CN106624427B - Low-cadmium silver solder with low melting point and excellent wettability - Google Patents
Low-cadmium silver solder with low melting point and excellent wettability Download PDFInfo
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- CN106624427B CN106624427B CN201611158520.0A CN201611158520A CN106624427B CN 106624427 B CN106624427 B CN 106624427B CN 201611158520 A CN201611158520 A CN 201611158520A CN 106624427 B CN106624427 B CN 106624427B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
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Abstract
The invention belongs to the technical field of brazing materials of metal materials, and particularly relates to a low-cadmium silver brazing filler metal with low melting point and excellent wettability. The invention aims to provide a low-cadmium silver solder which has low Cd content, a solder liquidus temperature close to BAg25CuZnCd solder, good wetting and spreading properties, a low melting point and excellent wetting property, and a soldered joint mechanical property. The invention is realized by the following technical scheme: a low-cadmium silver solder with low melting point and excellent wettability comprises the following components in percentage by mass: 24.0 to 26.0 wt.% Ag, 30.0 to 41.0 wt.% Cu, 0.05 to 0.13 wt.% Cd, 0.001 to 0.005 wt.% In, 0.001 to 0.005 wt.% Ga, 0.001 to 0.005 wt.% Sn, and the balance Zn.
Description
Technical Field
The invention belongs to the technical field of brazing materials of metal materials, and particularly relates to a low-cadmium silver brazing filler metal with low melting point and excellent wettability.
background
the BAg25CuZnCd solder recommended in the prior art (GB/T10046-2008 silver solder) has the melting temperature range of 607 ℃ of solidus and 682 ℃ of liquidus, and the lower melting temperature range of the solder enables the operation to be convenient and the process to be simple and convenient during the brazing production, and is one of the solders popular with solder users. However, due to the RoHS directive and the restriction on the use of Cd elements by Chinese 'part 39 directive' (American Standard AWS A5.8/A5.8M: 2004 Table 1 requires that the Cd content be less than 0.15%), the use of BAg25CuZnCd solders has been affected. As a substitute of BAg25CuZnCd solder, the BAg25CuZn solder has the melting temperature range of 700 ℃ at the solidus and 790 ℃ at the liquidus as the main elements of Ag, Cu and Zn and the Ag content of 24.0-26.0 percent in the chemical components; the BAg25CuZnSn solder, although added with 1.5-2.5% of Sn element, has a melting temperature range reduced to 680 ℃ of the solidus and 760 ℃ of the liquidus, which is still greatly higher than the melting temperature range of 607 ℃ of the solidus and 682 ℃ of the BAg25CuZnCd solder. How to reduce the melting temperature range of the silver solder and enable the silver solder to have excellent wetting and spreading performance and brazing seam mechanical property, and meet the requirements of industrial 4.0 times of brazing connectors on high performance, high efficiency and low cost is a very difficult subject.
The published Chinese patent documents refer to technical information of various novel silver solders, such as "gallium and cerium-containing cadmium-free silver solder" disclosed in CN200510095769.7, wherein the solidus temperature is 605-615 ℃, and the liquidus temperature is 635-645 ℃; CN200510122730.X discloses "cadmium-free silver solder containing gallium, indium and cerium", which has solidus temperature of 640-650 deg.C and liquidus temperature of 685-710 deg.C; CN200610097767.6 discloses a cadmium-free silver-based solder containing gallium, indium and cerium, which has a solidus temperature of 650-665 ℃ and a liquidus temperature of 730-745 ℃. In addition, the common feature of the existing cadmium-free silver solder capable of reducing the melting temperature is that at least more than 1% of one or more low-melting point elements such as Sn, Ga, In and the like are added. Because Ga and In belong to rare elements, the annual output all over the world is also very limited, and the price is equivalent to or higher than that of silver, so the Ga-In-Ag alloy has no value of large-scale application; the Sn element is not high in price and abundant in reserves, but the silver solder is difficult to process due to the fact that a large amount of Sn is added, a hard and brittle intermetallic compound Cu6Sn5 is easily formed, the addition amount of Sn in the BAg60CuSn solder can reach 9.5-10.5%, the addition amount of Sn in Ag-Cu-Zn-Sn series solders is generally 1.5-2.5%, and the addition amount of Sn in BAg56CuZnSn is 4.5-5.5% respectively (see GB/T10046-2008 silver solder Table 2).
