CN1836823A - Cadmium-free silver solder containing indium and cerium - Google Patents

Cadmium-free silver solder containing indium and cerium Download PDF

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Publication number
CN1836823A
CN1836823A CN 200610039659 CN200610039659A CN1836823A CN 1836823 A CN1836823 A CN 1836823A CN 200610039659 CN200610039659 CN 200610039659 CN 200610039659 A CN200610039659 A CN 200610039659A CN 1836823 A CN1836823 A CN 1836823A
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cerium
cadmium
brass
indium
25mpa
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CN100408255C (en
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薛松柏
顾文华
顾立勇
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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Abstract

The Ag-base no-Cd brazing alloy as one kind of welding material consists of: Cu 25.0-32.0 wt%, Zn 25.0-35.0 wt%, In 0.5-5.0 wt%, Sn 0.01-1.0 wt%, Ce 0.002-0.10 wt%, except Ag. The brazing alloy wire is produced through smelting in a conventional MF smelting furnace, casting, extrusion, and drawing. The Ag-base no-Cd brazing alloy has solid phase temperature line of 660-685 deg.c and liquid phase line temperature of 715-735 deg.c. Without harmful Cd, the Ag-base no-Cd brazing alloy is favorable to worker's health and environment. The Ag-base no-Cd brazing alloy has brazing mechanical performance similar to that of brazing alloy BAg45CuZnCd and BAg45CuZn.

