated binary
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44 alloy at constant temperature and pressure. So, it was suggested that Cu8Hf3 was
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46 formed by exhausting Cu10Hf7 in this annealed alloy. Y. Zhong [8] suggested that
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48 formation of Cu8Hf3 is very sluggish and it might not be formed during casting.
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50 Cu10Hf7 should disappear in alloy A8 after annealed at 800 °C for enough time.
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52 Therefore, it is considered that Cu8Hf3 is stable at 800 °C and it forms by a peritectoid
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54 reaction, Cu51Hf14+ Cu10Hf7→Cu8Hf3.
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Fig. 6. Backscattered electron images of the alloy A8: (a) as-cast; (b) annealed at 800 °C for 60 days.
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17 Based on the present results from diffusion triple and alloy samples, isothermal
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19 section of the Cu-Ti-Hf ternary system at 800 °C is constructed (Fig. 7). All the
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21 composition raw data are presented as circles and the tie-lines are demonstrated as
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23 dotted lines in Fig. 7(a). It can be seen from Fig. 7(b), the isothermal section consists
24
25 of 10 three-phased regions and 22 two-phased regions. It is notable that CuHf2 and
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27 CuTi2 form a continuous solid solution. Additionally, Hf can substitute about 20% Ti
28
29 in CuTi, while solubility of Ti in Cu10Hf7 and Cu51Hf14 can be up to 13 at% and 10
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31 at%, respectively.
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55 Fig. 7. Isothermal section of Cu-Ti-Hf system at 800 °C: (a) with experimental data from the present work;
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(b) without experimental data.
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 3.2 Phase relationship at 700 °C
1
2 Fig. 8 shows the BSE image of the tri-junction region of Cu-Ti-Hf diffusion
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4 triple annealed at 700 °C for 40 days. There are some obvious crocks observed in the
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6 formed diffusion layers, which may form in the process of diffusion. In spite of this,
7
8 we can achieve partial phase equilibrium data by using EPMA. Similar to the case at
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10
800 °C, the CuTi2 and CuHf2 phases are solid solution with each other. It’s worth
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noting that β(Ti,Hf) phase was observed in α(Ti)-α(Hf) part, β(Ti,Hf) phase is stable
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15 at above 800 °C according to Cu-Hf binary diagram [11]. Therefore, α(Ti,Hf)/β(Ti,Hf)
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17 phase-transition temperature reduce above 100 °C with addition of Cu.
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Fig. 8. Diffusion couple annealed at 700 °C for 40 days
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39 For supplementing phase equilibrium data of Cu-Ti-Hf ternary system, 13 topical
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41 equilibrated alloys were annealed at 700 °C for 120 days. Microstructures and
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43 constituent phases of all equilibrated alloys were further analyzed by both EPMA and
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45 XRD techniques. The constituent phases and compositions in these annealed alloys
46
47 are summarized in Table 3.
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 1
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Table 3 Constituent phases and their compositions in the Cu-Ti-Hf alloys equilibrated at 700 °C.
