CN101562081A - Silver-saving laminating composite contact terminal piece and preparation method thereof - Google Patents
Silver-saving laminating composite contact terminal piece and preparation method thereof Download PDFInfo
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- CN101562081A CN101562081A CNA2008100936637A CN200810093663A CN101562081A CN 101562081 A CN101562081 A CN 101562081A CN A2008100936637 A CNA2008100936637 A CN A2008100936637A CN 200810093663 A CN200810093663 A CN 200810093663A CN 101562081 A CN101562081 A CN 101562081A
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Abstract
The invention relates to a silver-saving laminating composite contact terminal piece and a preparation method thereof. The silver-saving laminating composite contact terminal piece comprises four layers of structure materials of a silver oxide layer, a transition silver layer, a conducting pure copper layer and a welding layer, wherein the silver oxide layer is an AgSnO or AgCdO material prepared by a powder metallurgic method, the second-phase oxide of the silver oxide layer is uniformly distributed in the whole metallurgical structure, and the vicinity in the middle of the silver oxide layer has no poor oxide bands. Because the silver oxide layer can be fully used in the turn-on and turn-off process of the piece, the silver-saving effect of the material reaches 20 percent-40 percent, and the electrical performance and the mechanical performance of the material are equal to and even better than those of a material with an original design structure. The silver-saving laminating composite contact terminal piece is manufactured according to the following steps: firstly, a silver-based composite material plate or band is extruded by powder metallurgy, isostatic pressing and sintering; secondly, the laminating composite material is prepared by a controlled atmosphere thermal compounding method; and finally, the piece is prepared by a thickness rolling and punch forming procedure of a finished product.
Description
Technical field
The present invention relates to a kind of stratiform composite contact sheet spare that saves silver and preparation method thereof, be mainly used in electrical contact material and manufacturing thereof in the low voltage electrical apparatus industry.
Background technology
The electric equipment products of the medium and small electric current of low voltage electrical apparatus industry use silver-based material as its contact material mostly at present.This contact material has selected to have that electrical and thermal conductivity is good, again the silver of certain anti-galvano-cautery to be arranged be main matrix, but fine silver hardness is too low, wear resistance is relatively poor, therefore on silver matrix, generally need to add MeO (metal oxide) second phase, just can prepare satisfy good, the anti-electrical arc erosion of resistance fusion welding and mar proof good electrically contact application requirements.Wherein traditional silver-based material mostly is Agcdo greatly, and along with the environmental requirement of increasingly stringent, silver tin oxide material is also replacing Agcdo gradually.But no matter be Agcdo or silver tin oxide material, because the oxide that wherein exists has hindered being connected of this contact material and other material parts, in actual use all need be at the multiple last layer weld layer material of the one side (another side is then for electrically contacting functional layer) of these silver-based materials, to satisfy the effect that is welded to connect of this contact blade spare and all the other material parts, this weld layer material is generally fine silver or the silver alloy good with the silver-based material connectivity, and promptly the electric contact piece spare in the practical application is the two-layer layer structure of silver oxide layer/weld layer.The present conventional process for preparing this stratiform composite contact sheet spare is to make and the corresponding silver alloy of siluer metal oxide with smelting process earlier, for example the siller tin oxide correspondence be silver-colored tin indium (wherein promoting the oxidation of tin must add phosphide element) alloy, the Agcdo correspondence then be silver-cadmium alloy; Then silver alloy and fine silver (or silver alloy) are combined into the sheet material or the band of double-layer structure.Sheet material or band process finished product rolling process become the thickness of final products, strike out the size of final contact blade spare then, carry out 600 ℃～700 ℃, 10 in the oxidation at last in high pressure
-1～10
2MPa oxygen is pressed, the not high pressure oxidation processing of equal time in several hours to tens hours.The technology of this preparation silver oxide contact blade spare commonly used is called as the alloy inner oxidation method.This method technology is simple thereby adopted in a large number, but can't avoid " poor oxide bright band " phenomenon (seeing accompanying drawing 1) in the middle of the silver oxide layer that the alloy inner oxidation technical process must occur: the distribution of metal oxide is in the middle of layer carefully to slightly gradually from laminar surface, and presents banded white bright sample because of oxide-free in the middle of the layer.Oxygen overall balance result of symmetrical diffusion process in the export-oriented layer is relevant simultaneously to the external symmetry diffusion for alloying element in the formation of poor oxide strip and the silver alloy oxidizing process.Existing a large amount of experimental evidences show, with the alloy inner oxidation method prepare contact blade spare in the switch on and off process, when frequent repeatedly arcing make the silver oxide layer wear up in the middle of near the poor oxide strip time, this contact material is oxide-free arc extinguishing or opposing galvanic action and cause contact sticking dead therefore the time, promptly electrically contact function complete failure, this in fact also means simultaneously will have the silver oxide layer that accounts for about a nearly half thickness to be wasted.Silver itself add silver-colored in recent years valency and be in sharply soaring situation always, and the application of contact material all will consume a large amount of silver every year as the precious metal material, and the technology that therefore saves silver-colored aspect is subjected to extensive concern always.Yet for the alloy inner oxidation method, no matter be to add element or increase oxygen to press, or other application technology can't realize still that at present mass production do not have the silver oxide type stratiform composite contact sheet spare of poor oxide strip.Therefore, how to realize that it is the important directions of the silver-colored engineering and technological research of joint that silver oxide layer in the stratiform composite contact sheet spare is fully utilized.
