CN102632237B - Method for manufacturing pure copper/ copper-chromium alloy composite contact material by spray deposition - Google Patents
Method for manufacturing pure copper/ copper-chromium alloy composite contact material by spray deposition Download PDFInfo
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Abstract
The invention provides a method for manufacturing a pure copper/ copper-chromium alloy composite contact material by spray deposition. The method concretely comprises the steps of: based on pure copper as a base material, putting two metals namely 70-80% of Cu and 20-30% of Cr into a spray deposition medium-frequency induction furnace according to the weight percent; vacuumizing, and melting under the protection of high-purity argon; injecting molten Cu-Cr alloy solution into a liquid delivery tube; adopting inert gas to crush and atomize the alloy solution flow out from the liquid delivery tube, and leading the alloy solution to deposit on a pure copper plate base body which is treated in advance; and finally, forming a Cu-Cr alloy layer firmly combined with the copper base body. The pure copper/ copper-chromium alloy composite material is used for a contact, the central part of the material maintains the good electrical and thermal conductivity of pure copper, and the surface Cu-Cr alloy layer fully exerts the performance characteristics of high current breaking capacity, high voltage resistance, good fusion welding resistance, low arc burning loss rate, low contact abrasion, etc.
Description
technical field:
The invention belongs to metal material technical field, be specifically related to a kind of method that jet deposition is manufactured pure copper/copper chromium alloy composite contact material.
background technology:
For vacuum circuit breaker electrical contact, its desirable material should have following performance: 1. high electric current breaking capacity; 2. the high voltage capability of bearing; 3. high conductance and thermal conductivity; 4. resistance fusion welding can be good; 5. low electrical arc erosion rate; 6. low contact abrasion; 7. low shut off value; 8. good processing characteristics.Owing to being conflicting between these performances, in actual application, be often subject to the impact of various factors, and can not meet above indices simultaneously.
According to the performance requirement of vacuum contact material, although fine copper possesses high conductance and thermal conductivity and good processing characteristics, mechanical strength is low, resistance to wear, anti-galvanic corrosion and resistance fusion welding poor, for making vacuum contact material, it obviously shows the deficiency of self.
The Cu-Cr alloy of high-Cr (15% ~ 50%, mass fraction) is considered to desirable contact material always.It is advantageous that, between Cu and Cr, there is very little mutual solubility, from Cu-Cr alloy phase diagram, during 1080 ℃ of the solid solubility of Cr in Cu, only have 0.7%, almost insoluble in the time of 600 ℃, thereby make Cu and Cr all fully retain good separately performance, that is: there is the Cu constituent element compared with low melting point, high conductivity and thermal conductivity, be conducive to improve the breaking capacity of vacuum switch; Cr constituent element has higher fusing point, can impel alloy substrate grain refinement, be conducive to form stable hardening constituent even, that disperse distributes, thereby can keep the high conductivity of material, can improve its connecting-disconnecting function and mechanical property again, and be difficult for producing thermionic emission.This material possesses good proof voltage, anti-scorching, anti-melting welding and the low characteristic such as dam.But its inferior position is, the adding of Cr element in copper, must weaken electric conductivity and the thermal conductivity of fine copper, take that to reduce the conductance of fine copper and thermal conductivity be cost.In addition, because Cu-Cr alloy belongs to monotectic, be associated gold, the Cu-Cr alloy gross segregation that adopts common method of smelting to prepare is serious.In order to address this problem, current countries in the world are prepared Cu-Cr alloy and are mainly contained three kinds of methods: 1) powder metallurgic method, the Cr powder of main component and a certain proportion of Cu powder are evenly mixed, and through colding pressing and hot pressed sintering shaping, be prepared into block contact material; 2) infiltration method, by appropriate Cu powder and all Cr powder make precast framework, then utilize gravity under vacuum to infiltration cu in skeleton; 3) vacuum arc melting method, is pressed into consutrode rod base by a certain proportion of Cu powder and Cr powder, and then preparation has the contact material of rapid solidification tissue.First two method, owing to being subject to the restriction of larger-size Cr particle in raw material, is difficult to obtain high-quality contact material, and yield rate is lower simultaneously; And vacuum arc melting method complicated process of preparation, cost is high, and much technological parameter need to further be groped and be perfect.
