CN103624418A - Low-silver-copper-based brazing filler metal and preparation method thereof - Google Patents
Low-silver-copper-based brazing filler metal and preparation method thereof Download PDFInfo
- Publication number
- CN103624418A CN103624418A CN201310673027.2A CN201310673027A CN103624418A CN 103624418 A CN103624418 A CN 103624418A CN 201310673027 A CN201310673027 A CN 201310673027A CN 103624418 A CN103624418 A CN 103624418A
- Authority
- CN
- China
- Prior art keywords
- copper
- filler metal
- preparation
- brazing filler
- melting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005219 brazing Methods 0.000 title claims abstract description 52
- 239000000945 filler Substances 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006263 metalation reaction Methods 0.000 title 1
- 229910052709 silver Inorganic materials 0.000 claims abstract description 49
- 230000008018 melting Effects 0.000 claims abstract description 44
- 238000002844 melting Methods 0.000 claims abstract description 44
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910000679 solder Inorganic materials 0.000 claims description 56
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 41
- 239000004332 silver Substances 0.000 claims description 41
- 229910045601 alloy Inorganic materials 0.000 claims description 28
- 239000000956 alloy Substances 0.000 claims description 28
- 150000002739 metals Chemical class 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 12
- 229910002482 Cu–Ni Inorganic materials 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- 238000009749 continuous casting Methods 0.000 claims description 7
- 239000010949 copper Substances 0.000 abstract description 29
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 abstract description 19
- 238000005204 segregation Methods 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 3
- 238000009472 formulation Methods 0.000 abstract 1
- 239000011135 tin Substances 0.000 description 86
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 238000007499 fusion processing Methods 0.000 description 16
- 230000004927 fusion Effects 0.000 description 13
- 238000005476 soldering Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000005662 electromechanics Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 229910017888 Cu—P Inorganic materials 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B23K35/302—Cu as the principal constituent
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
The invention relates to a low-silver-copper-based brazing filler metal and a preparation method thereof. The low-silver-copper-based brazing filler metal comprises Ag, Cu and P, wherein Sn, Ni and rare earth are further added, the weight percentages of the components are as follows: 1.5%-2.5% of Ag, 5.5%-6.6% of P, 5%-7% of Sn, 1.0-2.5% of Ni, not more than 0.05% of rare earth and the balance of Cu; the preparation method of the low-silver-copper-based brazing filler metal comprises the following steps of preparing Sn to filament Sn, smelting, continuously casting, continuously extruding, forming and cleaning to obtain the brazing filler metal. The brazing filler metal has the advantages of reasonable formulation design, lower brazing filler metal melting temperature, good wettability and mobility, stable quality of a soldered joint and long service life; a BCu80AgP copper-phosphorus brazing filler metal can be replaced, and the production cost of motor brazing is greatly reduced. The preparation method of the brazing filler metal can effectively solve a segregation problem of Sn, a preparation process is optimized, and the quality of the prepared brazing filler metal is remarkably improved.
Description
Technical field
The present invention relates to a kind of low silver copper-base filler metals and preparation method thereof, be applicable to the soldering of the industries such as motor, machinery, belong to brazing material field.
Background technology
In recent years, due to the continuous fierceness of market competition and limited Precious Metals Resources, the requirement of " reducing costs, reduce noble metal silver consumption " has been proposed being usually used in the brazing material of the industries such as machinery, motor, for replacing the BCu80AgP at the common argentiferous 15% of electromechanics trade, the lower brazing material of silver content that requires the exploitation of solder manufacturer to make new advances.
The less copper-phosphorus brazing alloy of common silver content in the market, as BCu91PAg copper-phosphorus brazing alloy of the BCu89PAg copper-phosphorus brazing alloy of argentiferous 5%, argentiferous 2% etc., although these copper-phosphorus brazing alloy prices are lower, but the decay resistance of soldered fitting, anti-fatigue performance etc. all do not reach instructions for use, on motor, do not reach the result of use of BCu80AgP during soldering, therefore cannot meet client's requirement.
Also there is now some performances solder relatively preferably, if open day is on 07 28th, 2010, publication number is in the Chinese patent of CN101786208A, a kind of novel active copper-phosphorus brazing alloy is disclosed, although the content of Ag is lower in this solder, but creep strength relative deficiency after its soldering motor, is difficult to substitute completely BCu80AgP copper-phosphorus brazing alloy.
In sum, also do not have at present a kind of formula Design reasonable, be suitable for the low silver-bearing copper phosphorus brazing alloy of motor soldering.The solidus of existing low silver-bearing copper phosphorus brazing alloy and liquidus temperature interval are too large, and high silver-bearing copper phosphorus brazing alloy silver content is higher, production and use cost high, will can not meet user demand in soldering on motor gradually, thereby hinder the development of solder in electromechanics trade.
