CN104551434A - Cadmium-free silver-based medium-temperature solder and preparation method thereof - Google Patents
Cadmium-free silver-based medium-temperature solder and preparation method thereof Download PDFInfo
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- CN104551434A CN104551434A CN201410652854.8A CN201410652854A CN104551434A CN 104551434 A CN104551434 A CN 104551434A CN 201410652854 A CN201410652854 A CN 201410652854A CN 104551434 A CN104551434 A CN 104551434A
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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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
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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
- B23K35/40—Making wire or rods for soldering or welding
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Abstract
The invention relates to cadmium-free silver-based medium-temperature solder and a preparation method thereof. Silver, copper and zinc-series high-silver solder with silver content of more than 40 percent is universally adopted on the current market, and the production cost is high. The cadmium-free silver-based medium-temperature solder is characterized by consisting of the following metal materials in percentage by weight: 5 to 40 percent of Ag, 33 to 36 percent of Zn, 0.01 to 3 percent of Sn, 1 to 9 percent of Mn, 0.1 to 2 percent of Ni, 0.05 to 1.0 percent of Te, 0.0001 to 0.4 percent of RE and the balance of Cu. The cadmium-free silver-based medium-temperature solder and the preparation method thereof have the advantages that the content of noble metal Ag is reduced; moreover, the solder is free of harmful elements and less harmful for a human body and the environment; the cost of the solder can be greatly lowered on the premise of meeting the requirement of a four-way valve on soldering performance; the preparation method is simple, and the solder has broad market prospect.
Description
Technical field
The present invention relates to the alternative Alloy And Preparation Method of the high silver solder of a kind of brazing material, particularly cross valve.
Background technology
Cross valve, has the control valve of four hydraulic fluid ports, is indispensable critical component in refrigeration plant, cold circulation of hot gases, and working environment is relatively more severe, needs to adopt the stronger silver solder of reliability to weld.Cross valve to welding requirement extreme high reliability, anti-fatigue performance, good decay resistance, and higher weld strength.Generally employing silver content is the high silver solder of Ag-Cu-Zn series of more than 40% in the market.Along with the needs of social development, enterprise is more and more stricter to the control of cost, and silver is in the continuous reduction of global storage capacity, and price continues surging, causes solder cost significantly to rise, and is badly in need of the alternative materials of silver.Therefore, in order to reduce enterprise's production cost, reduce the dependence to noble metal, utilize other ordinary metallic material inexorable trend that the alloy of alternative precious metal material and manufacturing process thereof have become development of modern industry.
Summary of the invention
For prior art Problems existing, the invention provides a kind of cadmium-free silver-base intermediate temperature solder and preparation method thereof, utilize ordinary metallic material to carry out Substitute For Partial precious metal material, reduce production cost.
For achieving the above object, the present invention adopts following technical scheme: a kind of cadmium-free silver-base intermediate temperature solder, it is characterized in that being made up of the metal material of following percentage by weight: Ag 5 ~ 40%, Zn 33 ~ 36%, Sn 0.01 ~ 3%, Mn 1 ~ 9%, Ni 0.1 ~ 2%, Te 0.05 ~ 1.0%, RE0.0001 ~ 0.4%, Cu surplus.
As preferably, the present invention is made up of the metal material of following percentage by weight: Ag15 ~ 40%, Zn 33 ~ 36%, Sn 0.01 ~ 3%, Mn 1 ~ 9%, Ni 0.1 ~ 2%, Te0.05 ~ 1.0%, RE 0.0001 ~ 0.4%, Cu surplus.
As preferably, the present invention is made up of the metal material of following percentage by weight: Ag15 ~ 40%, Zn 34%, Sn 2%, Mn 1 ~ 9%, Ni1.0%, Te0.5%, Re 0.1%, Cu surplus.
Another object of the present invention is to provide the preparation method of above-mentioned solder
(1) get part Cu melting, smelting temperature 1100 ~ 1200 DEG C, by RE with bottom press-in copper liquid after Copper Foil parcel, obtain the Cu-RE intermediate alloy that RE content is 0.5 ~ 5%;
(2) get above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, come out of the stove after fully stirring, cast in steel die, naturally cool;
(3) at 400 ~ 500 DEG C of temperature, alloy cast ingot is crushed to the bar of 1 ~ 3mm, more finally makes bar through operations such as follow-up drawing alignings, the various forms of products such as silk material.
In the present invention, the selection of each raw metal and proportioning are considered based on following factor:
1, in the present invention, Mn element and the unlimited solid solution of yellow gold, adding of Mn element can significantly reduce solder fusing point, and reinforcing material plasticity improves solder wetting and mechanical property simultaneously, is host element in this invention.The Mn adding 1 ~ 9% significantly can reduce the fusing point of solder, improves solder spreading wetting performance, lower than 1% time DeGrain, solder processing difficulties can be made higher than 9%, be unfavorable for preparation processing.Solder Mn content of the present invention selects 1 ~ 9% for this reason.