Until now, all silver solders with Ag, Cu and Zn elements (containing no phosphorus element and classified as the silver solder of GB/T10046-2008) as main components and Ga, In and Sn elements with the content lower than 0.15 percent have no report of cadmium-free silver solders with the liquidus temperature of less than or equal to 705 ℃ and the liquidus temperature of 682 ℃ close to that of BAg25CuZnCd solders.
Disclosure of Invention
The invention aims to provide a low-cadmium silver solder which has the advantages that the content of Cd is lower than 0.15%, the liquidus temperature of the solder is close to that of BAg25CuZnCd, the solder has good wetting and spreading properties, the mechanical properties of soldered joints are good, the melting point is low, and the wetting property is excellent.
The task of the invention is realized by the following technical scheme: a low-cadmium silver solder with low melting point and excellent wettability comprises the following components in percentage by mass: 24.0 to 26.0 wt.% Ag, 30.0 to 41.0 wt.% Cu, 0.05 to 0.13 wt.% Cd, 0.001 to 0.005 wt.% In, 0.001 to 0.005 wt.% Ga, 0.001 to 0.005 wt.% Sn, and the balance Zn.
In the low-cadmium silver solder with low melting point and excellent wettability, the component Ag of the solder is a silver plate (IC-Ag99.99) with the purity of 99.99 percent.
In the low-cadmium silver solder with low melting point and excellent wettability, the component Cu of the solder is electrolytic copper (one or more of Cu-cath-1, Cu-cath-2 and Cu-cath-3).
In the low-cadmium silver solder with low melting point and excellent wettability, the component Cd of the solder is cadmium ingot.
In the low-cadmium silver solder with low melting point and excellent wettability, the component In of the solder is metallic indium.
In the low-cadmium silver solder with low melting point and excellent wettability, the component Ga of the solder is metal gallium.
In the low-cadmium silver solder with low melting point and excellent wettability, the component Sn of the solder is metallic tin.
in the low-cadmium silver solder with low melting point and excellent wettability, the component Zn of the solder is a zinc ingot.
In the low-cadmium silver solder with low melting point and excellent wettability, the method for preparing the low-cadmium silver solder comprises the following steps: the low-cadmium silver solder wire is prepared by adding the components of the low-cadmium silver solder into a crucible of a medium-frequency smelting furnace according to the mass percentage, and smelting, casting, extruding and drawing by adopting a medium-frequency smelting process.
the solidus temperature of the brazing filler metal is within the range of 630-640 ℃, the liquidus temperature is within the range of 695-705 ℃, is greatly lower than the solidus temperature of BAg25CuZn (the solidus temperature is 700 ℃, and the liquidus temperature is 790 ℃), the solidus temperature of BAg25CuZnSn (the solidus temperature is 680 ℃, and the liquidus temperature is 760 ℃) and is very close to the solidus temperature and the liquidus temperature (the solidus temperature is 607 ℃, and the liquidus temperature is 682 ℃) of BAg25CuZnCd, and the brazing filler metal meets the brazing process requirements of products such as a plurality of non-electronic and electric equipment without restriction of RoHS instructions.
The invention mainly solves the following two key technical problems:
1. The low-cadmium silver solder contains Cd element limited by RoHS instruction. However, the content of Cd element is less than or equal to 0.13 percent and meets the American standard AWS A5.8/A5.8M: 2004 rules for silver-containing solder, the low cadmium silver solder of the invention has the characteristics of lower melting point, excellent wetting and spreading performance and excellent mechanical property of soldering seams.
2. By adding a proper proportion of Ga, In and Sn elements into the low-cadmium silver solder, the low-cadmium silver solder has excellent wetting spreading performance on red copper, brass (such as H62 brass), Q235 steel and 304 stainless steel, has a spreading area and soldering seam joint shearing strength which are larger than those of BAg25CuZn solder and BAg25CuZnSn solder and are equivalent to those of BAg25CuZnCd solder.