3
4 Alloys’ Phase equilibria Composition(at.%)
5 number Phase1/ Phase2/Phase3 Phase1 Phase2 Phase3
6
7 Cu Ti Hf Cu Ti Hf Cu Ti Hf
8 B1 Cu/Cu5Hf/Cu4Ti 97.9 2.0 0.1 81.5 4.2 14.3 79.7 1.6 1.7
9
10 B2 Cu51Hf14/Cu4Ti/Cu4Ti3 78.0 9.2 12.8 78.3 20.0 1.7 57.6 41.7 0.7
11 B3 Cu51Hf14/CuTi /Cu4Ti3 75.2 7.9 16.9 48.8 48.9 2.3 55.8 42.2 2.0
12 B4 Cu51Hf14/CuTi 77.7 2.6 19.7 50.1 43.4 6.5 /
13
14 B5 Cu51Hf14/CuTi 77.4 2.0 20.6 49.6 41.4 9.0 /
15 B6 Cu51Hf14/Cu10Hf7/CuTi 77.6 1.2 21.2 59.5 14.3 26.2 51.0 36.6 12.4
16
B7 Cu51Hf14/Cu10Hf7 77.6 0.9 21.5 60.0 6.6 33.4 /
17
18 B8 Cu51Hf14/Cu10Hf7 78.0 0.5 21.5 60.4 2.7 36.9 /
19 B9 Cu51Hf14/Cu10Hf7 78.2 / 21.8 60.4 / 39.6 /
20
21 B10 Cu10Hf7/CuTi/Cu(Ti,Hf)2 59.6 10.8 29.6 49.7 34.3 16 34.2 23.3 42.5
22 B11 Cu10Hf7/Cu(Ti,Hf)2 59.0 28.7 12.3 34.2 40.1 25.7 /
23 B12 Cu(Ti,Hf)2/α(Ti,Hf) 31.5 68.3 0.2 1.1 98.8 0.1 /
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25 B13 Cu(Ti,Hf)2/β(Ti,Hf) 33.7 30.7 35.6 2.4 84.7 12.9 /
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29 Seen from the BSE image in Fig. 9(a), the alloy B1 consists of white Cu5Hf, gray
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31 Cu4Ti and dark Cu phases recognized by EPMA. The BSE image in Fig. 9(c) and
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33 XRD pattern shown in Fig. 10(a) prove that alloy B2 located in
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35 Cu51Hf14+Cu4Ti+Cu4Ti3 three-phase region. In addition, many researches [31-34]
36
37 insist that the Cu3Ti2 phase is stable at 700 °C. It is expected that the three-phase
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39 region of Cu3Ti2+Cu4Ti+Cu4Ti3 is existent. Similarly based on the EPMA and XRD
40
41 as illustrated in Figs. 9(b) and 9(d), the microstructures of alloys B4 and B6 consist of
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43 CuTi+Cu51Hf14 and Cu51Hf14+CuTi+Cu10Hf7, respectively. The XRD results of alloys
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45 B2, B3 and B9 are shown in Fig. 10(a), (b) and (c), agreeing with the results of
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47 EPMA. The microstructure of alloy B9 with nominal composition Cu75Hf25 shows in
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Fig. 10(d), which consists of white Cu10Hf7 phase and gray Cu51Hf14 phase. The result
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52
indicates the Cu8Hf3 phase is unstable at 700 °C.
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 1
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26 Fig. 9. Backscattered electron images of the alloys annealed at 700 °C for 120 days: (a) alloy B1; (b) alloy B4;
27
(c) alloy B2; (d) alloy B6.
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54 Fig. 10. BSE image and XRD patterns of the alloys annealed at 700 °C for 120 days: (a) XRD patterns of alloy B2;
55
56 (b) XRD patterns of alloy B4; (c) XRD patterns of alloy B9; (d) BSE image of alloy B9.
57
58 Based on the investigative results from the diffusion triple and the alloy samples,
59
60 the constructed isothermal section of the Cu-Ti-Hf ternary system at 700 °C is shown
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 in Fig. 11. All the composition raw data are labeled as open circles and the tie-lines
1
2
3
are presented as dotted lines in Fig. 11(a). We can see from Fig. 11(b), there are 9
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5
three-phase regions and 19 two-phase regions in the isothermal section.
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25
26
27 Fig. 11. Isothermal section of Cu-Ti-Hf system at 700 °C: (a) with experimental data from the present work;
28 (b) without experimental data.
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30
31
32 3.3 Comparison of phase relations at 800 °C and 700 °C
33
34
35 Here, a preliminary comparison of phase relations at 800 °C and 700 °C is
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37 carried out. As seen in Figs. 7(b) and 11(b), there are some evident differences which
38
39 are worthy further discussion.