On the other hand, the melting containing Sn copper base solder easily be there is in industry the segregation of Sn, cause containing the copper base solder Composition Control of Sn not goodly, cause solder performance not enough, in the urgent need to developing a kind of smelting preparation process that can avoid Sn segregation.
China Patent No. 200510023129.5 discloses the patent that name is called " a kind of copper-base brazing alloy ", it selectively adds manganese, zinc, silver, nickel, silicon, tin, aluminium, lithium, rare earth in conventional copper-base brazing alloy (being copper base solder), welding technological properties and silver solder are close, and cost is lower more than 1 times than general silver solder; But this brazing alloy can not replace the BCu80AgP at the common argentiferous 15% of electromechanics trade, the yet scheme of not mentioned solution Sn segregation problem also in patent, does not overcome above-mentioned defect of the prior art.
China Patent No. 200710102635.2 discloses the patent that name is called copper-phosphorus brazing alloy of nickel " stanniferous and ", it is except traditional copper-phosphorus brazing alloy Constitution Elements, also comprise tin (Sn) and nickel (Ni), tensile strength is better, and not containing silver element, operating temperature reduces, soldering can operate at low temperatures, reduced base oxidation and the deformation of material, cost; But this brazing alloy can not replace the BCu80AgP at the common argentiferous 15% of electromechanics trade, the yet scheme of not mentioned solution Sn segregation problem also in patent, does not overcome above-mentioned defect of the prior art.
China Patent No. 200910097437.0 discloses the patent that name is called " a kind of low silver copper base medium temperature brazing filler ", it has added P, In, Ni, Ga in copper base solder, and Ag content is only 1.8%-5%, can replace completely BAg25CuZnSn silver solder for freezing, the soldering of the industry such as machinery, electromechanics, electrical equipment, instrument and meter, valve pipe fitting; But this solder can not replace the BCu80AgP at the common argentiferous 15% of electromechanics trade, in formula, not containing Sn, do not overcome above-mentioned defect of the prior art yet.
Summary of the invention
The object of the invention is to overcome above shortcomings in prior art, and provide that a kind of formula Design is reasonable, price is low, cost performance is high, the low silver copper-base filler metals of fusion temperature narrow range, joint performance excellence.
The present invention addresses the above problem adopted technical scheme: this low silver copper-base filler metals contains Ag, Cu and P, it is characterized in that: also added Sn, Ni and rare earth; Each weight percentages of components of described low silver copper-base filler metals is: the Ag of 1.5-2.5%, and the P of 5.5-6.6%, the Sn of 5-7 %, the Ni of 1.0-2.5%, rare earth≤0.05%, surplus is Cu.
Each weight percentages of components of low silver copper-base filler metals described in the present invention is preferably: the Ag of 1.8-2.2%, and the P of 5.8-6.4%, the Sn of 5.5-6.5 %, the Ni of 1.5-2.0%, rare earth≤0.03%, surplus is Cu.
Each weight percentages of components of low silver copper-base filler metals described in the present invention is more preferably: 2.0% Ag, and 6.1% P, the Sn of 6.0 %, 1.7% Ni, 0.02% rare earth, surplus is Cu.
Solder of the present invention be take Ag-Cu-P as matrix, and Cu is surplus, and other each compositions and content are determined in the following manner:
Ag: by considering performance and cost requirement, selecting Ag content range is 1.5 ~ 2.5%;
P: known with reference to Cu-P binary phase diagraml, when P content is 8.4%, be eutectic composition, there is minimum fusion temperature, still the Cu in solder under this kind of composition
3p fragility is mutually more, is unfavorable for the production and processing of solder, and can cause the decline of soldered fitting intensity; In hypoeutectic composition range, the rising of P content can effectively reduce the fusion temperature of solder, but when P content is greater than 6.6%, the Cu in solder
3p fragility is mutually more, is difficult to be processed into thread or strip, and weld strength is also because declining appears in the existence of fragility phase, easily occurs fracture; For P content, higher than 8.4% hypereutectic composition solder, also have a large amount of fragility phases, and fusion temperature is higher, does not also have actual serviceability; For obtaining good serviceability, by lot of experiment validation, the P content of solder is decided to be to 5.5%-6.6%;
Sn: for further optimizing the brazing property of solder, obtain having the solder of good comprehensive brazing property, be chosen in solder and add chemical element Sn, mainly play the fusion temperature that reduces solder, and improve wetability and the mobility of brazing filler metal alloy; But the content of Sn can not be too high, once surpassing 7%, the content of Sn just easily forms Ag
3sn and Cu
41sn
11frangible compounds, causes solder poor processability, cannot make solder finished product;
Ni: because Ni element can be solidly soluted into the effect of playing solution strengthening in Cu matrix, can improve the intensity of solder, so select to add chemical element Ni, increase intensity, the toughness of solder; Ni element can also play the effect of the resistance to corrosion that improves soldered fitting simultaneously, thereby has improved the comprehensive brazing property of solder; But the content of Ni can not be too high, by experiment, once the content of Ni surpasses 2.5%, can make the fusion temperature of brazing filler metal alloy raise, and Ni can form Ni with P
3p fragility phase, increases solder hardness, is unfavorable for the further machine-shaping of solder;
Rare earth: add trace rare-earth to have regulating action to solder tissue, tissue that can refinement brazing filler metal alloy, promotes the processing characteristics of solder, reduces the oxide content in ingot casting simultaneously, improves the wettability of solder.
