CN100352597C - Cadmium-free silver solder comprising Ga, Im and Ce - Google Patents
Cadmium-free silver solder comprising Ga, Im and Ce Download PDFInfo
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- CN100352597C CN100352597C CNB200510122730XA CN200510122730A CN100352597C CN 100352597 C CN100352597 C CN 100352597C CN B200510122730X A CNB200510122730X A CN B200510122730XA CN 200510122730 A CN200510122730 A CN 200510122730A CN 100352597 C CN100352597 C CN 100352597C
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Abstract
The present invention relates to a cadmium-free silver solder containing gallium, indium and cerium, which belongs to soldering material. The present invention has the components by weight of 26.0 to 32.0% of copper (Cu), 24.0-32.0% of zinc (Zn), 2.0-6.0% of stannum (Sn), 2.0-5.0% of gallium (Ga), 0.2-2.0% of indium (In), 0.002-0.10% of cerium (Ce) and residual argentum (Ag). The present invention has the advantages that the constituents do not contain the toxic cadmium element to guarantee operators' safety and avoid the environmental impact, silver solder of BAg45CuZnCd and BAg40CuZnCdNi can be completely replaced and has good wettability and spreadability to base material and good soldering seam mechanical properties (sigma b, tau), appropriate amounts of Sn, Ga and In are taken to effectively reduce the melting point of the main constituent alloy (Ag-Cu-Zn alloy), and the Ce of the rare-earth element is added to refine crystal grains of the solder and improve the plasticity and the comprehensive mechanical properties of the solder.
Description
Technical field
The present invention relates to a kind of cadmium-free silver brazing alloy that contains gallium, indium and cerium, particularly a kind of cadmium-free silver brazing alloy that is applicable to metal material solderings such as red copper, brass, carbon steel, stainless steel and nickel-base alloy belongs to welding material.
Background technology
The silver solder that uses is mainly BAg45CuZnCd and BAg40CuZnCdNi at present, wherein: contain the cadmium (Cd) of 23.0%-25.0% in the chemical composition of BAg45CuZnCd, contain the cadmium (Cd) of 25.1%-26.5% in the chemical composition of BAg40CuZnCdNi.Because the promulgation of European Union " WEEE " and " ROHS " two instructions, and will be in enforcement on July 1 in 2006.Therefore, the material that contains cadmium will not allow to use in many household electrical appliances are produced, and it is Gospel that this health safety for the protection operator be can yet be regarded as to the pollution of environment with elimination, but for the production firm of welding material, challenge beyond doubt.Given this, as the production firm of welding material, for up time is fitted the necessary notes power of gesture in the research and development of cadmium-free silver brazing alloy.Undoubtedly, to have good brazing property, suitable solid-liquid phase line temperature and to have that to substitute the aforesaid cadmium brazing silver alloy that contains with the cadmium-free silver brazing alloy that traditional contains the suitable combination property of cadmium brazing silver alloy (BAg45CuZnCd and BAg40CuZnCdNi), be suitable for metal material solderings such as red copper, brass, carbon steel, stainless steel and nickel-base alloy be the direction that industry is pursued.
Summary of the invention
Task of the present invention is will provide a kind of can not have the good cadmium-free silver brazing alloy that contains gallium, indium and cerium of poisonous element cadmium, brazing property and comprehensive mechanical property fully in the welding position in brazing process and after the soldering.
Task of the present invention is finished like this, a kind of cadmium-free silver brazing alloy that contains gallium, indium and cerium, it consists of by weight percentage 26.0～32.0% bronze medals, 24.0～32.0% zinc, 2.0～6.0% tin, 2.0～5.0% galliums, 0.2～2.0% indium, 0.002～0.10% cerium, Yu Weiyin.
The advantage that the present invention has: 1) no longer contain poisonous cadmium element in the composition, can guarantee operator's safety and the influence of avoiding environment; 2) silver solder of complete alternative BAg45CuZnCd and BAg40CuZnCdNi is to mother metal wetability, good, the brazed seam mechanical property (σ of spreadability
b, τ) good; 3) amount of getting of tin (Sn), gallium (Ga), indium (In) is suitable, can reduce the fusing point of principal component alloy (Ag-Cu-Zn alloy) effectively, and wetability on red copper, brass, carbon steel, stainless steel and nickel-base alloy is improved, added rare-earth element cerium (Ce) simultaneously, the crystal grain of fined solder, the plasticity and the comprehensive mechanical property of raising solder.
The specific embodiment
1), use commercially available silver, cathode copper, zinc ingot metal, tin slab, gallium, indium metal, metallic cerium, by said ratio, adopt that conventional intermediate frequency smelting furnace is smelted, casting, by extruding, drawing, promptly obtain needed solder wire material then; 2), according to producing needs, tin slab, gallium, indium metal, metallic cerium can be smelted into alloy respectively in advance, add then in silver-copper-zinc alloy smelt, casting, by extruding, drawing, promptly obtain needed solder wire material again.The solidus temperature of resulting solder wire material at 640 ℃～650 ℃ scopes, liquidus temperature 685 ℃～710 ℃ scopes; Cooperate FB102 (QJ102) brazing flux, brazing material is following combination: red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, σ
b=180～380MPa scope, τ=160～300MPa scope.