2, Te element has strong oxidation resistance, can reduce the oxidation of solder in welding process, improves weld strength, and can suppress Mn, the volatilization of Zn element, make face of weld smooth, attractive in appearance.The Te of interpolation 0.05 ~ 1% can improve the wetting and spreading performance of solder, can improve again the plastic deformation ability of solder.When content lower than 0.05% time, its effect is not obvious, when content higher than 1% time intensity too high, processing difficulties.Solder Te content of the present invention selects 0.05 ~ 1% for this reason.
3, add 1 ~ 2%Sn element, can fusing point be reduced, increase solder intensity simultaneously.Content lower than 1% time DeGrain, content higher than 2% time, solder processability reduces, and solder Sn content of the present invention selects 1 ~ 2% for this reason.
4, adding 0.05 ~ 1%Ni both can fining metal grain structure, can improve plasticity again.When content lower than 0.05% time, its DeGrain, when content higher than 1% time, solder fusing point is too high.Ni content of the present invention selects 0.05 ~ 1% for this reason.
If 5 add 0.0001 ~ 0.4Re element in above-mentioned solder, energy refinement brazing filler metal alloy tissue, improves solder mechanical property.When Re content is less than 0.0001%, act on not obvious, content higher than 0.4% time easy segregation cause solder performance poor in crystal boundary.Re content of the present invention is selected 0.0001 ~ 0.4% for this reason.
General solder compared to existing technology, the invention has the advantages that and reduce precious metals ag content, and not containing harmful element, to human body and environmental hazard little.Because precious metals ag content reduces, cost can reduce 10% ~ 20%, can produce excellent metallurgical reaction with cross valve mother metal, generates high, the specious solder joint of unfailing performance.Solder of the present invention can meet under the requirement of cross valve brazing property, significantly reduces solder cost, and preparation method is simple, has wide market prospects.
Detailed description of the invention
Below by embodiment, the present invention will be described.Embodiment is only limitted to that the present invention will be further described; do not represent protection scope of the present invention; present invention encompasses all alternatives, improvement project and the equivalents that may comprise in Claims scope, the nonessential amendment made according to the present invention and adjustment all belong to protection scope of the present invention.
Embodiment one
(1) after getting the Cu melting of 48.5kg, the RE of 1.5kg is added in copper liquid, obtain the Cu-RE intermediate alloy of Re content 3%;
(2) according to Ag 5%, Zn33%, Sn 0.01%, Mn9%, Ni0.1%, Te0.05%, Re 0.4%, the formula of Cu surplus is prepared burden, and gets above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, come out of the stove after abundant stirring, cast on steel die, naturally cool.
(3) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment two
(1) according to Ag 5%, Zn33%, Sn 0.01%, Mn9%, Ni0.1%, Re 0.4%, Cu the formula of surplus prepare burden, get above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, comes out of the stove after fully stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment three
(1) according to formula Ag 15%, Zn34%, Sn 0.5%, Mn9%, Ni0.5%, Te0.5%, Re 0.3%, the formula of Cu surplus is prepared burden, and gets above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, come out of the stove after abundant stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment four
(1) according to formula Ag 15%, Zn34%, Sn 0.5%, Mn9%, Ni0.5%, Re 0.3%, Cu the formula of surplus prepare burden, get above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, comes out of the stove after fully stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment five
(1) according to formula Ag 20%, Zn35%, Sn 1%, Mn6%, Ni1.0%, Te1.0%, Re 0.2%, the formula of Cu surplus is prepared burden, and gets above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, come out of the stove after abundant stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment six
(1) according to formula Ag 20%, Zn35%, Sn 1%, Mn6%, Ni1.0%, Re 0.2%, Cu the formula of surplus prepare burden, get above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, comes out of the stove after fully stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment seven
(1) according to formula Ag 30%, Zn35%, Sn 2%, Mn3%, Ni1.5%, Te1.5%, Re 0.1%, the formula of Cu surplus is prepared burden, and gets above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, come out of the stove after abundant stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment eight
(1) according to formula Ag 30%, Zn35%, Sn 2%, Mn3%, Ni1.5%, Re 0.1%, Cu the formula of surplus prepare burden, get above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, comes out of the stove after fully stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment nine
(1) according to formula Ag 40%, Zn36%, Sn 3%, Mn1%, Ni2%, Te2%, Re0.0001%, the formula of Cu surplus is prepared burden, and gets above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, come out of the stove after abundant stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Embodiment ten
(1) according to formula Ag 40%, Zn36%, Sn 3%, Mn1%, Ni2%, Re 0.0001%, Cu the formula of surplus prepare burden, get above-mentioned Cu-RE intermediate alloy, other raw metals melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, comes out of the stove after fully stirring, cast on steel die, naturally cool.
