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Microstructure and mechanical properties of TC4/oxygen-free copper joint with silver interlayer prepared by diffusion bonding Qiang Shen, Huiying Xiang, Guoqiang Luo, Chuanbin Wang, Meijuan Li, Lianmeng Zhang

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S0921-5093(13)01380-4 http://dx.doi.org/10.1016/j.msea.2013.12.017 MSA30570

Materials Science & Engineering A

Received date: 26 October 2013 Revised date: 2 December 2013 Accepted date: 3 December 2013 Cite this article as: Qiang Shen, Huiying Xiang, Guoqiang Luo, Chuanbin Wang, Meijuan Li, Lianmeng Zhang, Microstructure and mechanical properties of TC4/oxygen-free copper joint with silver interlayer prepared by diffusion bonding, Materials Science & Engineering A, http://dx.doi.org/10.1016/j. msea.2013.12.017 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Microstructure and mechanical properties of TC4/oxygen-free copper joint with silver interlayer prepared by diffusion bonding

Qiang Shen, Huiying Xiang, Guoqiang Luo , Chuanbin Wang, Meijuan Li, Lianmeng Zhang

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

Abstract Diffusion bonding of two dissimilar materials, Ti-6Al-4V (TC4) and oxygen-free copper (OFC), was investigated at low temperature. A 30-m silver foil was used as interlayer and the bonding was carried out at various bonding temperatures and times. The diffusion bonded joint microstructures were studied using an S-4800 field emission scanning electron microscope, JXA-8100 electron probe micro-analyzer, and Rigaku Ultima II X-ray diffractometer. Joint tensile strengths were measured by tensile tests. The silver interlayer prevented the formation of Ti-Cu compounds, AgTi and AgTi2 were generated at the TC4/Ag interface and a solid solution formed at the Ag/OFC interface. The tensile strength of the TC4/Ag/OFC joint increased first and decreased with bonding temperature or bonding time. The joint bonded at 700C for 120 min at 10 MPa showed a maximum tensile strength of 161.9 MPa. Fracture morphology showed that ductile fracture initiation and propagation took place at the Ag/OFC interface, which was the weak point of the joint. Keywords: Diffusion bonding; Silver interlayer; Mechanical properties; Titanium alloys; Oxygen-free copper.

Corresponding author. Tel.: +86 027 87168606; Fax: +86 027 87879468. Email: luogq@whut.edu.cn.

1. Introduction Ti-6Al-4V (TC4) is an + alloy used extensively in aircraft structure parts because of its high specific strength and erosion resistance [1, 2]. The high cost of processing and fabrication of TC4 is a major factor limiting its use. To expand on its potential applications, the bonding of TC4 to copper has been suggested. TC4 is chemically reactive at high temperatures and extracts oxygen and nitrogen from the atmosphere easily [3]. It is therefore difficult to bond TC4 to copper by traditional welding. Diffusion bonding is a joining method for similar and dissimilar materials in vacuum and can minimize dimensional tolerance and structural inhomogeneities [4, 5]. The joint quality is affected by the interfacial structure, compound formation and morphology. Process parameters such as temperature, pressure, and diffusion time should be optimized to obtain a high quality joint [6]. Ti-Cu intermediate phases are produced according to the Ti-Cu binary diagram [7]. An appropriate interlayer can be applied to eliminate brittle intermetallic compounds and accommodate chemical compatibilities [810]. The interlayer also needs to react with or process substantial solid solubility in copper and titanium. Recently, TC4 and oxygen-free copper (OFC) were bonded with a 0Cr18Ni9 stainless steel interlayer [11]. Good bonding with a maximum tensile strength of 140.3 MPa was achieved for the TC4/OFC joint at 880C and a 30-min bonding time. Although the 0Cr18Ni9 stainless steel interlayer suppresses the direct reaction between parent metals, such high bonding temperatures can lead to the undesirable deformation of OFC and - transformation of TC4. Titanium has two phase structures and above 880C it transforms to bcc beta titanium from hcp alpha titanium, which can change the original microstructure and mechanical properties of the TC4 base metal [12]. The higher bonding temperature also makes industrial fabrication more difficult and deformation and microstructural changes at higher temperature are detrimental to the tensile strength of the bonded joints [13]. Several experiments have been conducted to decrease brazing temperatures using filler alloys [14, 15]. The filler metal Incusil-ABA (Ag-27.2Cu-12.5In-1.25Ti, wt. %) was applied to decrease the brazing temperature of titanium and its alloys [16]. To facilitate bonding at a low temperature, a silver interlayer may be appropriate because of its low melting point, high ductility, and high diffusivity and