In addition, domestic in recent years some patents of invention of having reported silver-economizing low-voltage electrical-appliance contact materials, as to represent patent be " silver-economizing low-voltage electrical-appliance contact materials " (patent No. is 200610046594.5) for " copper base low-voltage electrical apparatus electrician contact alloy material " (patent No. 94102452.0) and patent.It is the alloy material of matrix that these patents are with copper, the element that adds mainly comprises cadmium, ceria, lanthanum sesquioxide, diadust, silver, in any case but this design added elements all can't change the essence of material based on the copper matrix, thereby the anti-galvanic corrosion of copper main defect poor, the oxidation resistance difference the silver based contact material (practical application proof copper-based electrical contact material under the big current conditions more than the 15A all can not use) that makes these copper-base contact materials still can't replace low-voltage electrical apparatus to a great extent to use.
Summary of the invention
The objective of the invention is to: avoid the appearance of the poor oxide strip in centre of silver oxide layer fully, the enough quilts of function that electrically contact of silver oxide layer are utilized cmpletely in the stratiform composite contact sheet spare thereby make, the final significantly silver-colored effect of joint that realizes.
Technical scheme of the present invention is achieved in that this silver-saving laminating composite contact terminal piece is made of the four-layer structure material of silver oxide layer/mistake silver-plating layer/conduction pure copper layer/weld layer, substitutes the double-layer structure material design of original silver oxide/weld layer.Wherein, the silver oxide layer is siller tin oxide or the silver cadmium oxide material with the powder metallurgic method preparation.The manufacturing process of this silver-saving laminating composite contact terminal piece is at first by static pressure-sintering such as powder metallurgy-wait-squeeze out silver oxide material sheet material or band, prepare laminar composite through the hot composite algorithm of controlled atmosphere again, after finished product thickness is rolling and the punch forming operation is made sheet spare.
Well-knownly be, why low-voltage electrical apparatus prepares with the alloy inner oxidation method with the compound silver contact of stratiform at present, what mainly consider is materials processing, be material before interior oxidation because for single-phase alloy (for example silver-colored tin-indium alloy, silver-cadmium alloy), there is not the second phase strengthening mechanism in its material structure, make its working plasticity excellence, help the laminar composite that processing and preparing obtains final size, oxidation operation can obtain being directly used in the contact blade spare that is assembled on the electric equipment products in carrying out at last again.But as previously mentioned, oxidation operation is inevitable in carrying out after processing again poor oxide bright band occurs in the centre position of material physical dimension, and the appearance of the poor oxide strip in this centre has caused the anti-melting welding ability of contact sharply to descend, and loses efficacy until adhesion occurring.This means that also remaining half the silver oxide layer of thickness that is about can not obtain electrically contacting application on the function, promptly can't avoid a large amount of waste noble metals silver of alloy internal oxidation material.