(2) at 450 DEG C of temperature, alloy cast ingot is crushed to the bar of 2.0mm, more finally makes the product of rod form through operations such as follow-up drawing alignings.
Table 1 solder composition percentage composition
Raw metal cost price of the present invention is as the criterion with on April 14th, 2014 " metal quotation net " nonferrous metal price: Ag-4175 unit/kg, Cu-48.5 unit/kg, Zn-15 unit/kg, Sn-142 unit/kg, Mn-12.3 unit/kg, Ni-121.7 unit/kg, Te-1000 unit/kg.Table 2 is the Cost comparisons between the embodiment of the present invention and comparative example, and as shown in Table 2, embodiment of the present invention cost is well below the cost of comparative example, and raw metal cost significantly reduces, and this is conducive to reducing production cost greatly, improves product competitiveness in the market.
The cost of table 2 embodiment and comparative example
| Sequence number | Cost (unit/kilogram) | |
| Embodiment 1 | BAg5CuZnSn | 224.01 |
| Embodiment 2 | BAg5CuZnSn | 219.01 |
| Embodiment 3 | BAg15CuZnSn | 640.4 |
| Embodiment 4 | BAg15CuZnSn | 635.4 |
| Embodiment 5 | BAg20CuZnSn | 849.89 |
| Embodiment 6 | BAg20CuZnSn | 845.89 |
| Embodiment 7 | BAg30CuZnSn | 1267.02 |
| Embodiment 8 | BAg30CuZnSn | 1262.02 |
| Embodiment 9 | BAg40CuZnSn | 1684.27 |
| Embodiment 10 | BAg40CuZnSn | 1679.27 |
| Comparative example | BAg45CuZn | 1892.9 |
Adopt synchronous solving to carry out test fusion temperature to embodiment each in the present invention and comparative example, test result is in table 3.From data in table 3, each embodiment performance indications are suitable with each comparative run, can meet 820 DEG C of soldering processes requirements.Select the alloy material in embodiment and BAg45CuZn welding wire respectively, carry out gas brazing with equipment on the same stage.By Cr30 stainless steel braze welding on brass tube, then the product welded is carried out strength test, the tensile strength recorded and shearing strength data are shown in Table 3.
The Mechanics Performance Testing of table 3 solder joint contrasts
Rate of spread test has been carried out, corrosion resistant plate, thickness 1mm by GB GB/T 11364-2008 " solder wetting test method " national standard; Copper plate, thickness is 0.5mm.Each solder rate of spread test technology is all identical, and probe temperature is 820 DEG C, and the time is 15s, and adopt identical brazing flux (trade mark: FB102), test result is in table 4, and the visible rate of spread of the present invention and comparative example are more or less the same, and has good wetting and spreading performance.
Table 4 solder wetting performance comparison
| Sequence number | To the stainless steel rate of spread (%) | To the red copper rate of spread (%) | |
| Embodiment 1 | BAg5CuZnSn | 90.0 | 90.2 |
| Embodiment 2 | BAg5CuZnSn | 88.2 | 88.5 |
| Embodiment 3 | BAg15CuZnSn | 89.5 | 90.5 |
| Embodiment 4 | BAg15CuZnSn | 88.5 | 89.7 |
| Embodiment 5 | BAg20CuZnSn | 90.0 | 91.0 |
| Embodiment 6 | BAg20CuZnSn | 89.5 | 89.5 |
| Embodiment 7 | BAg30CuZnSn | 90.9 | 89.9 |
| Embodiment 8 | BAg30CuZnSn | 90.1 | 89.0 |
| Embodiment 9 | BAg40CuZnSn | 89.5 | 92.1 |
| Embodiment 10 | BAg40CuZnSn | 88.2 | 90.0 |
| Comparative example | BAg45CuZn | 91.8 | 93.1 |
Tested by above solder performance, environmental protection of the present invention is described, and without silver-base solder warm in cadmium, not only mechanical property is higher, has good wetting and spreading performance, can meet the soldering processes requirement that stainless steel welds with red copper to stainless steel and red copper.All be better than corresponding without Te element solder in embodiment containing the solder properties test index of Te element, and, relative contrast's example significantly can reduce the cost of raw material, reduces significant to the cost of processing and manufacturing enterprise, is conducive to improving the competitiveness of product in market.
Claims (4)
1. a cadmium-free silver-base intermediate temperature solder, is characterized in that being made up of the metal material of following percentage by weight: Ag5 ~ 40%, Zn33 ~ 36%, Sn0.01 ~ 3%, Mn1 ~ 9%, Ni0.1 ~ 2%, Te0.05 ~ 1.0%, RE0.0001 ~ 0.4%, Cu surplus.