Utilize spray forming technology to prepare Cu-Cr alloy contact material, deposition blank density high (more than 95%), there is typical rapid solidification tissue, second-phase Cr particle is tiny, size uniform, be distributed in to disperse on Cu matrix, can increase substantially the electric property such as electric current breaking capacity, withstand voltage properties, anti-electrical breakdown performance of material, can successfully prepare whole Cu-Cr alloy contact material at present.But because wearing and tearing and the galvanic corrosion of contacts of vacuum switch mainly occurs in surface, be that vacuum contact has the Cu-Cr layer that 0.8-1.2mm is thick can meet instructions for use, if can utilize on fine copper surface spray forming technology to prepare certain thickness Cu-Cr alloy-layer, form Cu/Cu-Cr composite contact material, can make full use of fine copper and Cu-Cr alloy advantage performance separately.Through retrieval, about prepare the method for pure copper/copper chromium alloy composite contact material in fine copper jet surface deposition, have not been reported.
summary of the invention:
The object of the invention is the advantages and disadvantages for whole fine copper and Cu-Cr alloy, and provide a kind of jet deposition to manufacture the method for pure copper/copper chromium alloy composite contact material, specifically, to take fine copper as matrix material, adopt spray-deposition method, under the effect of high pressure high-purity argon gas, by after the atomization of Cu-Cr alloy solution, be deposited on fine copper substrate surface, form fine copper/Cu-Cr alloy composite materials.Fine copper/Cu-Cr the alloy composite materials obtaining with the present invention is for contact, its heart portion keeps the good electrical and thermal conductivity performance of fine copper, and surface C u-Cr alloy-layer fully represents its high electric current breaking capacity, high voltage capability, good resistance fusion welding energy, low electrical arc erosion rate and the low performance characteristics such as contact abrasion of bearing.
Technical scheme of the present invention is achieved in that
Jet deposition is manufactured the method for pure copper/copper chromium alloy composite contact material, and the method comprises the following steps:
The first step, fine copper plate surface degreasing is purified, sandblast roughening, makes it to expose after fresh matrix, is placed in spray atomization & deposition indoor, and simultaneously by Cu, two kinds of metal materials of Cr are Cu70-80% by weight percentage, and Cr20-30% puts into jet deposition intermediate frequency furnace;
Second step, banking Hou Jiang settling chamber are evacuated to 10
-2-10
-1pa;
The 3rd step, by the Cu being placed in jet deposition intermediate frequency furnace, Cr metal material is fusing under high-purity argon gas protection, smelting temperature is 1750 ℃-1850 ℃;
The 4th step, the Cu-Cr alloy solution of fusing is injected in catheter, adopt inert gas by the alloy solution flowing out from catheter pulverize, atomization, deposit on pretreated fine copper board substrate, thickness is 2-4mm;
The 5th step, at 800 ℃, carry out compactly extruding processing, according to contact dimensional requirement, carry out machined.
Further, the described first step processes fine copper plate surface degreasing to refer to, cleans fine copper treat deposition surface with acetone, reach surface degreasing and purify object.
Further, the described first step is processed the roughening of fine copper plate surface sand-blasting to refer to, fine copper surface is treated to deposition site granularity is 25 object palm fibre corundum, under 0.3 ~ 0.5MPa compressed air, sample is carried out to blast, clean and roughening processing, 45 ° of sandblast angles, sandblast is apart from 200mm, so that removal surface film oxide, and make surperficial roughening, be conducive to improve the combination of sedimentary deposit and fine copper base material.
Further, the raw metal of the described first step is selected tough cathode and pyrolysis Cr.
Further, the 4th described step jet deposition is to complete on high vacuum high-temperature injection former, atomization gas is high-purity Ar, atomizing pressure is 0.8 ~ 1.2MPa, receiving range is 400 ~ 600mm.
Further, described 800 ℃ are carried out compactly extrudingization and process and refer to; fine copper/Cu-Cr alloy composite materials after reaction-injection moulding is preheated to 800 ℃ in argon shield stove, then in stove, takes out rapidly, put into die; on 300t hydraulic press, push, exerting pressure is 1.4 * 10
5n, so that Cu-Cr sedimentary deposit dense structure.
good effect of the present invention is:
1, jet deposition Cu-Cr alloy-layer of the present invention, main component is copper, has close physical parameter with base material fine copper, and wetability is good, and affinity is high, and before jet deposition, fine copper base material has carried out purification roughening processing, and coating adhesion is strong.
When 2, the alloy solution through pulverizing, atomization of the present invention is deposited on fine copper substrate surface, due to the effect of moment high temperature, can make fine copper substrate surface occur micro-molten, fine copper base material and Cu-Cr alloy-layer form firmly metallurgical binding; After high temperature extrusion densification, bond strength, compactness further promote.
3, the electrical contact material that adopts the present invention to make, its heart portion keeps the good electric conductivity of fine copper, surface possesses electric current breaking capacity that Cu-Cr alloy is high, high voltage capability, good resistance fusion welding energy, low electrical arc erosion rate and the low combination properties such as wear rate of bearing, and can also save the chromium resource that price is relatively high.