because the silver oxide is unstable at the bonding temperature [17]. Silver interlayers have high solid solubility in copper. Gawde reported on a Cu-Ag diffusion zone free of intermetallic compounds [18]. It has also been reported that a metallurgical bond was produced in the Ti-Ag diffusion zone [19]. In this paper, we bonded TC4 and OFC at low temperature using a silver interlayer. The effect of bonding parameters on joint microstructure and their corresponding effect on mechanical properties was investigated. 2. Experimental procedure The base metal used in the experiment was TC4 with chemical composition (wt. %) of 89.15 Ti, 5.5 Al and 4.5 V. The OFC (99.9 wt %) and base metal had a 25-mm diameter and were 21 mm long. The 30-m-thick silver foil was cut to a diameter of 25 mm. The flat faces of the cylindrical samples were polished using various grades of SiC grit paper and finally with slurry containing 0.05 m alumina particles. The silver foil, TC4, and OFC were cleaned ultrasonically in acetone and were then assembled into a sandwich structure (Fig. 1). A series of diffusion bonding tests were performed with variable bonding temperatures from 550 to 800C, bonding times from 30 to 150 min, and a constant pressure of 10 MPa. The vacuum pressure was less than 1 10-3 Pa. During the bonding, the assemblies were heated at 10C/min to 10C less than the bonding temperature and then at 1C/min until the bonding temperature had been reached. The assemblies were cooled to room temperature in the chamber under vacuum. Cross sections of the joints were prepared using standard metallographic techniques. Joint microstructures were observed with an S-4800 field emission scanning electron microscope (FESEM) in back-scattered electron mode. The redistribution of various elements in the bonded zone was analyzed using a JXA-8100 electron probe micro-analyzer (EPMA). Fig. 2 showed the specimen in the tensile test, the specimens were cut to a diameter of 8 mm and a length of 21 mm by wire-electrode cutting. The tensile strength of the joints was determined using a MTS-810 universal machine at a loading speed of 5 10-5 m/s at room temperature according to ASTM: E8/E8M-11 standard [20]. The fracture surface morphology and phase constitution was examined using FESEM in secondary electron mode and a Rigaku Ultima II X-ray diffraction (XRD) system.

3. Results and discussion 3.1 Microstructure of bonded joints FESEM images of TC4/Ag/OFC joints bonded at different temperatures for 60 min are shown in Fig. 3. Microvoids appeared at the Ag/OFC interface in Fig. 3 (a), indicating that a bonding temperature of 650C was insufficient for reaction across the bond interface. At higher bonding temperatures (700 and 750C), voids at the interface were eliminated by enhanced diffusion. Excellent physical contact and good metallurgical bonding were established in Fig. 3 (b) and (c). The silver layer impeded the formation of Ti-Cu compounds. A continuous reaction layer along the silver layer and TC4 parent metal was observed. The reaction layer increased in thickness after the bonding temperature had been extended. This is in accordance with the theory of diffusion bonding. In contrast, a reaction layer was not observed at the Ag/OFC interface. At 800C, a significant change was observed in the interfaces (Fig. 3 (d)). The silver interlayer disappeared and several reaction layers were observed. Copper and titanium atoms moved fast and diffused continuously into the silver layer. Once the concentration of copper and titanium reached a finite amount, brittle Ti-Cu intermetallic compounds were generated, which had a detrimental effects on joint strength. Changes in the concentration of copper, silver, and titanium along the interface are shown in Fig. 4 (a, b). On the Ag/OFC side, the concentration of silver and copper changed significantly in layer b because of the low inter-diffusion coefficients. The presence of copper in the silver side indicated substantial diffusion of copper atoms to the silver layer side. Significant quantities of silver also migrated to the OFC substrate. A reaction layer was observed (marked as a) at the TC4/Ag interface and the concentration profiles of titanium and silver show plateaus indicating the presence of Ag-Ti compounds. Figure 4 (c, d) shows a high magnification microstructure of the TC4/Ag interface and the variation of elements across this interface. The reaction layer in Fig. 4 (c) consisted of a gray matrix with small dark particles. EPMA analysis across the gray matrix and dark particles showed two plateaus indicating that the concentrations of titanium and silver were relatively constant. The elemental compositions of the different regions marked 16 were measured by energy dispersive spectroscopy (Table 1). Region 1 was the TC4 base metal. Region 2 was identified as a Ti-base solid solution layer of silver, aluminum, and vanadium. The stoichiometric