And the another kind of preparation method of silver oxide material is a powder metallurgic method.It has the evenly characteristics of (the oxide second-phase dispersion distributes, and sees accompanying drawing 2) of metallographic structure, because microstructure decision performance, so the performance of each regional area of material also tends to uniformity consistency.Be applied to the laminar composite structure Design that low-voltage electrical apparatus is used if powder metallurgic method can be prepared the silver oxide material that, because local organization non-uniform phenomenon such as poor oxide strip in the middle of the silver oxide layer does not have, thereby promptly be equivalent to electrically contacting function and can being fully used and reaching the silver-colored effect of remarkable joint of whole silver oxide layer.This moment, we can (refer to: the silver oxide layer for preparing with powder metallurgic method) with the material of the silver oxide layer thickness about 50% that is equivalent to former design (with alloy inner oxidation method preparation), the performance that just can realize unitary pieces meets or exceeds intrinsic electric life requirement, certainly in order to ensure the electric life of unitary pieces involved in the present invention, the general silver oxide layer thickness of selecting is about 50%～70% of intrinsic material respective thickness.When the internal structure of low-pressure electronic equipment product designs under the immovable situation, when promptly requiring the gross thickness of contact material to change, the mentality of designing that saves silver-colored type stratiform composite sheet part is: in remarkable attenuation compound certain thickness pure copper material (compensating the thickness space that actual forfeiture unnecessary in the former design electrically contacts the silver oxide layer of function) on the basis of silver oxide material of bed thickness, between the two with thin fine silver layer (accounting for total thickness 5%) transition, and on the opposite side of pure copper layer is compound weld layer.As long as the electric arc when pure copper layer can not worked with sheet spare break-make directly contacts, because fine copper itself has than better conductivity of silver oxide and thermal conductivity (meaning that the more intrinsic electrical and thermal conductivity of material of the present invention better helps reducing contact temperature rise), such design both can guarantee the general shape size constancy of material, the electrical property that can make integral material again near in addition surpass former (with the preparation of alloy inner oxidation method) design, promptly finally realized the silver-colored effect of remarkable joint with the mode of copper material thickness compensation.Account for total thickness by silver oxide layer in the former project organization and be about 85%～90%, and silver content is about 85%～90% in the silver oxide, convert out the more former design joint of material involved in the present invention silver amount and be about 20%～40%.
In order to realize material structure design of the present invention, preparation method's step is as follows:
At first must be ready to the compound preceding group element material that is useful on: silver oxide, fine silver, copper, wlding.Fine silver, copper, wlding all are buyings very easily or produce the raw material of realizing; Silver tin oxide material then adopts conventional powder metallurgic method preparation, and its basic production flow process is: static pressure-sintering such as powder-processed-wait-be squeezed into silver oxide sheet material or band.
Subsequently, the present invention adopts the hot composite algorithm of a kind of controlled atmosphere to realize the firmly compound of silver oxide/fine silver/four kinds of group element materials of copper/wlding.Compound is a kind of in constituent element near interface input higher-energy and the plastic deformation by each constituent element moderate finite deformation amount, makes the process that forms firm Physical Metallurgy bonding between constituent element.In fact involved in the present invention four layer by layer the realization key of the production in enormous quantities of shape structural composite material also be its combination process, and the hot composite algorithm of controlled atmosphere exactly is fit to the recombination process of the layer structure material of being made up of different constituent elements involved in the present invention very much, and be characterized in: 1, different constituent elements can be realized machinability and the reduction resistance of deformation of independent heating temperature control to guarantee recombination process.Owing in the group element material involved in the present invention the very poor silver oxide material of cold-forming property (it has good processing characteristics in 250 ℃ ~ 450 ℃) is arranged, and other fine silver, copper and wlding also have different optimal process temperature range, and (temperature that definition here not only had been not easy oxidation but also the working plasticity ability is increased largely is the optimal process temperature, for example silver can be selected 100 ℃ ~ 200 ℃, selecting copper is 200 ℃～300 ℃), therefore to realize that the compound rolling temperature of each group element material that must make of project organization material of the present invention can independently control, the present invention choose four group element materials rolling compound before respectively by four groups of continuous heaters, all can reach the purpose that group element material independently heats temperature control.2, constituent element logical controlled atmosphere protection in entering rolling recombination process helps the compound of interface between constituent element.Realize the Physical Metallurgy bonding; to treat also must guarantee when compound material constantly forms fresh interface (this also the purpose of plastic deformation) just that this fresh interface forms afterwards a period of time not oxidized making; this is even more important to hot recombination process; because the formation that oxide layer that high temperature easily generates down or oxide will hinder compound interface; therefore in rolling hot recombination process, feed the fresh interface that wherein a kind of atmosphere such as hydrogen, decomposed ammonia, inert gas all help protective material, i.e. compound between constituent element.Therefore, adopt the hot composite algorithm of controlled atmosphere can realize producing in enormous quantities the layer structure composite material (seeing accompanying drawing 3) of (the powder metallurgic method preparation) silver oxide/mistake silver-plating layer/fine copper/welding material fully.