4, the associativity at the prepared fine copper/Cu-Cr alloy composite plate interface of the present invention, electric conductivity, electrical erosion resistance are excellent.
the specific embodiment:
Below in conjunction with embodiment, the present invention is described in further detail.
embodiment 1:
The fine copper sheet material that the thickness of take is 5mm is example, at its surface atomizing deposition one deck Cu-Cr wear resistant anti-electric corrosion alloy.
Jet deposition is manufactured the method for pure copper/copper chromium alloy composite contact material, and the method comprises the following steps:
The first step, by the fine copper plate surface of 5mm with acetone except oil purification, by granularity, be 25 object palm fibre corundum, under 0.3MPa compressed air, sample carried out to blasting treatment, 45 ° of sandblast angles, sandblast is apart from 200mm, so that removal surface film oxide, and make surperficial roughening, be conducive to improve the combination of sedimentary deposit and fine copper base material, make it to expose after fresh matrix, be placed in spray atomization & deposition indoor, simultaneously by Cu, two kinds of metal materials of Cr are put into jet deposition intermediate frequency furnace by weight Cu80%, Cr20%;
Second step, banking Hou Jiang settling chamber are evacuated to approximately 10
-2pa;
The 3rd step, by the Cu being placed in jet deposition intermediate frequency furnace, Cr metal material is fusing under high-purity argon gas protection, smelting temperature is 1750 ℃;
The 4th step, the Cu-Cr alloy solution of fusing is injected in catheter, adopt the high-purity Ar atomization gas that pressure is 0.8MPa, by the alloy solution flowing out from catheter pulverize, atomization, deposit on pretreated fine copper board substrate, thickness is 2mm, and receiving range is 400mm;
The 5th step, on 300t hydraulic press, carry out compactly extruding processing after the fine copper/Cu-Cr alloy composite materials after reaction-injection moulding is preheated to 800 ℃ in argon shield atmosphere, exerting pressure is 1.4 * 10
5n, carries out machined according to contact dimensional requirement.
embodiment 2:
The fine copper sheet material that the thickness of take is 8mm is example, at its surface atomizing deposition one deck Cu-Cr wear resistant anti-electric corrosion alloy.
Jet deposition is manufactured the method for pure copper/copper chromium alloy composite contact material, and the method comprises the following steps:
The first step, by the fine copper plate surface of 8mm with acetone except oil purification, by granularity, be 25 object palm fibre corundum, under 0.4MPa compressed air, sample carried out to blasting treatment, 45 ° of sandblast angles, sandblast is apart from 200mm, so that removal surface film oxide, and make surperficial roughening, be conducive to improve the combination of sedimentary deposit and fine copper base material, make it to expose after fresh matrix, be placed in spray atomization & deposition indoor, simultaneously by Cu, two kinds of metal materials of Cr are put into jet deposition intermediate frequency furnace by weight Cu75%, Cr25%;
Second step, banking Hou Jiang settling chamber are evacuated to approximately 5 * 10
-2pa;
The 3rd step, by the Cu being placed in jet deposition intermediate frequency furnace, Cr metal material is fusing under high-purity argon gas protection, smelting temperature is 1800 ℃;
The 4th step, the Cu-Cr alloy solution of fusing is injected in catheter, adopt the high-purity Ar atomization gas that pressure is 1.0MPa, by the alloy solution flowing out from catheter pulverize, atomization, deposit on pretreated fine copper board substrate, thickness is 3mm, and receiving range is 500mm;
The 5th step, on 300t hydraulic press, carry out compactly extruding processing after the fine copper/Cu-Cr alloy composite materials after reaction-injection moulding is preheated to 800 ℃ in argon shield atmosphere, exerting pressure is 1.4 * 10
5n, carries out machined according to contact dimensional requirement.
embodiment 3:
The fine copper sheet material that the thickness of take is 10mm is example, at its surface atomizing deposition one deck Cu-Cr wear resistant anti-electric corrosion alloy.