Compared with the prior art, the invention provides the technical scheme with creativity that:
1. Researches find that the wetting and spreading performance of the solder is obviously improved and the melting temperature is also obviously reduced by adding 0.05 wt.% of trace Cd element into the BAg25CuZn solder. With the increase of Cd content, the wetting spreading area of the solder is increased, and the melting temperature of the solder is reduced by an increasing range. The phase diagram of the binary alloy of Cu-Cd and Zn-Cd is theoretically analyzed, and the phase diagram is known to be caused by that Cu and Cd can form a low-melting eutectic with the melting point of 549 ℃ and Zn and Cd can form the melting point of 266 ℃.
Based on the American Standard AWS A5.8/A5.8M: 2004 that the total amount of other elements is less than or equal to 0.15%, the adding amount of Cd element is controlled to be 0.013%.
2. Researches find out the rule of the influence of the 'synergistic effect' of trace Ga, In and Sn elements added and Cd elements on the wetting and spreading performance and the brazing seam mechanical property of the low-cadmium silver brazing filler metal. By optimizing the addition ranges of Ga, In and Sn elements and controlling the addition amounts of Ga, In and Sn within the range of 0.001-0.005%, the spreading area and the shearing strength of a brazing seam joint of the low-cadmium silver brazing filler metal disclosed by the invention are larger than those of a BAg25CuZn brazing filler metal and a BAg25CuZnSn brazing filler metal, and are equivalent to those of the BAg25CuZnCd brazing filler metal. The phase diagram of the binary alloy of Cd-In and Cd-Ga is theoretically analyzed, and the phase diagram is known to be caused by that Cd and In can form a low-melting eutectic with the melting point of 127.7 ℃ and Cd and Ga can form the melting point of 282 ℃. Besides forming a low-melting-point eutectic compound at 177 ℃, the Sn element and the Cd can form a low-melting-point eutectic compound at 221 ℃ with Ag and a low-melting-point eutectic compound at 227 ℃ with Cu. The 'cumulative effect' of the formation of the eutectic compounds with various and small amounts of low melting points ensures that the brazing filler metal has a melting temperature range very close to that of the BAg25CuZnCd brazing filler metal, and brings great convenience to the brazing production.
In addition, the 'synergistic effect' and 'cumulative effect' of trace amounts of Ga, In and Sn elements and Cd elements are not enough to have fundamental influence on the melting point of the solder of the invention (In the invention, the influence of Cd on the melting point of the solder of the invention is a main factor), but have also generated significant influence. In addition, the alloy strengthening effect of Ga, In and Sn elements also obviously increases the spreading area of the low-cadmium silver solder and improves the shearing strength of the brazing seam joint.
In conclusion, compared with the existing BAg25CuZn, BAg25CuZnSn and BAg25CuZnCd solders, the low-cadmium silver solder disclosed by the invention not only has the characteristics of good wetting spreadability, excellent brazing seam mechanical property and the like, but also has a lower melting temperature range than the BAg25CuZn and BAg25CuZnSn solders, so that the solder is easier to operate during brazing, the technical difficulty of a brazing operator is reduced, the low-cadmium silver solder is particularly suitable for brazing of other industrial products except for the industries of electronic and electrical equipment and the like limited by RoHS instructions, and the problems of workpiece oxidation and even softening, brazed joint strength reduction and the like caused by overhigh brazing temperature are avoided.
Detailed Description
The following examples are provided to further illustrate the low cadmium silver solder of the present invention with low melting point and excellent wetting property.
Example 1
A low-cadmium silver solder with low melting point and excellent wettability comprises the following components in percentage by mass: 24.0 wt.% Ag, 41.0 wt.% Cu, 0.05 wt.% Cd, 0.001 wt.% In, 0.005 wt.% Ga, 0.001 wt.% Sn, and the balance Zn.
The solidus temperature of the novel low-melting-point low-cadmium silver solder prepared by the components is within the range of 630-640 ℃, and the liquidus temperature is within the range of 695-705 ℃. By using a flame brazing mode and matching FB102 brazing flux, the brazing seam strength of the brazing base metal is shown in data in brackets when the brazing base metal is combined as follows: red copper-H62 brass (sigma)b225 ± 25MPa, τ 215 ± 30MPa) brass-Q235 steel (σ)b280 ± 25MPa, τ 300 ± 30MPa), brass-304 stainless steel (σ ═ 30MPa)b＝±25MPa，τ＝280±30MPa)。
Example 2:
A low-cadmium silver solder with low melting point and excellent wettability comprises the following components in percentage by mass: 26.0 wt.% Ag, 30.0 wt.% Cu, 0.13 wt.% Cd, 0.001 wt.% In, 0.001 wt.% Ga, 0.005 wt.% Sn, and the balance Zn.