The layer structure composite plate of compound good silver oxide/mistake silver-plating layer/fine copper/welding material or band need be the finished product thickness size through hot rolling also, after punch ram is made the contact blade spare of user's necessary requirement specification.
Description of drawings
The present invention is further described below in conjunction with accompanying drawing.
Fig. 1 is the stratiform composite contact sheet spare cross section metallographic structure with the preparation of alloy inner oxidation method.
Fig. 2 saves silver-colored type (poor oxide strip in the middle of not having) stratiform composite contact sheet spare cross section metallographic structure.
Fig. 3 silver-saving laminating composite contact terminal piece structure chart of the present invention
1. middle poor oxide strips, 2. the silver oxide layer of powder metallurgic method preparation, 3. fine silver transition zone, 4. fine copper, 5. weld layer among the figure.
Embodiment
Embodiment 1:
Substitute intrinsic Agcdo (10)/fine silver stratiform composite contact sheet spare (total thickness 1.5mm, the specific embodiment of the invention of length * wide=5mm * 5mm).To account for the gross thickness ratio be 90% for Agcdo (10) layer in the stratiform composite contact sheet spare of former project organization, it is 10% that the fine silver layer then accounts for total thickness, and concrete enforcement of the present invention is designed to the purpose that the four-layer structure composite contact sheet spare of Agcdo (10)/fine silver/copper/fine silver can more former project organization reach remarkable joint silver.
Compare with the sheet spare of former project organization, it is all constant that the present invention specifically implements the sheet spare overall dimension of project organization, but the shared total thickness ratio of the Agcdo (10) of poor oxide strip feature layer is not reduced to 50% in the middle of wherein not having, the copper layer accounts for the total thickness ratio and is about 35%, transition fine silver layer total thickness ratio between copper layer and the Agcdo layer is about 5%, still is 10% and the welding fine silver layer of outermost accounts for the total thickness ratio.Amount to by the content of the silver-colored percentage by weight of each layer that the present invention is concrete to be implemented more former design joint silver and be about 31%.
The step of specifically preparing this enforcement project organization sheet spare is as follows.
At first adopt powder metallurgic method to prepare Agcdo (10) band.The concrete processing step of the specific embodiment of the invention is: 1, the powder pre-oxidation legal system is equipped with Agcdo (10) powder; 2, ball milling 2h, screening; 3, static pressure such as 250MPa goes out Agcdo (10) ingot that diameter is about 90mm; 4,800 ℃, 5 hours sintering; 5,880 ℃ to be hot extruded into thickness be that 6mm, width are Agcdo (10) sheet material or the band of 60mm.
Get Agcdo (10) band that squeezed out, outsourcing then and do other group element material (the outer welding of pure copper layer band, 1.2mm (thick) * 60mm (wide) that comprises 0.6mm (thick) * 60mm (wide) transition fine silver layer band, 4.2mm (thick) * 60mm (wide) with fine silver layer band) of processing slightly, it is compound that promptly four kinds of group element materials carry out heat on the controlled atmosphere thermal composite machine.The temperature that compound tense is controlled each constituent element is respectively: 300 ℃ of silver cadmium oxide materials, (two) fine silver material are 250 ℃ of 150 ℃, pure copper material; Controlled atmosphere is a purity nitrogen; Rolling recombination velocity is 5 meters/minute; The rolling deformation rate is 50%.Adopt above-mentioned technology to have the composite strip of Agcdo (10)/fine silver/copper/fine silver four-layer structure by the compound 6mm of going out (thick) * 60mm (wide).