The present invention also provides a kind of its preparation method of described low silver copper-base filler metals, and the technical scheme adopting is: the preparation method of this low silver copper-base filler metals, is characterized in that: before melting, described Sn is processed, the Sn of bulk is prepared into filamentous Sn; In fusion process, described Sn adds with the form of filament Sn; In fusion process, add the described rare earth of trace to regulate solder tissue; After melting, then by continuous casting, connect to squeeze, moulding, cleaning obtain brazing material.Because component segregation easily occurs when the melting high Sn copper-phosphorus brazing alloy, while causing actual use, there is infusibility or cross flow, there is no at present the generation that perfect method can be avoided segregation; Sn is carried out to pretreatment, and the form with filament Sn in fusion process adds, and has increased the contact area of Sn and melt, is conducive to Sn and is uniformly distributed in liquation, can solve the segregation problem of Sn.
The present invention is preferably in fusion process in described step (2), adds the described rare earth of trace to regulate solder tissue.Add trace rare-earth to have regulating action to solder tissue, tissue that can refinement brazing filler metal alloy, promotes the processing characteristics of solder, reduces the oxide content in ingot casting simultaneously, improves the wettability of solder.
Before the present invention is preferably melting in described step (1), described Ni and rare earth are first carried out to melting in advance with Cu, make respectively intermediate alloy Cu-Ni and Cu-RE, then carry out follow-up melting.By Cu-Ni alloy, prepare, reduced smelting temperature, avoid the too high transition loss that causes other raw materials of smelting temperature; Meanwhile, by the preparation of Cu-RE, prevent a large amount of oxidations of oxidizable elements RE, reduced loss; According to the actual needs of producing, adopt the mode of preparing intermediate alloy Cu-Ni and Cu-RE, and in molding procedure strict controlled working amount, in multi-step process, adopt intermediate annealing process simultaneously, by above method, effectively reduce the work hardening of material; In addition, if do not adopt this technique, the product composition of making has larger deviation.
The present invention is preferably in fusion process in described step (2), uses dry plant ash as coverture.In traditional smelting copper alloy process, take charcoal as coverture, and the present invention uses dry plant ash as coverture, plant ash has the advantages such as area coverage is large, covering is fine and close, the oxidization burning loss that has effectively guaranteed Sn and rare earth element in fusion process, has also reduced liquation suction hydrogen and oxygen content during refining.
The present invention compared with prior art, has the following advantages and effect:
1, the content of noble metal silver is few, than BCu80AgP, reduces silver content 13% left and right, greatly reduces production cost, has saved the consumption of noble metal silver, makes the limited resources of silver can access more reasonably utilization;
2, the mechanical strength of soldered fitting is high, compactness good, resistivity is low, joint corrosion resistance and creep strength are outstanding, feed back soldering processes performance good, soldered fitting steady quality after client uses, there is good fatigue behaviour, can effectively promote the service life of soldered fitting; Process performance index requires suitable with BCu80AgP copper-phosphorus brazing alloy, and part index number, also higher than BCu80AgP copper-phosphorus brazing alloy, can substitute BCu80AgP for the soldering of electromechanics trade;
3, fusion temperature of the present invention is 570 ℃～690 ℃, is starkly lower than conventional copper-phosphorus brazing alloy, during soldering, can reduce brazing temperature, prevent mother metal overheated cause fracture;
4, its tensile strength adopt low silver copper-base filler metals of the present invention to carry out brazed copper joint, more than can reach 300MPa;
5, applicable to the connection between stator line and lead-out wire in large and medium-sized alternating current generator.
The formula Design of low silver copper-base filler metals of the present invention is reasonable, and noble silver content is low, and cost performance is high; When for motor soldering, solder fusion temperature is lower, wetability, good fluidity, and soldered fitting steady quality, has good fatigue behaviour, the long service life of soldered fitting; High comprehensive performance, can replace the BCu80AgP copper-phosphorus brazing alloy that the scope of application is wide, consumption is large, thereby can greatly reduce the production cost of motor soldering.
The preparation method of low silver copper-base filler metals of the present invention can effectively solve the segregation problem of Sn, and preparation technology is optimized, and the solder quality preparing significantly improves.