Jet deposition is manufactured the method for pure copper/copper chromium alloy composite contact material, and the method comprises the following steps:
The first step, by the fine copper plate surface of 10mm with acetone except oil purification, by granularity, be 25 object palm fibre corundum, under 0.5MPa compressed air, sample is carried out to blasting treatment, 45 ° of sandblast angles, sandblast is apart from 200mm, so that removal surface film oxide, and make surperficial roughening, be conducive to improve the combination of sedimentary deposit and fine copper base material, make it to expose after fresh matrix, be placed in spray atomization & deposition indoor, simultaneously by Cu, two kinds of metal materials of Cr are put into jet deposition intermediate frequency furnace by weight Cu70%, Cr30%;
Second step, banking Hou Jiang settling chamber are evacuated to approximately 10
-1pa;
The 3rd step, by the Cu being placed in jet deposition intermediate frequency furnace, Cr metal material is fusing under high-purity argon gas protection, smelting temperature is 1850 ℃;
The 4th step, the Cu-Cr alloy solution of fusing is injected in catheter, adopt the high-purity Ar atomization gas that pressure is 1.2MPa, by the alloy solution flowing out from catheter pulverize, atomization, deposit on pretreated fine copper board substrate, thickness is 4mm, and receiving range is 600mm;
The 5th step, on 300t hydraulic press, carry out compactly extruding processing after the fine copper/Cu-Cr alloy composite materials after reaction-injection moulding is preheated to 800 ℃ in argon shield atmosphere, exerting pressure is 1.4 * 10
5n, carries out machined according to contact dimensional requirement.
Claims (1)
1. jet deposition is manufactured a method for pure copper/copper chromium alloy composite contact material, it is characterized in that: the method comprises the following steps:
The first step, fine copper plate surface degreasing is purified, sandblast roughening, sandblast roughening is processed and is referred to, fine copper surface is treated to deposition site granularity is 25 object palm fibre corundum, under 0.3 ~ 0.5MPa compressed air, sample is carried out to blast, clean and roughening is processed, 45 ° of sandblast angles, sandblast is apart from 200mm, so that removal surface film oxide, and make surperficial roughening, be conducive to improve the combination of sedimentary deposit and fine copper base material, make it to expose after fresh matrix, be placed in spray atomization & deposition indoor, simultaneously by Cu, two kinds of metal materials of Cr are Cu70-80% by weight percentage, Cr20-30% puts into jet deposition intermediate frequency furnace,
Second step, banking Hou Jiang settling chamber are evacuated to 10
-2-10
-1pa;
The 3rd step, by the Cu being placed in jet deposition intermediate frequency furnace, Cr metal material is fusing under high-purity argon gas protection, smelting temperature is 1750 ℃-1850 ℃;
The 4th step, the Cu-Cr alloy solution of fusing is injected in catheter, adopt inert gas by the alloy solution flowing out from catheter pulverize, atomization, deposit on pretreated fine copper board substrate, jet deposition is to complete on high vacuum high-temperature injection former, atomization gas is high-purity Ar, atomizing pressure is 0.8 ~ 1.2MPa, and receiving range is 400 ~ 600mm, and thickness is 2-4mm;
The 5th step, at 800 ℃, to carry out that compactly extrudingization processes be that the fine copper/Cu-Cr alloy composite materials after reaction-injection moulding is preheated to 800 ℃ in argon shield stove; then in stove, take out rapidly; put into die, on 300t hydraulic press, push, exerting pressure is 1.4 * 10
5n, so that Cu-Cr sedimentary deposit dense structure carries out machined according to contact dimensional requirement.
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| CN201210153453.9A CN102632237B (en) | 2012-05-17 | 2012-05-17 | Method for manufacturing pure copper/ copper-chromium alloy composite contact material by spray deposition |
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| CN103834895B (en) * | 2014-04-01 | 2016-12-07 | 河南理工大学 | Spray atomization and deposition prepares the method for titanium nitride coating |
| CN106735207B (en) * | 2016-12-13 | 2018-06-15 | 合肥工业大学 | A kind of preparation method of high-compactness Cu/CuCr gradient composites |
| CN111799116B (en) * | 2020-06-22 | 2022-06-07 | 陕西斯瑞新材料股份有限公司 | Preparation method of rapidly-formed copper-chromium composite contact |
| CN113278963B (en) * | 2021-04-28 | 2022-12-20 | 陕西斯瑞新材料股份有限公司 | Copper-chromium alloy end ring prepared by cold spray forming and preparation method thereof |
| CN114226734B (en) * | 2021-12-17 | 2023-07-14 | 北京工商大学 | Copper-containing wear-resistant coating for additive manufacturing titanium alloy surface and preparation process thereof |
| CN114921634B (en) * | 2022-05-23 | 2023-05-23 | 河北科技大学 | Copper-chromium composite material and preparation method thereof |
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Inventor after: Yuan Qinglong Inventor after: Fan Guangxin Inventor after: Zhang Baoqing Inventor after: Deng Xiaoling Inventor before: Yuan Qinglong Inventor before: Fan Guangxin Inventor before: Zhang Baoqing Inventor before: Deng Xiaoling |
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