40
41
42 (1) Two three-phased regions, Cu+Cu51Hf14+Cu5Hf and Cu+Cu51Hf14+Cu4Ti at
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44 800 °C transform to other two three-phase regions, Cu+Cu5Hf+Cu4Ti and Cu5Hf
45
46 +Cu4Ti+Cu51Hf14 at 700 °C due to a peritectoid-eutectoid reaction.
47
48
49 (2) The Cu51Hf14+Cu8Hf3+Cu10Hf7 three-phased region disappeared because the
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51 metastable Cu8Hf3 phase faded away at 700 °C.
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53
(3) Two three-phased regions, Cu51Hf14+Cu4Ti+Cu3Ti2 and Cu51Hf14+Cu3Ti2+Cu4Ti3
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55
56
transform to another two three-phased regions, Cu51Hf14+Cu4Ti+Cu4Ti3 and Cu4Ti+
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58 Cu3Ti2+Cu4Ti3, due to dilute solid solutions of Hf in Cu3Ti2 phase from 800 °C to
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60 700 °C.
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 (4) The β(Ti, Hf) phase region obviously narrow down from 800 °C to 700 °C.
1
2
3 3.4 Modulus and hardness of Cu(Ti,Hf)2 phase
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5
6 Nano-indentation test [35] can be performed to determinate modulus and
7
8 hardness of Cu(Ti,Hf)2 phase at room temperature. By combining EPMA,
9
10 composition dependent elastic modulus and hardness data for the Cu(Ti,Hf)2 phase
11
12 were obtained. Nano-indentation tests can be useful to effectively obtain the trend of
13
14 the elastic modulus and hardness with alloy composition, which would be very
15
16 helpful in finding the optimum composition with the best choice of the elastic
17
18 modulus and hardness. The deduced topical curve according to the measurement is
19
20 shown in Fig. 12, indicating that the modulus and hardness rose with increased Ti
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22
(0%~21%) and then declined with increased Ti (21%~50%) in Cu(Ti,Hf)2 phase. The
23
24
25
maximum modulus and hardness were about 183 Gpa and 7.3 Gpa when Ti substrate
26
27 for about 21 at. % Hf in Cu(Ti,Hf)2 phase.
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44
45
46 Fig.12. The modulus and hardness curve of the Cu(Ti,Hf)2 phase.
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48
49
50
51 4. Conclusions
52
53 In this contribution, isothermal sections of the Cu-Ti-Hf ternary system at 800 °C
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55 and 700 °C were experimentally constructed using diffusion triples and several key
56
57 equilibrated alloys. 10 three-phased regions and 9 three-phased regions exist in
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59 Cu-Ti-Hf isothermal section at 800 °C and 700 °C, respectively. The Cu8Hf3 phase is
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65
 confirmed stable at 800 °C and unstable at 700 °C. There are biggish solubility of Ti
1
2
3
in Cu10Hf7, Cu51Hf14 phases and of Hf in CuTi phase. While, Ti can substitute for all
4
5
the Hf in CuHf2 phase and form continuous solid solution Cu(Ti,Hf)2. The phase
6
7 transformation temperature of α(Ti, Hf)/β(Ti, Hf) reduces above 100 °C with addition
8
9 of Cu. In addition, the elastic modulus and hardness change in a parabola shape with
10
11 increased Ti in Cu(Ti,Hf)2 phase. The maximum modulus and hardness are about 183
12
13 Gpa and 7.3 Gpa when the about 21 at.% Hf replaced by Ti.
14
15
16
17 Acknowledgment
18 Financial supports by grants from the National Key Research and Development
19
20
21
Plan (No. 2016YFB0701301) and Major State Basic Research Development Programs
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23
of China (No. 2014CB6644002) are gratefully acknowledged. The Project of
24
25 Innovation-driven Plan in Central South University (No. 2015CX004) and Project
26
27 supported by State Key Laboratory of Powder Metallurgy (Central South University,
28
29 Changsha, China) are gratefully acknowledged.
30
31
32
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35
36
37
38
39 Figure caption:
40
41 Fig. 1. Schematic view of Cu-Ti-Hf diffusion couple.
42
43 Fig. 2. Backscattered electron images (BSE) of diffusion couple annealed at 800 °C
44
45 for 20 days.