The specific embodiment
Below by specific embodiment, the present invention is described in further detail, and following examples are explanation of the invention and the present invention is not limited to following examples.
Referring to table 1-table 5, in each embodiment, each composition percentage by weight and parameter are write exactly in table, table 1 is embodiment of the present invention 1-embodiment 6 data table related, table 2 is embodiment of the present invention 7-embodiment 12 data table related, table 3 is embodiment of the present invention 13-embodiment 18 data table related, table 4 is embodiment of the present invention 19-embodiment 24 data table related, and table 5 is embodiment of the present invention 25-embodiment 30 data table related.
Table 1 embodiment 1-embodiment 6 data table related.
| Component and parameter name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Ag (% by weight) | 1.5 | 1.7 | 1.7 | 1.7 | 1.7 | 2.0 |
| P (% by weight) | 5.5 | 5.5 | 5.8 | 5.8 | 5.8 | 5.8 |
| Ni (% by weight) | 1.0 | 1.5 | 1.5 | 1.7 | 1.1 | 1.7 |
| Sn (% by weight) | 5.0 | 5.0 | 5.0 | 5.0 | 5.3 | 5.3 |
| Cu (% by weight) | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| RE (% by weight) | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing |
| Solder fusion temperature (℃) | 610~670 | 613~674 | 613~667 | 615~671 | 605~653 | 602~659 |
| Solder tensile strength (MPa) | 350 | 354 | 348 | 356 | 351 | 348 |
Table 2 embodiment 7-embodiment 12 data table related.
| Component and parameter name | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| Ag (% by weight) | 2.0 | 2.0 | 2.0 | 2.2 | 2.2 | 2.2 |
| P (% by weight) | 6.1 | 6.1 | 6.1 | 6.1 | 6.3 | 6.3 |
| Ni (% by weight) | 1.7 | 2.0 | 2.0 | 2.0 | 2.0 | 2.2 |
| Sn (% by weight) | 5.3 | 5.3 | 5.6 | 5.6 | 5.6 | 5.6 |
| Cu (% by weight) | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| RE (% by weight) | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing |
| Solder fusion temperature (℃) | 601~652 | 601~661 | 597~654 | 597~651 | 597~649 | 600~655 |
| Solder tensile strength (MPa) | 346 | 357 | 352 | 352 | 349 | 361 |
Table 3 embodiment 13-embodiment 18 data table related.
| Component and parameter name | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 |
| Ag (% by weight) | 2.2 | 2.3 | 2.3 | 2.3 | 2.3 | 2.5 |
| P (% by weight) | 6.3 | 6.3 | 6.4 | 6.4 | 6.4 | 6.4 |
| Ni (% by weight) | 2.2 | 2.2 | 2.2 | 2.4 | 2.4 | 2.4 |
| Sn (% by weight) | 6.0 | 6.0 | 6.0 | 6.0 | 6.3 | 6.3 |
| Cu (% by weight) | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| RE (% by weight) | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing |
| Solder fusion temperature (℃) | 595~647 | 592~645 | 592~642 | 597~652 | 587~645 | 583~641 |
| Solder tensile strength (MPa) | 358 | 355 | 353 | 352 | 363 | 361 |
Table 4 embodiment 19-embodiment 24 data table related.
| Component and parameter name | Embodiment 19 | Embodiment 20 | Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 |
| Ag (% by weight) | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| P (% by weight) | 6.6 | 6.6 | 6.6 | 6.6 | 6.6 | 6.1 |
| Ni (% by weight) | 2.4 | 2.5 | 2.5 | 2.5 | 1.7 | 1.0 |
| Sn (% by weight) | 6.3 | 6.3 | 6.7 | 7.0 | 7.0 | 6.0 |
| Cu (% by weight) | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| RE (% by weight) | Nothing | Nothing | Nothing | Nothing | Nothing | 0.02 |
| Solder fusion temperature (℃) | 581~639 | 584~643 | 577~636 | 572~634 | 570~631 | 590~653 |
| Solder tensile strength (MPa) | 356 | 354 | 371 | 377 | 354 | 352 |
Table 5 embodiment 25-embodiment 30 data table related.
| Component and parameter name | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 |
| Ag (% by weight) | 2.5 | 2.2 | 2.0 | 2.0 | 2.0 | 2.2 |
| P (% by weight) | 6.1 | 6.1 | 6.1 | 6.1 | 6.1 | 6.1 |
| Ni (% by weight) | 1.7 | 1.2 | 1.3 | 1.7 | 1.7 | 1.4 |
| Sn (% by weight) | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 |
| Cu (% by weight) | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| RE (% by weight) | 0.03 | 0.02 | 0.02 | 0.03 | 0.05 | 0.05 |
| Solder fusion temperature (℃) | 595~663 | 593~662 | 595~665 | 603~670 | 602~670 | 592~658 |
| Solder tensile strength (MPa) | 356 | 349 | 351 | 361 | 361 | 351 |
The process performance index of low silver copper-base filler metals of the present invention requires suitable with BCu80AgP silver solder, part index number is also better than BCu80AgP copper-phosphorus brazing alloy, make low silver copper-base filler metals of the present invention can replace BCu80AgP copper-phosphorus brazing alloy completely for the soldering of the industries such as motor, machinery, and greatly reduce the content of noble metal silver, reduce production cost, there is good economic and social benefit.