Description

The cadmium-free silver brazing alloy that contains indium and cerium
One, technical field
The cadmium-free silver brazing alloy that contains indium and cerium of the present invention belongs to the brazing material of class of metal materials and field of metallurgy.
Two, background technology
Present silver solder BAg45CuZnCd, the BAg45CuZn that uses, silver content is about 45% solder in its chemical composition.Because silver belongs to precious metal material, price is comparatively expensive, and therefore, research and development have quite or similar performance, brazing material that silver content is lower again, have important economic value and realistic meaning.The cadmium-free silver brazing alloy that contains indium and cerium of this invention is promptly finished under this technical background.
Three, summary of the invention
The task of this invention provide a kind of can the welding position in brazing process and after the soldering do not have fully poisonous element cadmium, brazing property is good, to have with traditional silver content be 45% the suitable combination property of solder (BAg45CuZnCd, BAg45CuZn), silver content is lower than the brazing material of 45% (being about about 40%) again.
This invention has mainly solved following two key technical problems: 1) develop no cadmium, combination property and traditional silver content be 45% silver solder quite or similar, the silver solder of alternative BAg45CuZnCd, BAg45CuZn, by optimizing the chemical composition of " cadmium-free silver brazing alloy that contains indium and cerium ", obtained mother metal wetability, good, the brazed seam mechanical property (σ of spreadability b, τ) good cadmium-free silver brazing alloy; 2) in cadmium-free silver brazing alloy, add an amount of indium (In) and trace tin (Sn) to reduce the fusing point of principal component alloy (Ag-Cu-Zn alloy), improve the wetability of cadmium-free silver brazing alloy on red copper, brass, carbon steel, stainless steel and nickel-base alloy simultaneously, add the crystal grain of rare-earth element cerium (Ce) simultaneously, improve the plasticity and the comprehensive mechanical property of cadmium-free silver brazing alloy with the neoteric cadmium-free silver brazing alloy of refinement.
The technical scheme that addresses the above problem is, 1), use commercially available silver, cathode copper, zinc ingot metal, tin slab, indium metal, metallic cerium, proportioning on demand adopts 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, 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 cadmium-free silver brazing alloy that contains indium and cerium of the present invention, its chemical composition by the mass percent proportioning is: 25.0%~32.0% copper (Cu), 25.0%~35.0% zinc (Zn), 0.5%~5.0% indium (In), 0.01%~1.0% tin (Sn), 0.002%~0.10% cerium (Ce), all the other are silver (Ag).Solidus temperature at 660 ℃~685 ℃ scopes, liquidus temperature 715 ℃~735 ℃ scopes; Cooperate FB102 (QJ102) brazing flux, brazing material is following combination: when red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, the brazed seam mechanical property is respectively: σ b=175~335MPa, τ=170~335MPa.
Adopt conventional intermediate frequency smelting furnace to smelt, cast, by extruding, drawing, promptly obtain needed solder wire material then; The neoteric cadmium-free silver brazing alloy that contains gallium and cerium is that 45% solder is an object of reference with silver content, cooperate FB102 (QJ102) 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=175~335MPa scope, τ=170~335MPa scope).The neoteric cadmium-free silver brazing alloy that contains indium and cerium does not have the harmful element cadmium fully, has protected operator's health safety effectively, has eliminated the pollution to environment.The brazed seam mechanical performance index of solder and BAg45CuZnCd, BAg45CuZn solder are suitable, and neoteric solder is just applied at the refrigeration part production industry as the substitute of BAg45CuZnCd, BAg45CuZn solder.
Four, explanation accompanying drawing-nothing
Five, the specific embodiment
According to the quality recipe ratio of " cadmium-free silver brazing alloy that contains indium and cerium " of the present invention, narration the specific embodiment of the present invention.
The specific embodiment one:
Press the mass percent proportioning, its composition is: 30.0% bronze medal (Cu), and 27.9% zinc (Zn), 1.0% tin (Sn), 1.2% indium (In), 0.02% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 675 ℃, liquidus temperature (considered experimental error) about 735 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment two:
Press the mass percent proportioning, its composition is: 25.0% bronze medal (Cu), and 32.0% zinc (Zn), 1.0% tin (Sn), 4.0% indium (In), 0.10% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 660 ℃, liquidus temperature (considered experimental error) about 715 ℃, 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 red copper-brass (σ b=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment three:
Press the mass percent proportioning, its composition is: 32.0% bronze medal (Cu), and 29.0% zinc (Zn), 0.05% tin (Sn), 0.5% indium (In), 0.002% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 685 ℃, liquidus temperature (considered experimental error) about 735 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment four:
Press the mass percent proportioning, its composition is: 30.0% bronze medal (Cu), and 27.0% zinc (Zn), 0.02% tin (Sn), 2.0% indium (In), 0.005% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 680 ℃, liquidus temperature (considered experimental error) about 720 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment five:
Press the mass percent proportioning, its composition is: 30.0% bronze medal (Cu), and 29.5% zinc (Zn), 0.02% tin (Sn), 2.0% indium (In), 0.02% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 675 ℃, liquidus temperature (considered experimental error) about 715 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment six:
Press the mass percent proportioning, its composition is: 31.0% bronze medal (Cu), and 27.0% zinc (Zn), 0.08% tin (Sn), 1.8% indium (In), 0.025% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 675 ℃, liquidus temperature (considered experimental error) about 725 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment seven:
Press the mass percent proportioning, its composition is: 32.0% bronze medal (Cu), and 27.0% zinc (Zn), 0.5% tin (Sn), 1.5% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 685 ℃, liquidus temperature (considered experimental error) about 730 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment eight:
Press the mass percent proportioning, its composition is: 25.0% bronze medal (Cu), and 35.0% zinc (Zn), 0.5% tin (Sn), 1.5% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 680 ℃, liquidus temperature (considered experimental error) about 730 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment nine:
Press the mass percent proportioning, its composition is: 27.0% bronze medal (Cu), and 29.0% zinc (Zn), 0.7% tin (Sn), 4.5% indium (In), 0.025% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 665 ℃, liquidus temperature (considered experimental error) about 715 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment ten:
Press the mass percent proportioning, its composition is: 26.5% bronze medal (Cu), and 28.5% zinc (Zn), 0.01% tin (Sn), 5.0% indium (In), 0.065% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 665 ℃, liquidus temperature (considered experimental error) about 720 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment 11:
Press the mass percent proportioning, its composition is: 28.0% bronze medal (Cu), and 29.0% zinc (Zn), 0.05% tin (Sn), 3.8% indium (In), 0.002% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 680 ℃, liquidus temperature (considered experimental error) about 725 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment 12:
Press the mass percent proportioning, its composition is: 26.0% bronze medal (Cu), and 30.0% zinc (Zn), 0.05% tin (Sn), 4.2% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 670 ℃, liquidus temperature (considered experimental error) about 720 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment 13:
Press the mass percent proportioning, its composition is: 26.5% bronze medal (Cu), and 32.5% zinc (Zn), 0.08% tin (Sn), 1.0% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 685 ℃, liquidus temperature (considered experimental error) about 730 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment 14:
Press the mass percent proportioning, its composition is: 29.5% bronze medal (Cu), and 29.8% zinc (Zn), 0.02% tin (Sn), 0.8% indium (In), 0.035% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 685 ℃, liquidus temperature (considered experimental error) about 735 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment 15:
Press the mass percent proportioning, its composition is: 29.6% bronze medal (Cu), and 29.5% zinc (Zn), 0.01% tin (Sn), 1.2% indium (In), 0.002% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 680 ℃, liquidus temperature (considered experimental error) about 735 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment 16:
Press the mass percent proportioning, its composition is: 27.0% bronze medal (Cu), and 29.0% zinc (Zn), 0.9% tin (Sn), 3.2% indium (In), 0.10% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 680 ℃, liquidus temperature (considered experimental error) about 725 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
The specific embodiment 17:
Press the mass percent proportioning, its composition is: 28.0% bronze medal (Cu), and 29.0% zinc (Zn), 0.02% tin (Sn), 2.8% indium (In), 0.005% cerium (Ce), all the other are silver (Ag).
" cadmium-free silver brazing alloy that contains indium and cerium " solidus temperature that the mentioned component proportioning obtains about 685 ℃, liquidus temperature (considered experimental error) about 725 ℃, 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=200 ± 25MPa, τ=200 ± 30MPa), brass-carbon steel (σ b=300 ± 25MPa, τ=300 ± 30MPa), stainless steel-nickel-base alloy (σ b=350 ± 15MPa, τ=260 ± 10MPa).
Another technical characterstic of the present invention is, because " cadmium-free silver brazing alloy that contains indium and cerium " of the present invention is to soldering mother metal red copper, brass, carbon steel, stainless steel, nickel-base alloy all has good wettability respectively, therefore any cadmium-free silver brazing alloy that contain indium and cerium of the above-mentioned specific embodiment one to the specific embodiment 17, 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 cadmium-free silver brazing alloy that contains indium and cerium is characterized in that, by the mass percent proportioning is: 25.0%~32.0% copper, 25.0%~35.0% zinc, 0.5%~5.0% indium, 0.01%~1.0% tin, 0.002%~0.10% cerium, all the other are silver.
CNB2006100396593A 2006-04-19 2006-04-19 Cadmium-free silver solder containing indium and cerium Active CN100408255C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008061406A1 (en) * 2006-11-26 2008-05-29 Changshu Huayin Filler Metals Co., Ltd. A cadmium less silver brazing filter metal
CN100420538C (en) * 2006-11-26 2008-09-24 常熟市华银焊料有限公司 Cadmium-free silver based solder containing gallium, indium and cerium
CN103418933A (en) * 2013-07-18 2013-12-04 浙江信和科技股份有限公司 Silver solder for connecting brass and stainless steel
CN103909363A (en) * 2014-04-01 2014-07-09 金华市三环焊接材料有限公司 Cadmium-free low-silver solder containing tin, manganese and indium
CN104439753A (en) * 2014-11-13 2015-03-25 杭州华光焊接新材料股份有限公司 Multi-element silver soldering material containing indium and tin and preparation method of multi-element silver soldering material
CN107662063A (en) * 2016-07-29 2018-02-06 金华市三环焊接材料有限公司 A kind of formula of high-strength environment-friendly section silver solder