Compound good band is the material that 350 ℃, four passages (25%, 30%, 30%, 31%) are made 1.5mm (thick) * 60mm (wide) through hot-rolled temperature again, after punch ram is made the contact blade spare that finally requires specification.
Embodiment
Embodiment 2:
Substitute intrinsic silver-tin oxide or indium oxide (oxide aggregate is 10%)/fine silver stratiform composite contact sheet spare (total thickness 1.5mm, the specific embodiment of the invention of length * wide=5mm * 5mm).To account for the gross thickness ratio be 90% to the silver-tin oxide or indium oxide layer in the stratiform composite contact sheet spare of former project organization, it is 10% that the fine silver layer then accounts for total thickness, and concrete enforcement of the present invention is designed to the purpose that the four-layer structure composite contact sheet spare of siller tin oxide (10)/fine silver/copper/fine silver can more former project organization reach remarkable joint silver, it is worthy of note because the present invention does not adopt the alloy inner oxidation method, therefore there is no need in silver-based material, to add indium and promote the oxidation of tin to finish, so also reached the purpose (the close prices silver of indium) of economizing indium.
Compare with the sheet spare of former project organization, it is all constant that the present invention specifically implements the sheet spare overall dimension of project organization, but the shared total thickness ratio of the siller tin oxide (10) of poor oxide strip feature layer is not reduced to 50% in the middle of wherein not having, the copper layer accounts for the total thickness ratio and is about 35%, transition fine silver layer total thickness ratio between copper layer and the Agcdo layer is about 5%, still is 10% and the welding fine silver layer of outermost accounts for the total thickness ratio.Amount to by the content of the silver-colored percentage by weight of each layer that the present invention is concrete to be implemented more former design joint silver and be about 30%.
The step of specifically preparing this enforcement project organization sheet spare is as follows.
At first adopt powder metallurgic method to prepare siller tin oxide (10) band.The concrete processing step of the specific embodiment of the invention is: be 10% proportional meter by the tin oxide weight content 1,, chemistry coats putty powder in silver nitrate, ammonia, hydrazine hydrate solution, prepares the siller tin oxide composite powder; 2, washing, 2 hours, 650 ℃ roasting 3h of 250 ℃ of dryings; 3, ball milling 5 hours, screening; 4, static pressure such as 250MPa goes out siller tin oxide (10) ingot that diameter is about 90mm; 5,800 ℃, 5 hours sintering; 5,850 ℃ to be hot extruded into thickness be that 6mm, width are siller tin oxide (10) sheet material or the band of 60mm.
Get siller tin oxide (10) band that squeezed out, outsourcing then and do other group element material (the outer welding of pure copper layer band, 1.2mm (thick) * 60mm (wide) that comprises 0.6mm (thick) * 60mm (wide) transition fine silver layer band, 4.2mm (thick) * 60mm (wide) with fine silver layer band) of processing slightly, it is compound that promptly four kinds of group element materials carry out heat on the controlled atmosphere thermal composite machine.The temperature that compound tense is controlled each constituent element is respectively: 350 ℃ of silver tin oxide materials, (two) fine silver material are 250 ℃ of 150 ℃, pure copper material; Controlled atmosphere is a purity nitrogen; Rolling recombination velocity is 5 meters/minute; The rolling deformation rate is 50%.Adopt above-mentioned technology to have the composite strip of siller tin oxide (10)/fine silver/copper/fine silver four-layer structure by the compound 6mm of going out (thick) * 60mm (wide).
Compound good band is the material that 350 ℃, four passages (25%, 30%, 30%, 31%) are made 1.5mm (thick) * 60mm (wide) through hot-rolled temperature again, after punch ram is made the contact blade spare that finally requires specification.
Claims (4)
1, a kind of silver-saving laminating composite contact terminal piece is characterized in that: the four-layer structure material by silver oxide layer/mistake silver-plating layer/conduction pure copper layer/weld layer constitutes.
2, by the described silver-saving laminating composite contact terminal piece of claim 1, it is characterized in that: the silver oxide layer is siller tin oxide or silver cadmium oxide material with the powder metallurgic method preparation, its oxide second evenly distributes in whole metallographic structure, near nothing " poor oxide strip " in the middle of the silver oxide layer.