The preparation method of embodiment 1-6 comprises the following steps:
(1) pretreatment before melting: before melting, Sn is processed, the Sn of bulk is prepared into filamentous Sn;
(2) melting: in fusion process, Sn adds with the form of filament Sn, has increased the contact area of Sn and melt, is conducive to Sn and is uniformly distributed in liquation, has solved the segregation problem of Sn; Use dry plant ash as coverture, plant ash has the advantages such as area coverage is large, covering is fine and close, has effectively reduced the oxidization burning loss of Sn in fusion process, has also reduced liquation suction hydrogen and oxygen content during refining;
(3) melting subsequent treatment: after melting, then by continuous casting, connect to squeeze, moulding, cleaning obtain brazing material.
The preparation method of embodiment 7-12 comprises the following steps:
(1) pretreatment before melting: before melting, Sn is processed, the Sn of bulk is prepared into filamentous Sn;
(2) melting: in fusion process, first add Cu, P, Ni, Ag element when reinforced, add until completely melted Sn, add immediately coverture to play insulation after having fed in raw material, prevent the effect of the scaling loss of oxidizable element; Sn adds with the form of filament Sn, has increased the contact area of Sn and melt, is conducive to Sn and is uniformly distributed in liquation, has solved the segregation problem of Sn; Use dry plant ash as coverture, plant ash has the advantages such as area coverage is large, covering is fine and close, has effectively reduced the oxidization burning loss of Sn in fusion process, has also reduced liquation suction hydrogen and oxygen content during refining;
(3) melting subsequent treatment: after melting, then by continuous casting, connect to squeeze, moulding, cleaning obtain brazing material.
The preparation method of embodiment 13-23 comprises the following steps:
(1) pretreatment before melting: before melting, Sn is processed, the Sn of bulk is prepared into filamentous Sn; According to the actual needs of producing, Ni is first carried out to melting in advance with Cu, make intermediate alloy Cu-Ni, then carry out follow-up melting;
(2) melting: in fusion process, first add Cu-P, Cu, Cu-Ni, Ag element when reinforced, add until completely melted Sn, add immediately coverture to play insulation after having fed in raw material, prevent the effect of the scaling loss of oxidizable element; Sn adds with the form of filament Sn, has increased the contact area of Sn and melt, is conducive to Sn and is uniformly distributed in liquation, has solved the segregation problem of Sn; Use dry plant ash as coverture, plant ash has the advantages such as area coverage is large, covering is fine and close, has effectively reduced the oxidization burning loss of Sn in fusion process, has also reduced liquation suction hydrogen and oxygen content during refining;
(3) melting subsequent treatment: after melting, then by continuous casting, connect to squeeze, moulding, cleaning obtain brazing material.
The preparation method of embodiment 24-28 comprises the following steps:
(1) pretreatment before melting: before melting, Sn is processed, the Sn of bulk is prepared into filamentous Sn; According to the actual needs of producing, Ni and rare earth are first carried out to melting in advance with Cu respectively, make intermediate alloy Cu-Ni and Cu-RE, then carry out follow-up melting;
(2) melting: in fusion process, first add Cu-P, Cu, Cu-Ni, Ag element when reinforced, add until completely melted Cu-RE, finally add Sn, add immediately coverture to play insulation after having fed in raw material, prevent the effect of the scaling loss of oxidizable element; Sn adds with the form of filament Sn, has increased the contact area of Sn and melt, is conducive to Sn and is uniformly distributed in liquation, has solved the segregation problem of Sn; Use dry plant ash as coverture, plant ash have area coverage large, cover the advantages such as fine and close, effectively reduced the oxidization burning loss of Sn and rare earth element in fusion process, also reduced liquation suction hydrogen and oxygen content during refining; Added the described rare earth of trace to regulate solder tissue.
(3) melting subsequent treatment: after melting, then by continuous casting, connect to squeeze, moulding, cleaning obtain brazing material.
The preparation method of embodiment 29-30 comprises the following steps:
(1) pretreatment before melting: before melting, Sn is processed, the Sn of bulk is prepared into filamentous Sn;
(2) melting: in fusion process, Sn adds with the form of filament Sn, has increased the contact area of Sn and melt, is conducive to Sn and is uniformly distributed in liquation, has solved the segregation problem of Sn; Use dry plant ash as coverture, plant ash have area coverage large, cover the advantages such as fine and close, effectively reduced the oxidization burning loss of Sn and rare earth element in fusion process, also reduced liquation suction hydrogen and oxygen content during refining; Added the described rare earth of trace to regulate solder tissue.
