CN100561621C - The silver-tungsten carbide base electric contact material of high resistance fusion welding and processing technology thereof - Google Patents
The silver-tungsten carbide base electric contact material of high resistance fusion welding and processing technology thereof Download PDFInfo
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- CN100561621C CN100561621C CNB2006100405107A CN200610040510A CN100561621C CN 100561621 C CN100561621 C CN 100561621C CN B2006100405107 A CNB2006100405107 A CN B2006100405107A CN 200610040510 A CN200610040510 A CN 200610040510A CN 100561621 C CN100561621 C CN 100561621C
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Abstract
The invention discloses a kind of silver-tungsten carbide base electric contact material and preparation method of high resistance fusion welding.Electrical contact material main body composition comprises: tungsten carbide 45～73wt%, nickel be less than 0.05wt%, Yu Weiyin.The weld layer composition comprises: silver 40～60wt%, and copper 20～30wt%, surplus is that zinc or phosphorus are at least a.The tungsten carbide particle particle diameter is 0.7～4 μ m.Tungsten carbide can adopt (W.Ti) C powder to substitute, and (W.Ti) ratio of tungsten carbide and titanium carbide is 7～8: 3～2 in the C powder.Adopt the present invention cheaply silver solder to be attached to the electrical contact product surface, it is more firm that scolder is engaged with electrical contact product matrix, reduces the quality problems risk that produces because of welding.This technology is not restricted to scolder is overlayed on the silver-colored tungsten carbide material.In fact, it is applicable to production sheet, band etc., and all contain the silver electric contact product, and the contact product is widely used on high pressure, low-voltage electrical apparatus and the vacuum switch of various grades.
Description
Technical field:
The present invention relates to a kind of metallic composite, particularly relate to a kind of material and processing technology thereof with isolation switch contact.
Technical background:
Vacuum circuit-breaker needs following requirement to contact: high current breaking capacity; Low shut off value; Voltage ability to bear preferably; Low and stable contact resistance and temperature rise; Than high abrasion and anti-melting welding ability; Yet these require contradiction each other, can not satisfy all these requirements with a kind of metal.Such as, current breaking capacity and shut off value are subjected to the influence of material melting point and vapour pressure.Vapour pressure height, alloy have very high tin shut off value, and on the contrary, then current breaking capacity can be subjected to tangible influence.Thereby, in the alloy material of a lot of practical applications, can be used in combination by complementary element to two kinds of its not enough performances of major general.
At present, in view of the diversity of load, more and more higher to the requirement of vacuum circuit-breaker.As be used for interrupting that faradic vacuum circuit-breaker is arranged, except requiring good voltage ability to bear, low and stable contact resistance and temperature rise, often require vacuum circuit-breaker to have contact material as requiring low shut off value and big current breaking capacity.
As the shut off value with you contact have: (bismuth-containing mostly is 0.5wt% or 10.0wt% etc. to the Guillaume metal of producing with melting method.The kuttern mechanism of action is identical with Guillaume metal, and characteristics are similar), with the copper chromium contact of sintering and infiltration method production.
The Guillaume metal contact, its shut off value can be guaranteed by the selective evaporation of bismuth, because bismuth has suitable vapour pressure.Meanwhile, bismuth exists with the form of separating on the crystal grain border, alloy is died down, thereby have anti-preferably melting welding ability.But bismuth has tangible negative interaction to the reactance voltage ability of alloy contact and the current breaking capacity of vacuum circuit-breaker.And along with the increase of access times, because of the volatilization of bismuth, the low performance of damming of alloy contact progressively degenerates.
For chromiumcopper, at high temperature chromium and copper have thermal characteristics preferably, contact material has excellent performance at anti-high pressure and high-current on-off aspect of performance, its discontinuous current performance (performance of damming) also shows quite good performance, but chromiumcopper resistance fusion welding can aspect be imperfect to miniaturization circuit breaker aspect, because of the operating mechanism that drives cu cr contact material needs bigger breakaway than the operating mechanism (miniaturization circuit breaker) with the Guillaume metal contact, waste economically, copper chromium makes alloy be used for large-scale switches such as vacuum load switch more.
Simultaneously, for a long time, the electrical contact product producer is responsible for making qualified product, uses the technology of merchant according to oneself, uses Ag-Cu-Zn or silver-bearing copper phosphorus scolder under the situation of adding scaling powder, and the contact product is welded on the copper stent.Because the Chang Yin of electrical equipment manufacturer is unfamiliar with the material property of contact, it is firm inadequately that the welding material that is adopted is engaged with electrical contact product matrix, and using influences power supply quality because of problems of welded quality often.
