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Microstructure and tensile properties of Sn9ZnxAg lead-free solder alloys

J.M. Song *, G.F. Lan, T.S. Lui, L.H. Chen
Department of Materials Science and Engineering, National Cheng-Kung University, No. 1, Ta-Hsueh Road, Tainan 701, Taiwan, ROC Received 25 August 2002; received in revised form 11 December 2002; accepted 16 December 2002

Abstract Microstructural features and tensile properties of SnZn eutectic alloys with varying Ag content were examined in this study. Results indicate that the main eects of Ag addition were reduced strength and greater ductility due to the dierences in the morphology and distribution of second phase particles. Also, a modied structure caused by rapid solidication resulted in better tensile properties. 2003 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
Keywords: SnZnAg; Microstructure; Mechanical properties

1. Introduction SnZn eutectic alloy has recently been considered as a candidate for lead-free solder material because of its low melting point (198 C), excellent mechanical properties and low cost [13]. However, since Zn-containing alloys have the problem of oxidation and wetting [4,5], new SnZn based alloys are still under development. Considering the improvement in wetting ability by Ag doping [6], SnZnAg alloys show potential as lead-free solder materials. McCormack and Jin [7] also reported that small additions of Ag can improve the ductility of SnZn base solders, and a larger Ag alloying content resulting in the presence of Ag Zn precipitates is not accompanied by an increase

in strength. However, the reason for this is not understood yet. Given the dearth of information concerning the eect of Ag addition on the mechanical properties of SnZn alloys, this study chose to investigate the microstructural features and tensile properties of near-eutectic SnZn alloys with varying Ag content. The eects of solidication rate and natural aging were also examined.

2. Experimental procedures Master alloys of near-eutectic SnZn alloys with Ag content ranging from 0.5 to 3.5 wt.% were prepared by melting pure tin, pure zinc and pure silver in a high frequency induction furnace. The chemical compositions of the test materials are listed in Table 1, where the specimens are designated according to their Ag content. The alloy ingots were then remelted and cast into a Y-shaped

Corresponding author. Tel./fax: +886-6-2380698. E-mail address: samsong@url.com.tw (J.M. Song).

1359-6462/03/$ - see front matter 2003 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved. doi:10.1016/S1359-6462(02)00647-4

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Table 1 Chemical compositions of Sn9ZnxAg alloys Sample 0.5Ag 1.0Ag 1.5Ag 2.5Ag 3.5Ag Ag 0.5 1.0 1.5 2.5 3.5 Zn 8.9 8.9 8.9 8.8 8.7 Sn Bal. Bal. Bal. Bal. Bal.

graphite mold (for specimens with a higher solidication rate) and gypsum mold (for specimens with a lower solidication rate), with a constant thickness of 2.4 mm. Tensile tests with an initial strain rate of 7:5 104 s1 were performed after a xed natural aging period at room temperature. Each datum was the average of three test results.

3. Results and discussion Fig. 1 shows the microstructure of the Sn9Zn xAg alloys. For the 0.5Ag specimens, the microstructure features were similar to those of SnZn eutectic, and the structure was ner in the graphite-cast specimen. Notably, the morphology of Zn-rich phase transformed from needle-like to

rod-like as the solidication rate was increased. AgZn compounds and primary Sn-rich dendrites could be observed in the specimens with higher Ag content and the amounts increased with increasing Ag content. Compared with the graphite-cast specimen, the AgZn compounds were more massive and the number of the retained Zn-rich particles was relatively high in the gypsum-cast specimen with a higher Ag content. Quantitative results and X-ray diraction patterns shown in Fig. 2 also indicate that AgZn compounds (AgZn3 and Ag5 Zn8 ) replaced Zn-rich phase in the high-Ag samples. This provides further evidence that the degree of transformation from Zn-rich phase to AgZn compounds was more signicant when the solidication rate was higher. Fig. 3 shows the hardness test results of the specimens after natural aging for 20 days, indicating that the hardness of Sn-rich phase decreased slightly with a higher Ag content. The hardness of the AgZn compound measured Hv 75, and the Zn-rich phase possessed a lower hardness of about Hv 36. Typical tensile stressstrain curves are shown in Fig. 4 and indicate that, for both the graphite and gypsum-cast samples, the tensile deformation resistance decreased when the Ag content was within

Fig. 1. Microstructure of the Sn9ZnxAg alloys: (a) graphite-cast 0.5Ag; (b) graphite-cast 2.5Ag; (c) graphite-cast 3.5Ag; (d) gypsumcast 0.5Ag; (e) gypsum-cast 2.5Ag; (f) gypsum-cast 3.5Ag samples.