(3) melting subsequent treatment: after melting, then by continuous casting, connect to squeeze, moulding, cleaning obtain brazing material.
All the other steps prepared by solder of the present invention are identical with conventional method or close, do not repeat them here.
It should be noted that, percentage composition used in the present invention is all weight percentage, and Ag represents that silver, P represent that phosphorus, Ni represent that nickel, Sn represent that tin, Cu represent that copper, RE represent rare earth, and this is common practise to one skilled in the art.
By foregoing description, those skilled in the art can implement.
Although the present invention with embodiment openly as above; but it is not in order to limit protection scope of the present invention; any technical staff who is familiar with this technology, not departing from change and the retouching of doing in the spirit and scope of the present invention, all should belong to protection scope of the present invention.
Claims (8)
1. a low silver copper-base filler metals, contains Ag, Cu and P, it is characterized in that: also added Sn, Ni and rare earth; Each weight percentages of components of described low silver copper-base filler metals is: the Ag of 1.5-2.5%, and the P of 5.5-6.6%, the Sn of 5-7 %, the Ni of 1.0-2.5%, rare earth≤0.05%, surplus is Cu.
2. low silver copper-base filler metals according to claim 1, is characterized in that: each weight percentages of components of described low silver copper-base filler metals is: the Ag of 1.8-2.2%, and the P of 5.8-6.4%, the Sn of 5.5-6.5 %, the Ni of 1.5-2.0%, rare earth≤0.03%, surplus is Cu.
3. low silver copper-base filler metals according to claim 2, is characterized in that: each weight percentages of components of described low silver copper-base filler metals is: 2.0% Ag, and 6.1% P, the Sn of 6.0 %, 1.7% Ni, 0.02% rare earth, surplus is Cu.
4. a preparation method for the low silver copper-base filler metals as described in claim as arbitrary in claim 1-3, is characterized in that: comprise the following steps:
(1) pretreatment before melting: described Sn is processed, the Sn of bulk is prepared into filamentous Sn;
(2) melting: described Sn adds with the form of filament Sn;
(3) melting subsequent treatment: again by continuous casting, connect to squeeze, moulding, cleaning obtain brazing material.
5. the preparation method of low silver copper-base filler metals according to claim 4, is characterized in that: in described step (2), add the described rare earth of trace to regulate solder tissue.
6. the preparation method of low silver copper-base filler metals according to claim 4, is characterized in that: in described step (1), described Ni is first carried out to melting in advance with Cu, make intermediate alloy Cu-Ni, then carry out follow-up melting.
7. the preparation method of low silver copper-base filler metals according to claim 5, is characterized in that: in described step (1), described Ni and rare earth are first carried out to melting in advance with Cu, make respectively intermediate alloy Cu-Ni and Cu-RE, then carry out follow-up melting.
8. according to the preparation method of the low silver copper-base filler metals described in the arbitrary claim of claim 4-7, it is characterized in that: in described step (2), use dry plant ash as coverture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310673027.2A CN103624418B (en) | 2013-12-12 | 2013-12-12 | A kind of low silver copper-base filler metals and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310673027.2A CN103624418B (en) | 2013-12-12 | 2013-12-12 | A kind of low silver copper-base filler metals and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103624418A true CN103624418A (en) | 2014-03-12 |
| CN103624418B CN103624418B (en) | 2015-10-07 |
Family
ID=50206059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310673027.2A Active CN103624418B (en) | 2013-12-12 | 2013-12-12 | A kind of low silver copper-base filler metals and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103624418B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028915A (en) * | 2014-06-09 | 2014-09-10 | 乐清市博特焊接材料有限公司 | Phosphor copper welding rod and preparation method thereof |
| 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 |
| CN105834613A (en) * | 2016-05-20 | 2016-08-10 | 南京理工大学 | Solder special for high-frequency soldering of four-way valve |