Summary of the invention:
The object of the present invention is to provide a kind of silver-colored diamondite contact material of high anti-melting welding, improve the serviceability and the useful life of contact, carry scolder simultaneously and make things convenient for the operation of electrical equipment manufacturer, this that scolder is engaged with electrical contact product matrix is more firm, reduces the quality problems risk that produces because of welding.Another object of the present invention is to provide the silver-colored diamondite preparation of contact material of high anti-melting welding.
The present invention is achieved in that a kind of silver-tungsten carbide base electric contact material of high resistance fusion welding, it is characterized in that, the main body composition comprises: tungsten carbide 45～73wt%, nickel be less than 0.05wt%, Yu Weiyin.The weld layer composition comprises: silver 40～60wt%, and copper 20～30wt%, surplus is that zinc or phosphorus are at least a.The tungsten carbide particle particle diameter is that 0.7～4 μ m. tungsten carbide can adopt (W.Ti) C powder to substitute, and (W.Ti) ratio of tungsten carbide and titanium carbide is 7～8: 3～2 in the C powder.
Realize the preparation method of the silver-tungsten carbide base electric contact material that this high resistance fusion welding can be high, may further comprise the steps:
1. at first silver powder, tungsten carbide powder are crossed sieve classification, selected specific particle diameter.
2. the silver powder that will have first particle diameter and the tungsten-carbide powder with second particle diameter are in 1～1.5: 9～8.5 ratio is mixed powder, by repeatedly (at least more than the secondary) repeatedly the processing of moulding crushing hot make A powder greater than the 3rd particle diameter of first, second particle diameter;
3. with adding the oxalates or the nitrate solution of nickel in the A powder, mix thoroughly, and dry processing, guarantee that the final composition of nickel is less than 0.05wt% when the oxalates of adding nickel or nitrate solution;
4. the powder compaction with above-mentioned oven dry is a shaping blank, and the shaping blank porosity can be adjusted porosity according to the ultimate constituent 30%～50% in scope;
5. in high temperature sintering furnace shaping blank is carried out preliminary treatment, pretreatment temperature is 850 ℃～1000 ℃, 5 minutes～120 minutes time, hydrogen atmosphere protection;
6. the blank after pre-burning being handled soaks burning, 2～3 hours time under 1100 ℃～1200 ℃ temperature;
7. will determine that the Ag-Cu-Zn of composition or silver-bearing copper phosphorus solder powder adopt mechanical means to carry out preliminary treatment, 400 ℃～450 ℃ annealing is 2～3 hours in hydrogen, the B powder, the B powder has laminated structure, or the powder with sheet should account for more than the 60wt% at least.
8. with at least a joining in terpinol or the glycerol in the group of methylcellulose, ethyl cellulose composition, the ratio in 1: 23～25 adds; 100 ℃～200 ℃ heat treatments, 30 minutes to 180 minutes time, be made into the organic substance slurry; By mechanical means the B powder is added in the organic substance slurry, mix thoroughly and obtain the scolder slurry, preserve being lower than under 10 ℃ the temperature;
9. the shaping blank that will soak the burnt together lattice neatly discharges, and above-mentioned scolder slurry evenly is coated in the shaping blank surface, and 300 ℃～650 ℃ stage intensification heat treatments in hydrogen, are carried out following process and got qualified electrical contact at 2～3 hours total times after the taking-up.
The present invention compared with prior art has following advantage:
Adopt the present invention cheaply silver solder to be attached to the electrical contact product surface, it is more firm that scolder is engaged with electrical contact product matrix, reduces the quality problems risk that produces because of welding.This technology is not restricted to scolder is overlayed on the silver-colored tungsten carbide material. and in fact, it is applicable to production sheet, band etc., and all contain the silver electric contact product, and the contact product is widely used on high pressure, low-voltage electrical apparatus and the vacuum switch of various grades.
Embodiment:
For silver-colored diamondite contact, it has the good low performance of damming, mainly be because: the having of WC helps the electronics emission; WC easily decomposes under arcing; Because the vibration of the electric field of emitting electrons,, and silver-coloredly has a higher vapour pressure because of the evaporation on the contact material surface that is heated obtains quickening.Can change the current breaking capacity and the shut off value of alloy contact by the content that changes anti-arc composition WC according to the data introduction, make contact reach the good comprehensive performance.Meanwhile, the size of preventing arc composition such as WC particle has clearly influence to the consistency of alloy material shut off value, and the material anti-pressure ability is also had negative influence.Because infiltrating factor between silver and the tungsten carbide, produce in the prior art of silver-colored tungsten carbide material, often add more sintering agent such as Fe Co and Ni, add sintering agent and help to obtain organizing more outstanding material, more obvious when especially adopting fine grain tungsten carbide powder to produce silver-colored tungsten carbide material, but in material, add too much sintering agent, can be because sintering agent forms a skim on preventing arc composition surface, thereby influence the hot electron heating, to the performance formation negative effect of material.