2. a kind of cross valve cadmium-free silver-base intermediate temperature solder as claimed in claim 1, it is characterized in that being made up of the metal material of following percentage by weight: Ag15 ~ 40%, Zn33 ~ 36%, Sn0.01 ~ 3%, Mn1 ~ 9%, Ni0.1 ~ 2%, Te0.05 ~ 1.0%, RE0.0001 ~ 0.4%, Cu surplus.
3. a kind of cadmium-free silver-base intermediate temperature solder as claimed in claim 1, is characterized in that being made up of the metal material of following percentage by weight: Ag15 ~ 40%, Zn34%, Sn2%, Mn1 ~ 9%, Ni1.0%, Te0.5%, Re0.1%, Cu surplus.
4. the preparation method of a kind of cadmium-free silver-base intermediate temperature solder as claimed in claim 1, is characterized in that comprising the following steps:
(1) get part Cu melting, smelting temperature 1100 ~ 1200 DEG C, by RE with bottom press-in copper liquid after Copper Foil parcel, obtain the Cu-RE intermediate alloy that RE content is 0.5 ~ 5%;
(2) get above-mentioned Cu-RE intermediate alloy, other raw metal melting together specified in mixing formula after conversion, smelting temperature 1100 DEG C, come out of the stove after fully stirring, cast on steel die, naturally cool;
(3) at 400 ~ 500 DEG C of temperature, alloy cast ingot is crushed to the bar of 1 ~ 3mm, the more various forms of product such as finally makes through operations such as follow-up drawing alignings.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106077995A (en) * | 2016-06-30 | 2016-11-09 | 杭州华光焊接新材料股份有限公司 | A kind of containing manganese, the cadmium-free low-silver solder and preparation method thereof of stannum |
| CN106216878A (en) * | 2016-08-16 | 2016-12-14 | 镇江市锶达合金材料有限公司 | A kind of cadmium-free silver brazing alloy |
| 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 |
| CN108406160A (en) * | 2018-01-31 | 2018-08-17 | 郑州机械研究所有限公司 | A kind of preparation method and its device of the compound medicine core solder cake of double helix state |
| CN112108790A (en) * | 2020-08-11 | 2020-12-22 | 杭州华光焊接新材料股份有限公司 | Cadmium-free low-silver brazing filler metal and preparation method thereof |
| CN112518169A (en) * | 2020-12-04 | 2021-03-19 | 杭州华光焊接新材料股份有限公司 | Low-melting-point high-strength low-silver cadmium-free manganese-free multi-element silver solder and preparation method thereof |
| CN114952079A (en) * | 2022-06-28 | 2022-08-30 | 浙江亚通焊材有限公司 | Silver-reducing flux-cored wire |
| CN118081179A (en) * | 2024-04-26 | 2024-05-28 | 龙门实验室 | Amorphous aluminum silicon-based brazing filler metal and preparation method and brazing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106077995A (en) * | 2016-06-30 | 2016-11-09 | 杭州华光焊接新材料股份有限公司 | A kind of containing manganese, the cadmium-free low-silver solder and preparation method thereof of stannum |
| 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 |
| CN106216878A (en) * | 2016-08-16 | 2016-12-14 | 镇江市锶达合金材料有限公司 | A kind of cadmium-free silver brazing alloy |
| CN108406160A (en) * | 2018-01-31 | 2018-08-17 | 郑州机械研究所有限公司 | A kind of preparation method and its device of the compound medicine core solder cake of double helix state |
| CN108406160B (en) * | 2018-01-31 | 2020-08-28 | 郑州机械研究所有限公司 | Preparation method and device of double-helix composite flux-cored brazing filler metal cake |
| CN112108790A (en) * | 2020-08-11 | 2020-12-22 | 杭州华光焊接新材料股份有限公司 | Cadmium-free low-silver brazing filler metal and preparation method thereof |
| CN112518169A (en) * | 2020-12-04 | 2021-03-19 | 杭州华光焊接新材料股份有限公司 | Low-melting-point high-strength low-silver cadmium-free manganese-free multi-element silver solder and preparation method thereof |
| CN114952079A (en) * | 2022-06-28 | 2022-08-30 | 浙江亚通焊材有限公司 | Silver-reducing flux-cored wire |
| CN114952079B (en) * | 2022-06-28 | 2023-06-23 | 浙江亚通新材料股份有限公司 | Silver-reducing flux-cored wire |
| CN118081179A (en) * | 2024-04-26 | 2024-05-28 | 龙门实验室 | Amorphous aluminum silicon-based brazing filler metal and preparation method and brazing method thereof |
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