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Of the 90 naturally occurring elements, only 13 can be practically combined with each other to form a practical solder (see Fig. 45.1).
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FIGURE 45.1 Highlighted elements can be combined to form solders useful for circuit board assembly.
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Of those elements that can combine to form solders, several have limitations that restrict their practical implementation for solder use (see Table 45.2). Gallium, gold, indium, platinum, and palladium cannot be mined or refined in sufficient quantity to satisfy the needs of the electronics industry and are prohibitively expensive, blocking their consideration as a major constituent of a worldwide solder supply. The Bismuth (Bi) supply, a by-product of lead refining, would be marginally sufficient. Mercury and antimony are too toxic. Both mercury and Pb are already on the EU s RoHS list of restricted materials. Gallium and mercury possess too low a melting point to be used on their own. This leaves five metals for practical solder alloy consideration: bismuth (Bi), copper (Cu), silver (Ag), tin (Sn), and zinc (Zn). Due to
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TABLE 45.2 Elemental Candidates for Solders Element Antimony Bismuth Copper Gallium Gold Indium Lead Mercury Palladium Platinum Silver Tin Zinc Symbol Sb Bi Cu Ga Au In Pb Hg Pd Pt Ag Sn Zn Melting point ( C) 630.5 217.5 1084.5 29.75 1063 156.3 327.5 38.83 1550 1768.3 960.15 231.89 419.6 Comments Toxic, used as a minor constituent of some solders Already in use Already in use Too expensive Too expensive Too expensive Banned for use in EU Toxic, restricted for use in EU Too expensive Too expensive Expensive but already used in solders in small quantities Already in use Already in use
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its value, silver, too, can be used only in small proportions for solder and is already in wide use that way today. Given the four remaining metals (Bi, Cu, Sn, and Zn), there are many possible metallurgical permutations available for solder alloying, but there are few that either possess low enough liquidus to be useful for circuit board assembly or have attractive physical properties as a solder. Although Pb-free solders have been in use for many years (jewelry making, plumbing, brazing, etc.), few have been studied sufficiently for electronics assembly, most have too high a melting point to be useful, and none come with the well-documented properties database as is the case for Sn-Pb solder.
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Candidate Pb-Free Solders Although many manufacturers completed the conversion to Pb-free soldering in time for the July 1, 2006, implementation of the RoHS directive in Europe, there was still no consensus across the industry for a single tin-lead solder replacement at the time. Pb-free alloy systems receiving the most attention include those listed in the Table 45.3.
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TABLE 45.3 List of Lead-Free Solders and Their Temperature Ranges Most common compositionsa (wt %) Sn-0.07Cu Sn-3.5Ag Sn-5.0Ag Sn-3.0Ag-0.05Cu Sn-3.5Ag-0.9Cu Sn-3.5Ag-0.7Cu Sn-3.8Ag-0.7Cu Sn-3.9Ag-0.6Cu Sn-4.0Ag-0.5Cu Sn-1.0Ag-57Bi Sn-3.4Ag-4.8Bi Sn-3.5Ag-5.0Bi Sn-3.5Ag-1.0Bi Sn-2.0Ag-7.5Bi Sn-2.5Ag-1.0Bi-0.5Cu Sn-2.0Ag-3.0Bi-0.75Cu Sn-58Bi Sn-8.0Sn-3.0Bi Sn-9.0Zn Solidus temperatureb ( C) 2273 2213 221 217 217c 217 217 217 217 137 200 208 219 191 214 207 138c 191 199c Liquidusb temperature ( C) 227c 221c 240 221 217c 220 220 223 225 139 216 215 220 216 221 218 138c 198 199c
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Alloy families Sn-Cu Sn-Ag Sn-Ag-Cu
Sn-Ag-Bi
Sn-Ag-Bi-Cu Sn-Bi Sn-Zn-Bi Sn-Zn
Notes: a There are too many non-eutectic formulations composed of the same elements in varying ratios to list comprehensively here. Each variation in composition will have its own melting range. The ones listed in this table are examples only to show approximate temperature range and composition. b There are discrepancies in the literature as to the exact melting point or melting range of alloys listed, but the table will be useful for approximating phase-change characteristics of the alloys listed. c Eutectic alloys have a distinct melting point; solidus and liquidus temperatures are the same. Non-eutectic alloy melting is characterized by a melting range where the alloy is present as both solid phase(s) and liquid phase simultaneously (pasty range). At the upper temperature of the melting range, only the liquid phases exist.
45.5.1.1 Characteristics of Pb-Free Solders. Pb-free solders generally exhibit poorer wetting and spreading characteristics than Sn-Pb alloys, but may offer an advantage in tensile strength and creep resistance. In terms of the soldering process, a whole new understanding of the various Pb-free alloys is required. Propensity for solder void formation, solder paste shelf-life, solder
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