proportions of titanium and silver in regions 3 and 4 were approximately 1:1 and 2:1, respectively. According to the Ti-Ag binary phase diagram, AgTi and AgTi2 were present. Aluminum atoms aggregated in region 4 leading to the formation of a eutectic mixture of Al and AgTi2. Region 5 was identified to be an Ag-base solid solution layer of titanium. Region 6 was a silver interlayer. We conclude that the reaction layer in Fig. 4 consists of an AgTi matrix with particles of AgTi2 and the formation of AgTi and AgTi2 contributed to the improvement in bonding strength. From the concentration distribution of the joint bonded at 800C (Fig. 5) it can be seen that diffusion occurred between copper and titanium. The diffusion distance from TC4 to OFC was long and there were plateaus (marked as d) in the element dispersion curve, which indicated that Ti-Cu intermetallic compounds formed in this area. Furthermore, the layer adjacent to the TC4 base metal (marked as c) showed mainly titanium with only a small amount of the other elements. As reported by Elrefaey, the diffusion of silver and copper in the TC4 base metal lowered the eutectoid transformation temperature of titanium [21]. It is assumed that the eutectoid transformation Ti + (Cu) Ti took place near the TC4 base metal. Therefore, -Ti formed as bright needles while -Ti formed as a dark plate-like structure between the -Ti needles. The bright dots distributed adjacent to the OFC base metal were identified to be silver. Increasing the bonding temperatures can promote the atomic diffusion of chemical species across the bonding interface. Up to a bonding temperature of 750C, the silver interlayer can prevent the diffusion of titanium into copper and vice versa. AgTi and AgTi2 are generated at the TC4/Ag interface. Ag (Cu) solid solution and Cu (Ag) solid solution are generated at the Ag/OFC interface. However, titanium and copper atoms can cross the intermediate layer and form Ti-Cu intermetallic compounds at 800C. The selection of an appropriate bonding temperature not only ensures complete diffusion of atoms, but also guarantees the absence of Ti-Cu compounds. 3.2 Mechanical properties of the bonded joints Bonding temperature affects atomic diffusion, influences compound formation and joint morphology, and is the dominant parameter in the diffusion bonding process. The effect of bonding temperature on tensile strength is shown in Fig. 6. The TC4/Ag/OFC joint could be