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Fig. 2. (a) X-ray diraction pattern and (b) area fraction of AgZn compounds for samples with various Ag contents.

Fig. 3. Hardness of the Sn-rich matrix and second phase particle.

the range 01:5 wt.%. Fig. 4(a) also shows that the sample with a higher Ag content exhibited a lower modulus of elasticity. Detailed tensile results (Fig. 5) display that the graphite-cast specimens possessed higher tensile stress and total elongation than the gypsum-cast specimens in spite of the Ag content. The strength of both the two specimens dropped drastically with increasing Ag content before remaining almost constant when the Ag content exceeded 1.5 wt.%. As for the elongation, the total elongation of the specimens was higher than 35% under all conditions. It rose with increasing Ag content and then remained constant

when the Ag content reached 1.5 wt.%. In addition, the uniform elongation of all specimens stayed at 10%. Cracks induced by Zn-rich needles might have been responsible for the low uniform elongation. Fig. 6(a) and (b) show the surface of the necked region of the tensile specimen under a strain of 35% before fracturing, revealing that cracks initiated at Zn-rich needles within the Snrich dendrites, whereas the AgZn particles did not cause cracks. According to the aforementioned results, the strengthening eect of hard AgZn compounds was not signicant since the amount of AgZn compounds increased but tensile strength and elastic modulus were reduced in the high-Ag specimens. This can be attributed to the dierence in the distribution of second phase particles. In the case of the specimen with low Ag content, the near-eutectic SnZn structure comprised large amounts of uniformly distributed ne Zn-rich needles which gave rise to a denite dispersestrengthening eect and thus greater stiness. As for the high-Ag samples, the massive AgZn compounds at the eutectic regions accompanied by the primary Sn-rich dendrites resulted in a weaker contribution to strengthening, though the AgZn compounds exhibited greater hardness. This also led to better ductility. In addition, increasing the solidication rate rened and modied the Zn-rich phase, and thus improved the tensile properties.

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Fig. 4. Tensile stressstrain curves of (a) graphite-cast samples and (b) gypsum-cast samples.

Fig. 5. Quantitative tensile data: (a) tensile strength and (b) elongation (the tensile data of SnZn eutectic alloy were redrawn from Chuang et al. [8]).

Fig. 6. (a) Unetched surface of the graphite-cast 1.5Ag sample under a strain of 35%, showing cracks and AgZn compound particles; (b) magnied etched structure of Fig. 6(a), indicating cracks initiated from the tip of Zn-rich phase and linked together.

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strength and lower elastic modulus. Results demonstrate that Sn9Zn alloys with an Ag content of 1.5 wt.% exhibited acceptable tensile properties. In addition, the specimens with a higher solidication rate had better tensile properties due to the ne structure and modied Zn-rich particles.

Acknowledgements This work has been supported by the Chinese National Science Council (Contract: NSC 912216-E-006-054), for which the authors are grateful.

Fig. 7. Tensile strength as a function of natural aging time.

Fig. 7 shows that the tensile strength of graphitecast specimens decreased with a prolonged naturalaging time and the decreasing trend slowed down when the aging time reached 20 days. Also, most of the SnZnAg alloys investigated in this study mainly possessed a greater strength than the Sn 40Pb alloy [9] and the much-discussed lead-free solder, Sn3.5Ag alloy [10].

References
[1] Yang W, Messler Jr RW. J Electron Mater 1994;23:765. [2] Mavoori H, Chin J, Vaynman S, Moran B, Keer L, Fine ME. J Electron Mater 1997;41:1269. [3] McCormack M, Jin S, Kammlott GW. In: Proceedings of the 1995 IEEE International Symposium on Electronics and the Environment, ISEE, May 13 1995, Orlando, FL, USA. p. 1716. [4] Hua F, Glazer J. Design & reliability of solders and solder interconnections. In: TMS Annual Meeting, 1997. p. 65. [5] Vaynman S, Fine ME. Scr Mater 1999;41:1269. [6] Takemoto T, Funaki T, Matsunawa A. Weld Res Abroad 2000;46:20. [7] McCormack M, Jin S. J Electron Mater 1994;23:715. [8] Chuang CM, Lui TS, Chen LH. J Mater Sci 2002;37:191. [9] Chuang CM, Lui TS, Chen LH. J Mater Res 2001;16:2644. [10] Yin TM, Chuang CM, Lui TS, Chen LH, in preparation.

4. Conclusions Ag additions gave rise to microstructural changes in SnZn eutectic alloys, that is, the appearance of Sn-rich dendrites and AgZn compounds (AgZn3 and Ag5 Zn8 ) which replaced Zn-rich phase. This led to higher ductility, reduced