Introduction
Literature Review of the Associated Sn-Cu and Sn-Ni Binary Systems
System | Authors | Reference No. | Temperature (°C) | Weight Percent of Cu or Ni |
---|---|---|---|---|
Sn-Cu | Harding and Pell Walpole (1948) | 227 | 0.754 | |
Thermo-Calc | 226.8 | 0.885 | ||
Hanson (1934) | 226.91 | 0.746 | ||
Sn-Ni | Nash et al. (1985) | 231.3 | 0.163 | |
Hanson et al. (1934) | 232 | 0.134 | ||
Ghosh (1999) | 231.1 | 0.167 | ||
Belyakov and Gourlay (2012) | 231.4 | 0.090 |
Literature Review of the Sn-Cu-Ni Ternary System
Authors | Method | Results | Remarks |
---|---|---|---|
Schmetterer et al. (2009) Sn-Cu-Ni Ref. 26 | equilibria/fast quenching/EPMA-XRD crucible: vacuumed silica ampoule | isothermal at 220 °C, 400 °C, 500 °C, 700 °C | not much information about Sn-rich composition ternary solubilities were characterized no indication of achievement of a glassy phase during quenching |
Lin et al. (2002) Sn-Cu-Ni Ref. 23 | equilibria/fast quenching/EPMA-XRD crucible: vacuumed silica ampoule | isothermal at 240 °C | only one reasonable result for equilibria Sn-Ni3Sn4-Cu6Sn5 at.pct Ni = 1.1, at.pct Cu = 0.6 no indication of achievement of a glassy phase during quenching |
Snugovsky et al. (2006) Sn-Cu-Ni Ref. 24 | equilibria/Fast quenching/EPMA of IMC. crucible: BN (boron nitride) | invariant lines 235 °C to 227 °C | reported of a ternary compound Cu33Ni23Sn44 no reported XRD. no indication of achievement of a glassy phase during quenching |
Gourlay et al. (2010) Sn-Cu-Ni Ref. 15 | equilibria/fast quenching/EPMA crucible: stainless-steel cups coated with BN. settling of the IMC on the bottom of the crucible | isothermal at 268 °C | no indication of achievement of a glassy phase during quenching |
Yu et al. and Vuorinen et al. (2007) Sn-Cu-Ni Ref. 12 | CALPHAD | isothermal at T = 240 °C and 250 °C | database constructed based on the experimental works of Wang et al., Lin et al., Oberndorff and Ho et al. |
Critical Review of the Experimental Works Reported in the Literature
Experimental Methodologies for Equilibrium Studies of Sn-Cu-Ni Alloy
Objective of the Present Work
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To identify the underlying reasons for the disparity in the existing results in the literature.
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To design a new experimental approach using state of the art phase equilibrium methodologies and analytical chemical analysis procedures.
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To generate a new Sn-Cu-Ni phase diagram based on reliable experimental data including four liquidus lines at 240 °C, 250 °C, 260 °C, and 270 °C.
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Characterize the invariant (or invariants) line for the equilibrium between a liquid phase with two IMCs
Corroboration of Attainment of Homogeneous Liquid During Fast Quenching
Experimental Procedure
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Produce a few large crystals by selection of initial composition to allow an easy physical separation between crystals and the liquid phase.
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Promote relatively fast quenching to distinguish the primary phase from what would appear during quenching.
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Ensure the sample is large enough to easily manipulate and to obtain between 0.1 and 0.2g for the ICP-AES analysis. The target parameters and verification of the experimental procedure and a summary of parameters used during the experimental work are indicated in Table III. The starting material included 99.99985 pct purity Sn chips, 99.98 wt pct purity Ni chips, 99.99 wt pct purity Cu chips (provided by the sponsor of the present work). The electric resistance furnace, schematically described in Figure 5, consist of 6-mm-diameter quartz tubes, an input controller with two Resistance Temperature Detectors (RTD) 3200 series and a power input controller Modal 3216. The electronic scale has an accuracy of 4 decimal digits.
Parameter | Technique | Target of Accuracy |
---|---|---|
Purity of metals | high purity materials | purities of materials are > 99.9 pct |
Temperature | controller vertical furnace assembled to allow fast quenching | hot zone > 0.5 mm control of temp. ± 0.1 °C |
Method of analysis IMC Liquid phase | electron probe micro analyze (EPMA) for IMC inductively Coupled Plasma (ICP) for the liquid phase | crystal composition accuracy better an 1 wt pct for major composition (Sn) and 0.01 wt pct for minor compositions (Ni and Cu) |
Achievement of equilibrium and settlement of large intermetallic phases | slow cooling from 700 °C to the target equilibrium temperature long-time of equilibration (> 12 hours) at the target temperature ± 1 °C equilibrium for 1 hour at the target temperature ± 0.1 °C | observation of large size (> 100 µm) intermetallic compounds no intermetallic compounds observed on top of the sample |
Cu (Weight Percent) | Ni (Weight Percent) | ||
---|---|---|---|
Initial | ICP Analysis | Initial | ICP Analysis |
0.44 | 0.36 | 0.08 | 0.07 |
0.48 | 0.40 | 0.10 | 0.09 |
0.50 | 0.52 | 0.12 | 0.11 |
0.55 | 0.53 | 0.15 | 0.14 |
0.80 | 0.78 | 0.00 | 0.00 |
0.00 | 0.001 | 0.00 | 0.00 |
1.80 | 1.83 | 0.00 | 0.00 |
0.00 | 0.001 | 1.00 | 1.02 |
Experimental Results and Discussion
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A low proportion of IMCs in the sample
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Good sedimentation with the IMCs of large size (> 100 μm) accumulating in the bottom of the sample
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A large liquid area in the upper side of the sample free of IMCs. The experimental results for the Sn-Cu and Sn-Ni binaries are summarized in Tables V and VI, respectively. The tables include the initial composition, the equilibrium composition of liquid and the composition of the IMC phases and also the results of experimental points where only a liquid phase was observed. Figures 6 and 7 show the equilibrium results for the binaries and the discrepancies between these results and those of Hanson et al.,[14] Harding et al.,[11] and the Thermo-calc. simulation for the system Sn-Cu. The differences of the results of the present work with those of Hanson et al.[14] and the Thermo-calc. simulation for the Sn-Ni system are also apparent.