obtained at lower temperature and its tensile strength reached 150.5 MPa compared with a maximum of 140.3 and 48.0 MPa for the TC4/0Cr18Ni9/OFC and TC4/OFC joints, respectively. The tensile strength of the TC4/Ag/OFC joint increased with an increase in bonding temperature up to 750C and decreased at 800C. When the bonding temperature was below 650C, the thermal excitation of the atoms was low. The solubility of Cu and Ag was limited, then voids at the interface appeared (Fig. 3 (a)) and the tensile strength was low. Increasing the bonding temperature to 700C promoted the atomic diffusivity. The Cu-Ag solid solution formed and existed at the Ag/OFC interface. It can be inferred that the solid solution was produced by the diffusion between Ag interlayer and Cu element in OFC at higher bonding temperatures. These Cu-Ag solid solutions reduced the risk of embrittlement of the joint and benefited its mechanical performance. As a result, the tensile strength of the joints at 700C (150.5 MPa) improved. The higher bonding temperature (at 750C) resulted in a small increase in tensile strength. With a further rise in bonding temperature, the joint tensile strength decreased. The higher bonding temperature resulted in more sufficient diffusion, the titanium and copper atoms crossed the silver interlayer to form brittle Ti-Cu intermetallic compounds, while, Cu-Ag solid solution rarely existed at the interface. The ductility of the joint was seriously weakened by Ti-Cu compounds which were distributed at the TC4/OFC interface, so the mechanical properties were reduced. The effect of bonding time on the tensile strength of the bonded joints at 700C is shown in Fig. 7. At 30 min, the tensile strength was 76.1 MPa and gradually increased up to 120 min. At lower bonding times, the bonding strength was low because of the poor contact between the surfaces of the dissimilar materials. A maximum tensile strength of 161.9 MPa was achieved at 120 min because the larger contact between the mating surfaces promoted the atomic diffusivity of the chemical species and Cu-Ag solid solutions were firmly generated. An increase in bonding time led to a decrease in tensile strength because the copper atoms moved more rapidly across the interface, creating an imbalance in flux transfer and resulting in the voids in the fracture surface of the joints [22].

3.3 Fracture morphology and phase composition of bonded joints The fracture morphology of the joints on the TC4 side at different bonding temperatures is shown in Fig. 8. The fracture surface of the joint bonded at 600C was scratched, as indicated by the vertical arrows in Fig. 8 (a). These scratches disappeared with increase in bonding temperature indicating that insufficient atomic diffusion at 600C had not changed the original base metal pattern. At 700C, all dimples were distributed uniformly over the entire fracture surface with torn ridges, as indicated by the slanted arrows in Fig. 8 (b). The dimples were of different sizes and depths and increased in size at 750C. The fracture surfaces are characterized by a ductile feature, which contributed to the bonded joint strength. Grain phases occurred on the surfaces at 800C (Fig. 8 (d)), indicating the brittle nature of the fracture surfaces, which was primarily responsible for reducing the tensile strength. XRD spectra confirmed the phase constitution on the fracture surfaces in Fig. 9. When the temperature was below 750C, intermetallic compounds were not present. The phase on the TC4 side was silver, while copper was the main phase on the OFC side. A small amount of silver was also observed on the OFC side, which increased with increasing bonding temperature. It can be inferred that the fracture occurred at the Ag/OFC interface. With an increase in bonding temperature, the crack extended to the silver interlayer. There was some deviation in diffraction angle of the silver peaks between the raw materials (44.15) and bonded materials (44.41), whose parameters were 700C for 60 min, indicating that Ag (Cu) solid solution and Cu (Ag) solid solution were generated in the Ag/OFC interface. This agrees with the Cu-Ag phase diagram. Silver and copper form a solid solution but their solubility is limited. The Ag (Cu) solid solution layer is therefore the weak point in the diffusion zone of the bonded joints. That is to say, the mechanical properties of the Ag (Cu) solid solution are inferior to those of the Ag-Ti compounds. Moreover, CuTi appeared on the TC4 side and Cu3Ti2 on the OFC side at 800C because of the reaction that occurred between titanium and copper. This led to the occurrence of brittle instead of ductile fractures in the bonded joints. Figure 10 shows the fracture surface microstructure at 700C for different bonding times. Dimples appeared on the fracture surfaces even for a bonding time of 30 min, indicating that