The solidus temperature of the novel low-melting-point low-cadmium silver solder prepared by the components is within the range of 630-640 ℃, and the liquidus temperature is within the range of 695-705 ℃. By using a flame brazing mode and matching FB102 brazing flux, the brazing seam strength of the brazing base metal is shown in data in brackets when the brazing base metal is combined as follows: red copper-H62 brass (sigma)b225 ± 25MPa, τ 215 ± 30MPa) brass-Q235 steel (σ)b280 ± 25MPa, τ 300 ± 30MPa), brass-304 stainless steel (σ ═ 30MPa)b＝260±25MPa，τ＝280±30MPa)。
Example 3:
A low-cadmium silver solder with low melting point and excellent wettability comprises the following components in percentage by mass: 25.0 wt.% Ag, 36.0 wt.% Cu, 0.10 wt.% Cd, 0.005 wt.% In, 0.005 wt.% Ga, 0.002 wt.% Sn, and the balance Zn.
The solidus temperature of the novel low-melting-point low-cadmium silver solder prepared by the components is within the range of 630-640 ℃, and the liquidus temperature is within the range of 695-705 ℃. By using a flame brazing mode and matching FB102 brazing flux, the brazing seam strength of the brazing base metal is shown in data in brackets when the brazing base metal is combined as follows: red copper-H62 brass (sigma)b＝22525MPa, 215 ± 30MPa) brass-Q235 steel (σ)b280 ± 25MPa, τ 300 ± 30MPa), brass-304 stainless steel (σ ═ 30MPa)b＝260±25MPa，τ＝280±30MPa)。
Example 4:
A low-cadmium silver solder with low melting point and excellent wettability comprises the following components in percentage by mass: 25.2 wt.% Ag, 40.3 wt.% Cu, 0.12 wt.% Cd, 0.002 wt.% In, 0.005 wt.% Ga, 0.002 wt.% Sn, and the balance Zn.
The solidus temperature of the novel low-melting-point low-cadmium silver solder prepared by the components is within the range of 630-640 ℃, and the liquidus temperature is within the range of 695-705 ℃. By using a flame brazing mode and matching FB102 brazing flux, the brazing seam strength of the brazing base metal is shown in data in brackets when the brazing base metal is combined as follows: red copper-H62 brass (sigma)b225 ± 25MPa, τ 215 ± 30MPa) brass-Q235 steel (σ)b280 ± 25MPa, τ 300 ± 30MPa), brass-304 stainless steel (σ ═ 30MPa)b＝260±25MPa，τ＝280±30MPa)。
Example 5:
A low-cadmium silver solder with low melting point and excellent wettability comprises the following components in percentage by mass: 24.3 wt.% Ag, 39.6 wt.% Cu, 0.11 wt.% Cd, 0.004 wt.% In, 0.002 wt.% Ga, 0.004 wt.% Sn, and the balance Zn.
the solidus temperature of the novel low-melting-point low-cadmium silver solder prepared by the components is within the range of 630-640 ℃, and the liquidus temperature is within the range of 695-705 ℃. By using a flame brazing mode and matching FB102 brazing flux, the brazing seam strength of the brazing base metal is shown in data in brackets when the brazing base metal is combined as follows: red copper-H62 brass (sigma)b225 ± 25MPa, τ 215 ± 30MPa) brass-Q235 steel (σ)b280 ± 25MPa, τ 300 ± 30MPa), brass-304 stainless steel (σ ═ 30MPa)b＝260±25MPa，τ＝280±30MPa)。
Examples of the solder of the invention and the comparison of the properties with BAg25CuZn, BAg25CuZnSn, BAg25CuZnCd solders are presented in Table 1.
Table 1: examples of the solder of the invention and comparison of the Performance with BAg25CuZn, BAg25CuZnSn, BAg25CuZnCd solders
Claims (9)
1. The low-cadmium silver solder with low melting point and excellent wettability is characterized by comprising the following components in percentage by mass: 24.0 to 26.0 wt.% Ag, 30.0 to 41.0 wt.% Cu, 0.05 to 0.13 wt.% Cd, 0.001 to 0.005 wt.% In, 0.001 to 0.005 wt.% Ga, 0.001 to 0.005 wt.% Sn, and the balance Zn.