| CN105965175A (en) * | 2016-05-20 | 2016-09-28 | 浙江新锐焊接科技股份有限公司 | Low-silver brazing filler metal used for high-frequency brazing of four-way valve |
| CN106041355A (en) * | 2016-07-20 | 2016-10-26 | 安徽华众焊业有限公司 | Copper-based soldering paste |
| CN106141496A (en) * | 2016-07-28 | 2016-11-23 | 华南理工大学 | A kind of copper phosphor tin nickel solder and its preparation method and application |
| CN106514050A (en) * | 2016-12-29 | 2017-03-22 | 安徽华众焊业有限公司 | Brass solder and preparation method thereof |
| CN106514041A (en) * | 2016-11-30 | 2017-03-22 | 安徽华众焊业有限公司 | Low-Ag Cu-based medium-temperature solder |
| CN106624448A (en) * | 2016-12-29 | 2017-05-10 | 安徽华众焊业有限公司 | Low-silver base brazing filler metal and preparation method thereof |
| CN106736017A (en) * | 2016-11-30 | 2017-05-31 | 安徽华众焊业有限公司 | Low-silver copper-base middle temperature solder paste |
| CN108381058A (en) * | 2018-02-27 | 2018-08-10 | 江苏远方动力科技有限公司 | One kind high-performance solder of low-silver copper-base containing Ga and preparation method thereof |
| CN108465974A (en) * | 2018-02-27 | 2018-08-31 | 江苏远方动力科技有限公司 | A kind of low-silver copper-base high-performance solder and preparation method thereof |
| CN113843546A (en) * | 2021-09-23 | 2021-12-28 | 金华市金钟焊接材料有限公司 | CuPSnAg Ni-Re ultra-silver solder, preparation method and application |
| CN114131241A (en) * | 2021-12-06 | 2022-03-04 | 浙江亚通焊材有限公司 | Bronze welding flux for tunnel furnace and welding method |
| CN114986023A (en) * | 2022-06-02 | 2022-09-02 | 杭州华光焊接新材料股份有限公司 | Process for prefabricating low-melting-point brazing filler metal, low-melting-point brazing filler metal and preparation method thereof |
| CN115283880A (en) * | 2022-06-20 | 2022-11-04 | 郑州机械研究所有限公司 | Copper-phosphorus welding wire for brazing copper alloy mirror frame and preparation method and preparation system thereof |
| CN117076892A (en) * | 2023-10-13 | 2023-11-17 | 广东美的制冷设备有限公司 | Solder design method, apparatus, and computer-readable storage medium |
| CN117486629A (en) * | 2024-01-02 | 2024-02-02 | 福建毫米电子有限公司 | Method for manufacturing nitride ceramic copper-clad plate through low-temperature brazing |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60127093A (en) * | 1983-12-12 | 1985-07-06 | Tanaka Kikinzoku Kogyo Kk | Brazing material |
| CN1759974A (en) * | 2005-10-25 | 2006-04-19 | 哈尔滨工业大学 | Mesothermal copper based solder without cadmium, and preparation method |
| CN101342644A (en) * | 2007-07-13 | 2009-01-14 | 金华市信和焊材制造有限公司 | High-ductility environment friendly silver-saving medium-temperature brazing filler metal |
| WO2012153925A2 (en) * | 2011-05-11 | 2012-11-15 | Cho Chu Hyon | Brazing alloy |
-
2013
- 2013-12-12 CN CN201310673027.2A patent/CN103624418B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60127093A (en) * | 1983-12-12 | 1985-07-06 | Tanaka Kikinzoku Kogyo Kk | Brazing material |
| CN1759974A (en) * | 2005-10-25 | 2006-04-19 | 哈尔滨工业大学 | Mesothermal copper based solder without cadmium, and preparation method |
| CN101342644A (en) * | 2007-07-13 | 2009-01-14 | 金华市信和焊材制造有限公司 | High-ductility environment friendly silver-saving medium-temperature brazing filler metal |
| WO2012153925A2 (en) * | 2011-05-11 | 2012-11-15 | Cho Chu Hyon | Brazing alloy |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028915A (en) * | 2014-06-09 | 2014-09-10 | 乐清市博特焊接材料有限公司 | Phosphor copper welding rod and preparation method thereof |
| 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 |
| CN105834613B (en) * | 2016-05-20 | 2018-10-02 | 南京理工大学 | A kind of solder being exclusively used in four-way valve high frequency brazing |
| CN105834613A (en) * | 2016-05-20 | 2016-08-10 | 南京理工大学 | Solder special for high-frequency soldering of four-way valve |
| CN105965175A (en) * | 2016-05-20 | 2016-09-28 | 浙江新锐焊接科技股份有限公司 | Low-silver brazing filler metal used for high-frequency brazing of four-way valve |
| CN106041355A (en) * | 2016-07-20 | 2016-10-26 | 安徽华众焊业有限公司 | Copper-based soldering paste |
| CN106141496A (en) * | 2016-07-28 | 2016-11-23 | 华南理工大学 | A kind of copper phosphor tin nickel solder and its preparation method and application |
| CN106514041A (en) * | 2016-11-30 | 2017-03-22 | 安徽华众焊业有限公司 | Low-Ag Cu-based medium-temperature solder |
| CN106736017A (en) * | 2016-11-30 | 2017-05-31 | 安徽华众焊业有限公司 | Low-silver copper-base middle temperature solder paste |
| CN106514050A (en) * | 2016-12-29 | 2017-03-22 | 安徽华众焊业有限公司 | Brass solder and preparation method thereof |