Through optimizing meticulously, adopted the granularity of the thin tungsten carbide powder of 0.7～4 μ m as the preventing arc composition.During the tungsten carbide powder fine size, cause difficult forming easily, molding blank mesopore rate is too high.Meanwhile, add or do not add as far as possible sintering agent less, production technology newly developed has adopted following two: 1. pair mixed powder is granulated, and granulates and takes moulding repeatedly, fragmentation and heat-treating methods, makes silver-colored composition and tungsten carbide burl form bigger particle together.When bigger particle has guaranteed moulding, the porosity of powder base and the percentage of head rice of base substrate.Meanwhile, because of bonding together of two kinds of compositions, the uniformity that guarantees the final tissue of material there is very big benefit.In fact, after handling by this technology, the distance in the material between the preventing arc composition particle has reached suitable effect of uniform.2. the base substrate after the moulding is carried out pre-burning and handle, pre-burning is handled and has been broken through the restriction of not crossing silver point in the prior art, has taked 850 ℃～1000 ℃ high temperature preliminary treatment.Guarantee that after pre-burning silver has been under the good wet face state with tungsten carbide particle, and follow-up soaking burnt a good induction.
Enclose the another breakthrough that one deck silver solder is this technology on the alloy material surface, mainly be based on following understanding and knowledge: will determine that the Ag-Cu-Zn of composition or silver-bearing copper phosphorus solder powder are processed into sheet, by the organic substance slurry is carrier, powder evenly is coated in product surface, by follow-up rational heat treatment, silver matrix in powder and the alloy is well become one, the high-quality when guaranteeing to weld.Simultaneously Related product has been saved the operation of preparation scolder, reduced human body and the harmful various interpolation auxiliary agents of environment.
During preparation, silver powder is crossed 500 mesh sieves, tungsten carbide powder carries out sorting, and getting particle diameter is the tungsten carbide powder of 0.8 μ m, and silver powder is mixed in 10: 90 ratio with tungsten carbide powder, adds to calculate good nickel oxalate solution, and the companion spares, oven dry.Powder is carried out heat-treating in 500 ℃/2 hours, with 6 tons/cm
2Pressure forming, fragmentation; Heat treatment in 600 ℃/2 hours is with 6 tons/cm
2Pressure forming, fragmentation; Heat treatment in 680 ℃/2 hours is with 6 tons/cm
2Pressure forming, fragmentation; At last with 7～8 tons/cm
2Pressure forming, the blank porosity is 41.2%.Pre-burning in 980 ℃/30 minutes is handled, and the blank after ready fine silver and the pre-burning is together soaked burning.
The Ag-Cu-Zn solder powder is carried out in the planetary ball mill ball milling 20 minutes, in hydrogen, handled 2 hours the sorting of sieving.To calculate accurately that ethyl cellulose joins in the terpinol, 150 ℃ of heat treatment 30 minutes is made into the organic substance slurry.By rolling mode the organic substance slurry is fully mixed with off-the-shelf solder powder, finished product scolder slurry, be stored in 4 ℃ the refrigerator standby.
The blank sign indicating number in good order that will soak the burnt together lattice is good, takes by weighing and calculates scolder slurry accurately, evenly applies.650 ℃ of heat treatment is 2 hours in hydrogen.Blank with scolder is suppressed, got finished product.
Produce the silver-colored tungsten carbide material that the tungsten carbide powder granularity is 1.0 μ m, 3.0 μ m and 4.0 μ m by same mode.
Material property is as follows:
| Sequence number | Ag | WC | Wc grain size μ m | Hardness MPa | Density g/cm 3 | Resistivity μ Ω .cm |
| 1 | 51.2 | 48.7 | 0.8 | 1751 | 12.48 | 3.15 |
| 2 | 50.3 | 49.65 | 1.0 | 1789 | 12.63 | 3.20 |
| 3 | 49.9 | 50.06 | 3.0 | 1902 | 12.55 | 3.17 |
| 4 | 50.2 | 49.76 | 4.0 | 1802 | 12.57 | 3.07 |
The successfully type approval test by the user of the silver-colored tungsten carbide material of Sheng Chaning according to the method described above.