Adopt conventional intermediate frequency smelting furnace to smelt, cast, by extruding, drawing, promptly obtain needed solder wire material then; The cadmium-free silver brazing alloy that contains gallium and cerium of the present invention is an object of reference with BAg45CuZnCd and BAg40CuZnCdNi, cooperate FB102 silver brazing flux (QJ102 silver brazing flux), during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～380MPa scope, τ=160～300MPa scope).The cadmium-free silver brazing alloy that contains gallium, indium and cerium of the present invention does not have the harmful element cadmium fully, has protected operator's health safety effectively, has eliminated the pollution to environment.Therefore the brazed seam mechanical performance index of solder and BAg45CuZnCd and BAg40CuZnCdNi solder are suitable, and solder of the present invention can be used as the substitute of BAg45CuZnCd and BAg40CuZnCdNi solder fully and is applied to the production industry of refrigeration part and so on.
Embodiment 1:
Percentage proportioning by weight, its composition is: 30.0% bronze medal (Cu), 27.0% zinc (Zn), 4.0% tin (Sn), 3.0% gallium (Ga), 1.2% indium (In), 0.02% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 645 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=200 ± 15MPa, τ=180 ± 10MPa), stainless steel-nickel-base alloy (σ
b=350 ± 15MPa, τ=260 ± 10MPa).
Embodiment 2:
Percentage proportioning by weight, its composition is: 26.0% bronze medal (Cu), 29.0% zinc (Zn), 6.0% tin (Sn), 5.0% gallium (Ga), 1.8% indium (In), 0.10% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=320 ± 15MPa, τ=260 ± 10MPa).
Embodiment 3:
Percentage proportioning by weight, its composition is: 26.0% bronze medal (Cu), 29.0% zinc (Zn), 6.0% tin (Sn), 5.0% gallium (Ga), 1.8% indium (In), 0.002% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=320 ± 15MPa, τ=260 ± 10MPa).
Embodiment 4:
Percentage proportioning by weight, its composition is: 30.0% bronze medal (Cu), 27.0% zinc (Zn), 2.0% tin (Sn), 5.0% gallium (Ga), 2.0% indium (In), 0.005% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=300 ± 15MPa, τ=230 ± 10MPa).
Embodiment 5:
Percentage proportioning by weight, its composition is: 30.0% bronze medal (Cu), 27.0% zinc (Zn), 3.0% tin (Sn), 5.0% gallium (Ga), 0.2% indium (In), 0.02% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains gallium, indium and cerium " solidus temperature that the mentioned component proportioning obtains about 645 ℃, liquidus temperature (considered experimental error) about 690 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=305 ± 15MPa, τ=230 ± 10MPa).
Embodiment 6:
Percentage proportioning by weight, its composition is: 30.0% bronze medal (Cu), 27.0% zinc (Zn), 4.0% tin (Sn), 3.0% gallium (Ga), 1.0% indium (In), 0.025% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 645 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=310 ± 15MPa, τ=230 ± 10MPa).
Embodiment 7:
Percentage proportioning by weight, its composition is: 32.0% bronze medal (Cu), 24.0% zinc (Zn), 5.5% tin (Sn), 3.5% gallium (Ga), 0.5% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 690 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=350 ± 15MPa, τ=260 ± 10MPa).
Embodiment 8:
Percentage proportioning by weight, its composition is: 26.0% bronze medal (Cu), 29.0% zinc (Zn), 5.5% tin (Sn), 4.5% gallium (Ga), 1.5% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=365 ± 15MPa, τ=260 ± 10MPa).
Embodiment 9:
Percentage proportioning by weight, its composition is: 27.0% bronze medal (Cu), 28.0% zinc (Zn), 3.5% tin (Sn), 4.5% gallium (Ga), 1.5% indium (In), 0.025% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=335 ± 15MPa, τ=240 ± 10MPa).
Embodiment 10:
Percentage proportioning by weight, its composition is: 31.0% bronze medal (Cu), 28.0% zinc (Zn), 4.5% tin (Sn), 5.0% gallium (Ga), 1.5% indium (In), 0.065% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=345 ± 15MPa, τ=240 ± 10MPa).
Embodiment 11:
Percentage proportioning by weight, its composition is: 28.0% bronze medal (Cu), 28.0% zinc (Zn), 5.5% tin (Sn), 5.0% gallium (Ga), 1.8% indium (In), 0.065% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=365 ± 15MPa, τ=290 ± 10MPa).
Embodiment 12:
Percentage proportioning by weight, its composition is: 26.0% bronze medal (Cu), 29.0% zinc (Zn), 5.5% tin (Sn), 2.0% gallium (Ga), 1.8% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 650 ℃, liquidus temperature (considered experimental error) about 695 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=335 ± 15MPa, τ=230 ± 10MPa).