46
47 Fig. 3. Schematic diagram of phase distribution in the 800 °C diffusion triple. The
48
49 numbered tri-junction points (1-10) represent ternary equilibria existing in the
50
51 Cu-Ti-Hf system.
52
53 Fig. 4. BSE images of the alloys annealed at 800 °C for 60 days: (a) alloy A4; (b)
54
55 alloy A10; (c) alloy A11; (d) alloy A12.
56
57 Fig. 5. XRD patterns of the alloys annealed at 800 °C for 60 days: (a) alloy A4; (b)
58
59 alloy A10; (c) alloy A11; (d) alloy A12.
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 Fig. 6. BSE images of the alloy A8: (a) as-cast; (b) annealed at 800 °C for 60 days.
1
2
3
Fig. 7. Isothermal section of Cu-Ti-Hf system at 800 °C: (a) with experimental data
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5
from the present work; (b) without experimental data.
6
7 Fig. 8. BSE image of diffusion couple annealed at 700 °C for 40 days.
8
9 Fig. 9. BSE images of the alloys annealed at 700 °C for 90 days: (a) alloy B1; (b)
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11 alloy B4; (c) alloy B2; (d) alloy B6.
12
13 Fig. 10. BSE image and XRD patterns of the alloys annealed at 700 °C for 90 days: (a)
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15 XRD patterns of alloy B2; (b) XRD patterns of alloy B4; (c) XRD patterns of alloy
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17 B9; (d) BSE image of alloy B9.
18
19 Fig. 11. Isothermal section of Cu-Ti-Hf system at 700 °C: (a) with experimental data
20
21 from the present work; (b) without experimental data.
22
23 Fig.12. The modulus and hardness curve of the Cu(Ti,Hf)2 phase.
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Table Click here to download Table Tables.docx

Table 1 Crystallographic data and stability range of solid phases of Cu-Ti-Hf system.
Phase Person symbol Space group Prototype Stability range (℃) References
Cu cF4 Fm3m Cu <1085 [11]
αHf hP2 P63/mmc Mg <1743 [11]
βHf Cl2 Im3m W 1743~2231 [11]
Cu5Hf cF24  AuBe5 <1055 [14]
F4 3 m
Cu51Hf14 hP68 P6/m Ag51Gd14 <1115 [11, 15]
Cu8Hf3 oP44 Pnma Cu8Hf3 <990 [11, 15]
Cu10Hf7 oS68 Aba2 Zr7Ni10 <1025 [11, 15]
CuHf2 tI6 I4/mmm CuZr2 <1310 [11, 16]
αTi hp2 P63/mmc Mg <882 [11]
βTi Cl2 Im3m W 882~1670 [11]
αCu4Ti oC12 Amm2 Au2V ~ [11, 17]
βCu4Ti oP20 I4/m Au4Zr <882 [11, 17]
Cu2Ti oC12 Amm2 Au2V 870~890 [11]
Cu3Ti2 tP10 P4/nmm Cu3Ti2 <875 [11, 18]
Cu4Ti3 tI14 I4/mmm Cu4Ti3 <925 [11, 19]
CuTi tP4 P4/nmm CuTi <982 [11, 20]
CuTi2 tI6 I4/mmm MoSi2 <1005 [11, 20]

Table 2 Constituent phases and their compositions in the Cu-Ti-Hf alloys equilibrated at 800 ℃.