Claims (2)
1. the silver-tungsten carbide base electric contact material of a high resistance fusion welding, the main body composition is: tungsten carbide 45～73wt%, nickel be less than 0.05wt%, Yu Weiyin; The weld layer composition is: silver 40～60wt%, and copper 20～30wt%, surplus is zinc or phosphorus; The tungsten carbide particle particle diameter is 0.7～4 μ m, it is characterized in that: adopt the following steps preparation:
1. at first silver powder is crossed the win silver powder of particle diameter of 500 mesh sieves, tungsten carbide powder carries out sorting, obtains the tungsten carbide powder that particle diameter is 0.7～4 μ m;
The silver powder that 2. will have first particle diameter and the tungsten-carbide powder with second particle diameter are in 1～1.5: 9～8.5 ratio is mixed powder, by at least more than the secondary repeatedly the processing of moulding crushing hot make A powder greater than the 3rd particle diameter of first, second particle diameter;
3. with adding the oxalates or the nitrate solution of nickel in the A powder, mix thoroughly, and dry processing, guarantee that the final composition of nickel is less than 0.05wt% when the oxalates of adding nickel or nitrate solution;
4. the powder compaction with above-mentioned oven dry is a shaping blank, and the shaping blank porosity is 30%～50%;
5. in high temperature sintering furnace shaping blank is carried out preliminary treatment, pretreatment temperature is 850 ℃～1000 ℃, 5 minutes～120 minutes time, hydrogen atmosphere protection;
6. the shaping blank after pre-burning being handled soaks burning, 2～3 hours time under 1100 ℃～1200 ℃ temperature;
7. will determine that the Ag-Cu-Zn of composition or silver-bearing copper phosphorus solder powder adopt mechanical means to carry out preliminary treatment, 400 ℃～450 ℃ annealing is 2～3 hours in hydrogen, the B powder, the B powder has laminated structure, or the powder with sheet should account for more than the 60wt% at least.
8. at least a joining in terpinol or the glycerol in the group that methylcellulose, ethyl cellulose are formed adds by 1: 23～25; 100 ℃～200 ℃ heat treatments, 30 minutes to 180 minutes time, be made into the organic substance slurry; By mechanical means the B powder is added slurry, mix thoroughly and obtain the scolder slurry, preserve being lower than under 10 ℃ the temperature;
9. the shaping blank that will soak the burnt together lattice neatly discharges, and above-mentioned scolder slurry evenly is coated in the shaping blank surface, and 300 ℃～650 ℃ stage intensification heat treatments in hydrogen, are carried out following process and got qualified electrical contact at 2～3 hours total times after the taking-up.
2. the silver-tungsten carbide base electric contact material of high resistance fusion welding according to claim 1 is characterized in that: described tungsten carbide adopts (W.Ti) C powder to substitute, and tungsten carbide is 7～8: 3～2 with the ratio of titanium carbide in described (W.Ti) C powder.
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| CN102509663B (en) * | 2011-10-27 | 2016-01-06 | 福达合金材料股份有限公司 | A kind of technique of contact electric spark sintering |
| CN102426873B (en) * | 2011-12-28 | 2014-12-10 | 彩虹集团公司 | Silicon solar battery positive silver paste and preparation method thereof |
| CN102522229B (en) * | 2011-12-30 | 2014-10-29 | 浙江天银合金技术有限公司 | Production process of silver-tungsten carbide and silver-nickel-copper compounded electric contact |
| CN104388739B (en) * | 2014-11-28 | 2016-04-06 | 桂林电器科学研究院有限公司 | A kind of silver-colored wolfram varbide nickel contact material and preparation method thereof |
| CN106548880B (en) * | 2015-09-21 | 2019-08-23 | 上海天固焊接器材有限公司 | A kind of Ag-based electrical contact that can be directly brazed and its manufacturing method |
| CN105405685A (en) * | 2015-12-10 | 2016-03-16 | 宋和明 | Disconnecting switch contact material and processing technology therefor |
| CN105671401A (en) * | 2016-01-22 | 2016-06-15 | 浙江亚通金属陶瓷有限公司 | Nanometer tungsten carbide silver contact material and manufacturing method |
| CN105695789A (en) * | 2016-04-08 | 2016-06-22 | 苏州捷德瑞精密机械有限公司 | Nontoxic welding-resistant electrical contact composite and preparation method thereof |
| EP3382730B1 (en) * | 2017-03-27 | 2020-03-04 | ABB Schweiz AG | Low voltage circuit breaker |
| CN108441668B (en) * | 2018-04-13 | 2021-02-26 | 上海和伍复合材料有限公司 | Silver-tungsten electric contact material and preparation method thereof |
| CN111063568B (en) * | 2019-12-15 | 2021-04-16 | 浙江大学 | Preparation method of silver tungsten carbide electrical contact material for circuit breaker |
| CN111575611B (en) * | 2020-06-19 | 2021-11-05 | 南京尚吉增材制造研究院有限公司 | SiC fiber-WC-Ni hard alloy composite material and preparation method thereof |
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