the failure was ductile in nature. The dimples of the bonded joint for 30 min in Fig. 10 (a) were shallow and without torn ridges because of the low elemental diffusivity at lower bonding time. Cracks appeared as indicated by the diagonal arrow in Fig. 10 (d). These cracks were applied as initiation sites of a permanent crack, inducing a poor tensile strength. A longer bonding time is therefore disadvantageous for bonding economy; it leads to undesirable effects that deteriorate the joint mechanical properties. XRD spectra of the fracture surfaces of the joints at different bonding times are shown in Fig. 11. Only silver was detected at the TC4 sides in Fig. 11 (a). Copper and residual silver was found at the OFC side in Fig. 11 (b), without any reaction products. No scratches or Ti-Cu intermetallic compounds appeared on the surfaces for 30120 min, indicating that the influence of bonding temperature with constant bonding time seemed much more obvious than the influence of bonding time. Schematic diagrams of the fracture failure of joints bonded at 700 and 800C for 60 min are shown in Fig. 12 (a, b). The fracture at 700C occurred at the Ag/OFC interface. Ti-Cu compounds formed at 800C and the fracture occurred on the CuTi and Cu3Ti2 boundaries. The joint bonding strength at 800C became smaller and we can conclude that the Ag-Ti compounds show better mechanical properties than the Ti-Cu compounds. The fracture failure of joints bonded at 700C for 150 min also occurred at the Ag/OFC interface (Fig. 12 (c)). The bonding strength was lower because of the flux transfer imbalance between silver atoms and copper atoms, which resulted in voids at the Ag/OFC interface. 4. Conclusion TC4 was bonded to OFC through diffusion bonding using a silver interlayer and by processing the assemblies from 550 to 800C for 30150 min at 10 MPa uniaxial pressure. The addition of a silver interlayer lowered the bonding temperature and improved the bonding strength. The results are summarized as follows: (1) Atomic migration of chemical species across interfaces increased with increasing bonding temperatures and times. The silver interlayer prevented interdiffusion between TC4 and OFC below 750C. AgTi and AgTi2 were generated at the TC4/Ag interface and a complete solid solution formed at the Ag/OFC interface. However, at 800C, Ti-Cu compounds were generated at the joint interface.

(2) The tensile strength of the bonded specimens increased with increasing temperature and decreased with a further increase in temperature. Tensile strength also first increased with increasing bonding time and then decreased. For the TC4/Ag/OFC joint, a maximum tensile strength of 161.9 MPa was obtained at 700C for 120 min at 10 MPa and was greater than that for the TC4/OFC joint with a 0Cr18Ni9 interlayer. (3) The fracture morphology for joints bonded at lower temperatures had ductile characteristics. XRD studies show that fracture initiation and propagation occurred at the Ag/OFC interface and this interface was the weak point in the joint. However, the fracture morphology of joints at 800C had brittle characteristics due to the formation of Cu-Ti compounds. The weak component of the joints that formed at the Ag/OFC interface transferred into the Cu-Ti compound layers. Acknowledgments This work has been supported by National Natural Science Foundation of China (51202175), the 111 Project (B13035) and the Fundamental Research Funds for the Central Universities (WUT: 2013-II-024), State Key Laboratory of Advanced Technology for Materials Synthesis and Processing (Wuhan University of Technology) (Grant No: 2014-KF-7). References [1] M.S. Kenevisi, S.M. Mousavi Khoie. Mater. Lett. 76 (2012) 144146. [2] M.S. Kenevisi, S.M. Mousavi Khoie. Mater. Des. 38 (2012) 1925. [3] E. Atasoy, N. Kahraman. Mater. Charact. 59 (2008) 14811490. [4] M.L. Huang, N. Kang, Q. Zhou, Y.Z. Huang. J. Mater. Sci. Technol. 28 (2012) 844852. [5] B. Kurt, N. Orhan, E. Evin, A. Calik. Mater. Lett. 61 (2007) 17471750. [6] M. Joseph Fernandus, T. Senthilkumar, V. Balasubramanian. Mater. Des. 32 (2011) 16511656. [7] A.A. NayebHashemi, J.B. Clark, L.J. Swartzendruber. Binary alloy phase diagram. Materials Park, OH: ASM international, 1990. [8] S. Kundu, S. Chatterjee. Mater. Charact. 59 (2008) 631637. [9] O. Torun, A. Karabulut, B. Baksan, I. elikyrek. Mater. Des. 29 (2008) 20432046. [10] H. Sabetghadama, A. Zarei Hanzaki , A. Araee. Mater. Charact. 61 (2010) 626634.