No. | Tem. °C | Initial (Weight Percent) | Liquid (Weight Percent) | IMC (Normalized Weight Percent) | ||
---|---|---|---|---|---|---|
Cu | Cu | Sn | Cu | IMC | ||
1 | 230 | 1.4 | 1.02 | 61.7 | 38.3 | Cu6Sn5 |
2 | 240 | 1.8 | 1.20 | 60.1 | 39.9 | Cu6Sn5 |
3 | 250 | 1.8 | 1.36 | 60.6 | 39.4 | Cu6Sn5 |
4 | 260 | 1.8 | 1.48 | 59.8 | 40.2 | Cu6Sn5 |
5 | 270 | 1.8 | 1.61 | 62.7 | 37.3 | Cu6Sn5 |
6* | 270 | 1.6 | 1.58 | n/a | n/a | n/a |
No. | Tem. °C | Initial (Weight Percent) | Liquid (Weight Percent) | IMC (Normalized Weight Percent) | ||
---|---|---|---|---|---|---|
Ni | Ni | Sn | Ni | IMC | ||
7 | 240 | 0.25 | 0.16 | 72.8 | 27.2 | Ni3Sn4 |
8 | 250 | 0.25 | 0.17 | 74.5 | 25.5 | Ni3Sn4 |
9* | 250 | 0.15 | 0.16 | n/a | n/a | n/a |
10 | 260 | 0.25 | 0.19 | 73.9 | 26.1 | Ni3Sn4 |
11* | 260 | 0.15 | 0.16 | n/a | n/a | n/a |
12 | 270 | 0.5 | 0.2 | 72.8 | 27.2 | Ni3Sn4 |
13* | 270 | 0.15 | 0.16 | n/a | n/a | n/a |
14 | 280 | 0.3 | 0.22 | 74.2 | 25.8 | Ni3Sn4 |
No. | Tem °C | Initial (Weight Percent) | Liquid (Weight Percent) | IMC (Normalized Weight Percent) | IMC | ||||
---|---|---|---|---|---|---|---|---|---|
Cu | Ni | Cu | Ni | Sn | Cu | Ni | |||
15 | 240 | 0.6 | 0.4 | 0.32 | 0.17 | 73.82 | 4.77 | 21.4 | (Ni, Cu)3Sn4 |
62.47 | 23.3 | 14.2 | (Cu, Ni)6Sn5 | ||||||
16* | 240 | 0.44 | 0.08 | 0.36 | 0.074 | n/a | n/a | n/a | n/a |
17 | 250 | 0.4 | 0.4 | 0.33 | 0.18 | 73.42 | 4.39 | 22.2 | (Ni, Cu)3Sn4 |
18* | 250 | 0.48 | 0.1 | 0.4 | 0.09 | n/a | n/a | n/a | n/a |
19* | 250 | 0.5 | 0.12 | 0.52 | 0.11 | n/a | n/a | n/a | n/a |
20 | 260 | 1.4 | 0.8 | 0.83 | 0.28 | 61.6 | 20.7 | 17.7 | (Cu, Ni)6Sn5 |
21 | 260 | 1.2 | 0.2 | 1.07 | 0.13 | 73 | 2.1 | 24.9 | (Ni, Cu)3Sn4 |
22 | 260 | 0.4 | 0.5 | 0.42 | 0.26 | 73.74 | 3.48 | 22.8 | (Ni, Cu)3Sn4 |
23 | 260 | 0.7 | 0.6 | 0.47 | 0.28 | 73.98 | 3.77 | 22.3 | (Ni, Cu)3Sn4 |
63.06 | 22.2 | 14.7 | (Cu, Ni)6Sn5 | ||||||
24 | 260 | 1 | 0.2 | 0.85 | 0.16 | 62.92 | 25.6 | 11.5 | (Cu, Ni)6Sn5 |
25 | 260 | 1.1 | 0.4 | 0.47 | 0.3 | 74.01 | 3.79 | 22.2 | (Ni, Cu)3Sn4 |
26 | 270 | 1.2 | 0.2 | 1.07 | 0.14 | 61.93 | 25.68 | 12.4 | (Cu, Ni)6Sn5 |
27 | 270 | 1 | 0.3 | 0.96 | 0.19 | 62.74 | 22.26 | 15.0 | (Cu, Ni)6Sn5 |
28 | 270 | 0.4 | 0.5 | 0.4 | 0.3 | 73.05 | 2.3 | 24.7 | (Ni, Cu)3Sn4 |
29 | 270 | 0.7 | 0.6 | 0.5 | 0.31 | 74.14 | 3.36 | 22.5 | (Ni, Cu)3Sn4 |
62.79 | 22.08 | 15.3 | (Cu, Ni)6Sn5 | ||||||
30* | 270 | 0.55 | 0.15 | 0.53 | 0.14 | n/a | n/a | n/a | n/a |