3, by the described silver-saving laminating composite contact terminal piece of claim 1, the silver oxide layer it is characterized in that: owing to can be fully used in sheet spare make and break process, material saves silver-colored effect and reaches 20%～40%, and its electrical property then material with former project organization is suitable even higher.
4, a kind of manufacture method of silver-saving laminating composite contact terminal piece, it is characterized in that: manufacturing process is at first by static pressure-sintering such as powder metallurgy-wait-squeeze out silver-based composite material sheet material or band, prepare laminar composite through the hot composite algorithm of controlled atmosphere again, after finished product thickness is rolling and the punch forming operation is made sheet spare.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389981A (en) * | 2011-06-21 | 2012-03-28 | 佛山通宝精密合金股份有限公司 | Method for continuously and homogeneously preparing silver tin oxide material |
| CN103302126A (en) * | 2013-06-26 | 2013-09-18 | 温州宏丰电工合金股份有限公司 | Method for continuously extruding and compositing laminar composite electric contact material |
| CN104205282A (en) * | 2012-03-22 | 2014-12-10 | 田中贵金属工业株式会社 | Electrode material having clad structure |
| CN104272419A (en) * | 2012-05-07 | 2015-01-07 | 田中贵金属工业株式会社 | Electrode material for thermal-fuse movable electrode |
| CN104541351A (en) * | 2012-07-05 | 2015-04-22 | 多杜科有限公司 | Electromechanical low voltage switch |
| CN105453206A (en) * | 2013-08-06 | 2016-03-30 | 株式会社德力本店 | Electric contact point and contact element |
| CN105483598A (en) * | 2015-12-03 | 2016-04-13 | 浙江帕特尼触头有限公司 | Silver-copper base composite contact material and preparing technology |
| CN110504119A (en) * | 2019-08-21 | 2019-11-26 | 哈尔滨东大高新材料股份有限公司 | A kind of preparation method of silver-bearing copper composite electric contact material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389981A (en) * | 2011-06-21 | 2012-03-28 | 佛山通宝精密合金股份有限公司 | Method for continuously and homogeneously preparing silver tin oxide material |
| CN104205282A (en) * | 2012-03-22 | 2014-12-10 | 田中贵金属工业株式会社 | Electrode material having clad structure |
| CN104272419A (en) * | 2012-05-07 | 2015-01-07 | 田中贵金属工业株式会社 | Electrode material for thermal-fuse movable electrode |
| CN104272419B (en) * | 2012-05-07 | 2017-04-05 | 田中贵金属工业株式会社 | For the electrode material of Thermal Cutoffs movable electrode |
| CN104541351A (en) * | 2012-07-05 | 2015-04-22 | 多杜科有限公司 | Electromechanical low voltage switch |
| CN103302126A (en) * | 2013-06-26 | 2013-09-18 | 温州宏丰电工合金股份有限公司 | Method for continuously extruding and compositing laminar composite electric contact material |
| CN103302126B (en) * | 2013-06-26 | 2016-02-03 | 温州宏丰电工合金股份有限公司 | The method of the continuously extruded compound of lamellar composite contact material |
| CN105453206A (en) * | 2013-08-06 | 2016-03-30 | 株式会社德力本店 | Electric contact point and contact element |
| CN105453206B (en) * | 2013-08-06 | 2018-07-10 | 株式会社德力本店 | Electric contact and contact |
| CN105483598A (en) * | 2015-12-03 | 2016-04-13 | 浙江帕特尼触头有限公司 | Silver-copper base composite contact material and preparing technology |
| CN110504119A (en) * | 2019-08-21 | 2019-11-26 | 哈尔滨东大高新材料股份有限公司 | A kind of preparation method of silver-bearing copper composite electric contact material |
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| CN101562081B (en) | 2012-03-21 |
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Address after: 528131 F7, Block 5, No. 71 North District, Foshan Electronic and Electrical Industry Base, National Torch Plan, Baini Town, Sanshui District, Foshan City, Guangdong Province Patentee after: FOSHAN TONGBAO ELECTRICAL PRECISION ALLOY Co.,Ltd. Address before: 528000 No. three, No. 60, Zhangcha Road, Chancheng District, Guangdong, Foshan Patentee before: FOSHAN TONGBAO ELECTRICAL PRECISION ALLOY Co.,Ltd. |
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