[11] Q. Shen, H.Y. Xiang, Q.Q. Luo, X.P. Su, L.M. Zhang. Mater. Des. 50 (2013) 230234. [12] S. Kundu, S. Chatterjee. Mater. Sci. Eng. A 425 (2006) 107113. [13] X.R. Li, W. Liang, X.G. Zhao, Y. Zhang, X.P. Fu, F.C. Liu. J. Alloys Comp. 471 (2009) 408411. [14] Jung G. Lee, Y.H. Choi, J.K. Lee, G.J. Lee, M.K. Lee, C.K. Rhee. Intermetallics 18 (2010) 7073. [15] Jung G. Lee, J.K. Lee, S.M. Hong, M.K. Lee, C.K. Rhee. J. Mater. Sci. 45 (2010) 68376840. [16] A. Elrefaey, W. Tillmann. J. Mater. Process Technol. 209 (2009) 48424849. [17] E. Ganjeh, H. Sarkhosh, H. Khorsand, H. Sabet, E.H. Dehkordi, M. Ghaffari. Mater. Des. 39 (2012) 3341. [18] P.S. Gawde, R. Kishore, A.L. Pappachan, G.B. Kale, G.K. Dey. T. Indian Metals 63 (2010) 853857 [19] A.H.M.E. Rahman, M.N. Cavalli. Mater. Sci. Eng. A 527 (2010) 51895193. [20] ASTM: E8/E8M-11. Standard Test Methods for Tension Testing of Metallic Materials. ASTM international, 2011. Available from: http://www.astm.org/Standards/E8.htm. [21] A. Elrefaey, W. Tillmann. J. Mater. Process Technol. 209 (2009) 27462752. [22] M. Ghosh, S. Das, P.S. Banarjee, S. Chatterjee. Mater. Sci. Eng. A 390 (2005) 217226.

Fig. 1. Schematic drawing of the sample assembly. Fig. 2. Photograph of the tensile testing specimen. Fig. 3. Microstructure of the joint bonded for 60 min at different temperatures: (a) 650C, (b) 700C, (c) 750C and (d) 800C. Fig. 4. Element concentration across the bonding interface for joint performed at temperature of 750C for 60 min: (a, b) TC4/Ag/OFC interface and (c, d) TC4/Ag interface. Fig. 5. Element concentration across the bonding interface (joint performed at temperature of 800C for 60 min). Fig. 6. The effect of bonding temperatures on the tensile strength of the joint for 60 min. Fig. 7. The effect of bonding times on the tensile strength of the joint at 700C. Fig. 8. Fracture surfaces of the bonded joints on TC4 side for 60 min: (a) 600C, (b) 700C, (c) 750C and (d) 800C. Fig. 9. XRD of fracture surfaces at different bonding temperatures for 60 min: (a) TC4 side and (b) OFC side. Fig. 10. Fracture surfaces of the bonded joints on TC4 side at 700C: (a) 30 min, (b) 60 min, (c) 120 min and (d) 150 min. Fig. 11. XRD of fracture surfaces at 700C for different bonding times: (a) TC4 side and (b) OFC side. Fig. 12. Schematic diagram of fracture failure of the joint: (a) 700C for 60 min, (b) 800C for 60 min and (c) 700C for 150 min.

Figure 1

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Figure 5

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Figure 9

Figure 10

Figure 11

Figure 12

Table 1 Chemical composition of layer 16 in Fig. 4 (at %)

Element

Ti

Ag

Al

Phase

87.53

10.91

1.56

TC4

85.86

3.74

9.34

1.04

Ti(ss,Ag)

48.92

48.87

1.89

0.32

AgTi

52.93

30.60

12.53

2.94

AgTi2(ss,Al)

19.59

79.34

0.84

0.23

Ag(ss,Ti)

100

Ag