Embodiment 13:
Percentage proportioning by weight, its composition is: 26.0% bronze medal (Cu), 29.0% zinc (Zn), 2.5% tin (Sn), 2.4% gallium (Ga), 1.0% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains gallium, indium and cerium " solidus temperature that the mentioned component proportioning obtains about 650 ℃, liquidus temperature (considered experimental error) about 700 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=305 ± 15MPa, τ=240 ± 10MPa).
Embodiment 14:
Percentage proportioning by weight, its composition is: 28.0% bronze medal (Cu), 28.0% zinc (Zn), 2.5% tin (Sn), 3.2% gallium (Ga), 0.4% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 650 ℃, liquidus temperature (considered experimental error) about 700 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=355 ± 15MPa, τ=260 ± 10MPa).
Embodiment 15:
Percentage proportioning by weight, its composition is: 28.0% bronze medal (Cu), 29.0% zinc (Zn), 5.5% tin (Sn), 4.2% gallium (Ga), 0.2% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=325 ± 15MPa, τ=260 ± 10MPa).
Embodiment 16:
Percentage proportioning by weight, its composition is: 26.0% bronze medal (Cu), 29.0% zinc (Zn), 5.5% tin (Sn), 4.2% gallium (Ga), 0.2% indium (In), 0.080% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=345 ± 15MPa, τ=260 ± 10MPa).
Embodiment 17:
Percentage proportioning by weight, its composition is: 28.0% bronze medal (Cu), 29.0% zinc (Zn), 3.5% tin (Sn), 4.2% gallium (Ga), 0.2% indium (In), 0.065% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=335 ± 15MPa, τ=240 ± 10MPa).
Embodiment 18:
Percentage proportioning by weight, its composition is: 32.0% bronze medal (Cu), 28.0% zinc (Zn), 3.0% tin (Sn), 2.0% gallium (Ga), 1.0% indium (In), 0.065% cerium (Ce), all the other are silver (Ag).
The cadmium-free silver brazing alloy solidus temperature that contains gallium, indium and cerium that the mentioned component proportioning obtains about 640 ℃, liquidus temperature (considered experimental error) about 685 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=180 ± 15MPa, τ=160 ± 10MPa), brass-carbon steel (σ
b=260 ± 15MPa, τ=200 ± 10MPa), stainless steel-nickel-base alloy (σ
b=335 ± 15MPa, τ=240 ± 10MPa).
Obvious, by the gallium that contains provided by the invention, the cadmium-free silver brazing alloy of indium and cerium is except having security, outside the feature of environmental protection, to soldering mother metal red copper, brass, carbon steel, stainless steel, nickel-base alloy all has good wettability respectively, so any gallium that contains in the foregoing description 1 to embodiment 18, the cadmium-free silver brazing alloy of indium and cerium, in soldering red copper-red copper, red copper-brass, brass-carbon steel, brass-stainless steel, carbon steel-stainless steel, carbon steel-nickel-base alloy, stainless steel-nickel-base alloy, red copper-nickel-base alloy, during different combined material (mother metal) such as brass-nickel-base alloy, combined material (mother metal) to institute's soldering all has good wetability, and soldered fitting has good comprehensive mechanical properties.
Claims (1)
1, a kind of cadmium-free silver brazing alloy that contains gallium, indium and cerium, it is characterized in that it consists of by weight percentage 26.0～32.0% bronze medals, 24.0～32.0% zinc, 2.0～6.0% tin, 2.0～5.0% galliums, 0.2～2.0% indium, 0.002～0.10% cerium, Yu Weiyin.
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| CNB200510122730XA CN100352597C (en) | 2005-11-25 | 2005-11-25 | Cadmium-free silver solder comprising Ga, Im and Ce |
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| CNB200510122730XA CN100352597C (en) | 2005-11-25 | 2005-11-25 | Cadmium-free silver solder comprising Ga, Im and Ce |
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| CN100352597C true CN100352597C (en) | 2007-12-05 |
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| EP2756914A1 (en) * | 2013-01-18 | 2014-07-23 | Umicore AG & Co. KG | Solder alloy |
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| JPH1029087A (en) * | 1996-07-12 | 1998-02-03 | Tanaka Kikinzoku Kogyo Kk | Low melting brazing filler metal for platinum ornaments |
| CN1404957A (en) * | 2001-09-18 | 2003-03-26 | 北京航空材料研究院 | Cadmium-free silver-base solder |
| GB2409209A (en) * | 2003-12-12 | 2005-06-22 | Smith International | A braze alloy, down hole cutting tool and a method of manufacture of said tool |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2756914A1 (en) * | 2013-01-18 | 2014-07-23 | Umicore AG & Co. KG | Solder alloy |
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|---|---|
| CN1775459A (en) | 2006-05-24 |
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