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052531A (en) * 1975-08-14 1977-10-04 Eutectic Corporation Indium-containing silver-copper-zinc brazing alloy
GB1532879A (en) * 1976-09-24 1978-11-22 Sheffield Smelting Co Ltd Brazing alloys
DE4315188C1 (en) * 1992-09-02 1994-04-07 Degussa Use of a cadmium-free silver alloy as a hard solder
DE4323227C1 (en) * 1993-07-12 1994-07-28 Degussa Cadmium-free silver alloy used as solder at temps. below 630 deg.C.
DE19940115A1 (en) * 1999-08-24 2001-03-01 Degussa Cadmium-free brazing alloys

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008061406A1 (en) * 2006-11-26 2008-05-29 Changshu Huayin Filler Metals Co., Ltd. A cadmium less silver brazing filter metal
CN100420538C (en) * 2006-11-26 2008-09-24 常熟市华银焊料有限公司 Cadmium-free silver based solder containing gallium, indium and cerium
US7985374B2 (en) 2006-11-26 2011-07-26 Changshu Huayin Filler Metals Co., Ltd. Cadmium-free silver brazing filler metal
CN103418933A (en) * 2013-07-18 2013-12-04 浙江信和科技股份有限公司 Silver solder for connecting brass and stainless steel
CN103909363A (en) * 2014-04-01 2014-07-09 金华市三环焊接材料有限公司 Cadmium-free low-silver solder containing tin, manganese and indium
CN104439753A (en) * 2014-11-13 2015-03-25 杭州华光焊接新材料股份有限公司 Multi-element silver soldering material containing indium and tin and preparation method of multi-element silver soldering material
CN107662063A (en) * 2016-07-29 2018-02-06 金华市三环焊接材料有限公司 A kind of formula of high-strength environment-friendly section silver solder

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