2. The low cadmium silver solder with low melting point and excellent wettability as claimed in claim 1, wherein the component Ag of said solder is silver plate with purity of 99.99%.
3. A low cadmium silver solder with low melting point and excellent wetting property according to claim 1 or 2, characterized in that the component Cu of the solder is electrolytic copper.
4. A low cadmium silver solder with low melting point and excellent wettability as claimed in claim 1 or 2, characterized in that the component Cd of said solder is cadmium ingot.
5. A low cadmium silver solder with low melting point and excellent wetting property according to claim 1 or 2, characterized In that the component In of the solder is metallic indium.
6. A low cadmium silver solder with low melting point and excellent wetting property according to claim 1 or 2, characterized in that the component Ga of the solder is metallic gallium.
7. A low cadmium silver solder with low melting point and excellent wetting property according to claim 1 or 2, characterized in that the component Sn of the solder is metallic tin.
8. A low cadmium silver solder with low melting point and excellent wetting property according to claim 1 or 2, characterized in that the component Zn of the solder is zinc ingot.
9. the low cadmium silver solder with low melting point and excellent wettability as claimed in claim 1, wherein the low cadmium silver solder with low melting point and excellent wettability is prepared by: the low-cadmium silver solder wire is prepared by adding the components of the low-cadmium silver solder into a crucible of a medium-frequency smelting furnace according to the mass percentage, and smelting, casting, extruding and drawing by adopting a medium-frequency smelting process.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0634495A1 (en) * | 1993-07-12 | 1995-01-18 | Degussa Aktiengesellschaft | Use of a cadmium free silver alloy as a low metting point solder |
| CN1435294A (en) * | 2002-12-03 | 2003-08-13 | 金华市金钟焊接材料有限公司 | Rareearth-silver solder and producing method thereof |
| CN1962159A (en) * | 2006-11-26 | 2007-05-16 | 常熟市华银焊料有限公司 | Cadmium-free silver based solder containing gallium, indium and cerium |
| CN101049655A (en) * | 2007-05-14 | 2007-10-10 | 骆华明 | Silver solder of containing gallium, indium, and rare earth neodymium and cerium without cadmium |
| CN104785951A (en) * | 2015-03-16 | 2015-07-22 | 杭州华光焊接新材料股份有限公司 | Low-silver brazing material for dissimilar metal connecting |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103056551B (en) * | 2013-01-04 | 2015-04-29 | 西安交通大学 | Novel tin-and-indium-containing multi-component cadmium-and-silver-free brazing filler metal |
| CN104759786A (en) * | 2015-04-17 | 2015-07-08 | 郑州机械研究所 | Multi-core seamless flux-cored silver wire |
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2016
- 2016-12-15 CN CN201611158520.0A patent/CN106624427B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0634495A1 (en) * | 1993-07-12 | 1995-01-18 | Degussa Aktiengesellschaft | Use of a cadmium free silver alloy as a low metting point solder |
| CN1435294A (en) * | 2002-12-03 | 2003-08-13 | 金华市金钟焊接材料有限公司 | Rareearth-silver solder and producing method thereof |
| CN1962159A (en) * | 2006-11-26 | 2007-05-16 | 常熟市华银焊料有限公司 | Cadmium-free silver based solder containing gallium, indium and cerium |
| CN101049655A (en) * | 2007-05-14 | 2007-10-10 | 骆华明 | Silver solder of containing gallium, indium, and rare earth neodymium and cerium without cadmium |
| CN104785951A (en) * | 2015-03-16 | 2015-07-22 | 杭州华光焊接新材料股份有限公司 | Low-silver brazing material for dissimilar metal connecting |
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Denomination of invention: A low cadmium silver solder with low melting point and excellent wettability Effective date of registration: 20220615 Granted publication date: 20191213 Pledgee: Agricultural Bank of China Limited by Share Ltd. Jinhua Economic Development Zone Branch Pledgor: JINHUA JINZHONG WELDING MATERIALS CO.,LTD. Registration number: Y2022330000951 |
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