Composition(at.%)
Alloys’ Phase equilibria
Phase1 Phase2 Phase3
number Phase1/ Phase2/Phase3
Cu Ti Hf Cu Ti Hf Cu Ti Hf
A1 Cu/Cu5Hf/Cu51Hf14 96.3 3.4 0.3 81.8 2.5 15.7 78.8 7.8 13.4
A2 Cu/Cu51Hf14/ Cu4Ti 95.1 4.5 0.4 78.6 8.9 12.5 79.0 18.7 2.3
A3 Cu5Hf /Cu51Hf14 81.9 1.3 16.8 78.6 3.4 18.0 / / /
A4 Cu51Hf14/Cu4Ti /Cu3Ti2 77.9 10.5 11.6 77.8 20.1 2.1 59.6 39.3 1.1
A5 Cu51Hf14/Cu10Hf7/CuTi 77.0 1.9 21.1 59.6 13.8 26.7 50.1 37.8 12.2
A6 Cu51Hf14/Cu4Ti3/CuTi 78.2 5.3 16.5 56.7 40.4 2.9 49.2 49.4 1.4
A7 Cu51Hf14/Cu10Hf7 77.6 1.2 21.2 60.0 9.8 30.2 / / /
A8 Cu51Hf14/Cu10Hf7/Cu8Hf3 78.2 / 21.8 60.8 / 39.2 73.4 / 26.6
A9 Cu51Hf14/Cu10Hf7/Cu8Hf3 77.4 0.2 22.4 59.8 0.8 39.4 73.4 0.3 26.3
A10 Cu10Hf7/CuTi /Cu(Ti,Hf)2 59.2 11.9 28.9 49.9 30.0 20.1 34.4 40.4 25.2
A11 αHf/β(Ti,Hf)/Cu(Ti,Hf)2 0.6 54.0 45.4 2.7 60.3 37.0 33.9 12.8 53.4
A12 αTi/β(Ti,Hf)/Cu(Ti,Hf)2 1.4 98.5 0.1 5.5 94.3 0.2 32.0 67.8 0.2
A13 Cu10Hf7/Cu(Ti,Hf)2 59.1 31.8 9.1 34.5 39.1 26.4 / / /
 Table 3 Constituent phases and their compositions in the Cu-Ti-Hf alloys equilibrated at 700 ℃.
Alloys’ Phase equilibria Composition(at.%)
number Phase1/ Phase2/Phase3 Phase1 Phase2 Phase3
Cu Ti Hf Cu Ti Hf Cu Ti Hf
B1 Cu/Cu5Hf/Cu4Ti 97.9 2.0 0.1 81.5 4.2 14.3 79.7 1.6 1.7
B2 Cu51Hf14/Cu4Ti/Cu4Ti3 78.0 9.2 12.8 78.3 20.0 1.7 57.6 41.7 0.7
B3 Cu51Hf14/CuTi /Cu4Ti3 75.2 7.9 16.9 48.8 48.9 2.3 55.8 42.2 2.0
B4 Cu51Hf14/CuTi 77.7 2.6 19.7 50.1 43.4 6.5 /
B5 Cu51Hf14/CuTi 77.4 2.0 20.6 49.6 41.4 9.0 /
B6 Cu51Hf14/Cu10Hf7/CuTi 77.6 1.2 21.2 59.5 14.3 26.2 51.0 36.6 12.4
B7 Cu51Hf14/Cu10Hf7 77.6 0.9 21.5 60.0 6.6 33.4 /
B8 Cu51Hf14/Cu10Hf7 78.0 0.5 21.5 60.4 2.7 36.9 /
B9 Cu51Hf14/Cu10Hf7 78.2 / 21.8 60.4 / 39.6 /
B10 Cu10Hf7/CuTi/Cu(Ti,Hf)2 59.6 10.8 29.6 49.7 34.3 16 34.2 23.3 42.5
B11 Cu10Hf7/Cu(Ti,Hf)2 59.0 28.7 12.3 34.2 40.1 25.7 /
B12 Cu(Ti,Hf)2/α(Ti,Hf) 31.5 68.3 0.2 1.1 98.8 0.1 /
B13 Cu(Ti,Hf)2/β(Ti,Hf) 33.7 30.7 35.6 2.4 84.7 12.9 /
Supplementary Material

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