| CN106624448A (en) * | 2016-12-29 | 2017-05-10 | 安徽华众焊业有限公司 | Low-silver base brazing filler metal and preparation method thereof |
| CN108381058A (en) * | 2018-02-27 | 2018-08-10 | 江苏远方动力科技有限公司 | One kind high-performance solder of low-silver copper-base containing Ga and preparation method thereof |
| CN108465974A (en) * | 2018-02-27 | 2018-08-31 | 江苏远方动力科技有限公司 | A kind of low-silver copper-base high-performance solder and preparation method thereof |
| CN113843546A (en) * | 2021-09-23 | 2021-12-28 | 金华市金钟焊接材料有限公司 | CuPSnAg Ni-Re ultra-silver solder, preparation method and application |
| CN114131241A (en) * | 2021-12-06 | 2022-03-04 | 浙江亚通焊材有限公司 | Bronze welding flux for tunnel furnace and welding method |
| CN114131241B (en) * | 2021-12-06 | 2023-02-24 | 浙江亚通新材料股份有限公司 | Bronze welding flux for tunnel furnace and welding method |
| CN114986023A (en) * | 2022-06-02 | 2022-09-02 | 杭州华光焊接新材料股份有限公司 | Process for prefabricating low-melting-point brazing filler metal, low-melting-point brazing filler metal and preparation method thereof |
| CN115283880A (en) * | 2022-06-20 | 2022-11-04 | 郑州机械研究所有限公司 | Copper-phosphorus welding wire for brazing copper alloy mirror frame and preparation method and preparation system thereof |
| CN115283880B (en) * | 2022-06-20 | 2023-08-15 | 郑州机械研究所有限公司 | Copper-phosphorus bonding wire for brazing copper alloy eyeglass frame, and preparation method and preparation system thereof |
| US12103113B2 (en) | 2022-06-20 | 2024-10-01 | Zhengzhou Research Institute Of Mechanical Engineering Co., Ltd. | Copper-phosphorus brazing wire for brazing copper alloy spectacle frame as well as preparing method and system thereof |
| CN117076892A (en) * | 2023-10-13 | 2023-11-17 | 广东美的制冷设备有限公司 | Solder design method, apparatus, and computer-readable storage medium |
| CN117076892B (en) * | 2023-10-13 | 2024-01-23 | 广东美的制冷设备有限公司 | Solder design method, apparatus, and computer-readable storage medium |
| CN117486629A (en) * | 2024-01-02 | 2024-02-02 | 福建毫米电子有限公司 | Method for manufacturing nitride ceramic copper-clad plate through low-temperature brazing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103624418B (en) | 2015-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103624418B (en) | A kind of low silver copper-base filler metals and preparation method thereof | |
| CN101786208B (en) | Novel active copper-phosphorus brazing alloy | |
| CN101780613B (en) | Special rare earth alloy silver-brazing filler metal | |
| CN102601542B (en) | A kind of brazing solder alloy | |
| CN101524798B (en) | Low silver copper base medium temperature brazing filler metal | |
| CN100579707C (en) | Silver-based cadmium-free medium-temperature solder and preparation method thereof | |
| CN101716702B (en) | Multi-component alloy cadmium-free low-silver solder | |
| CN102240870A (en) | Multielement rare-earth silver solder | |
| CN105149813A (en) | Low-silver-copper-phosphorus brazing material containing trace indium | |
| CN101130220A (en) | Solder without cadmium and silver | |
| CN101716705A (en) | Multi-alloy cadmium-free phosphor-free copper-based solder | |
| CN103624415A (en) | Boron-containing stannum-based lead-free solder and manufacturing method thereof | |
| CN1616182A (en) | A kind of medium temperature Ag-based solder and preparation method thereof | |
| CN100408255C (en) | Cadmium-free silver solder containing indium and cerium | |
| CN104339099A (en) | Medium-temperature solder containing copper and copper alloy | |
| CN100463763C (en) | A copper-phosphorus-silver solder containing gallium, indium and cerium | |
| CN102581514B (en) | Silver solder containing phosphorus, stannum and rare earth | |
| CN102689105B (en) | Indium-containing active copper-based solder | |
| CN101733578A (en) | Lead-free solder for high-temperature soldering | |
| CN115533366B (en) | High-tin rare earth copper-phosphorus solder and preparation method thereof | |
| CN103480979B (en) | Containing the copper-phosphorus brazing alloy of hafnium zirconium cobalt | |
| CN101879667A (en) | Universal low-silver leadless electronic brazing filler metal | |
| CN101524793B (en) | Cadmium-free silver filler containing lithium and niobium | |
| CN107538149B (en) | A kind of Sn-Cu-Co-Ni lead-free solder and preparation method thereof | |
| CN103358048A (en) | Silver, copper and phosphorus system vacuum brazing filler |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |