CN102051496B - Electric contact material made of silver-tungsten carbide graphite and preparation method thereof - Google Patents
Electric contact material made of silver-tungsten carbide graphite and preparation method thereof Download PDFInfo
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- CN102051496B CN102051496B CN2010105589777A CN201010558977A CN102051496B CN 102051496 B CN102051496 B CN 102051496B CN 2010105589777 A CN2010105589777 A CN 2010105589777A CN 201010558977 A CN201010558977 A CN 201010558977A CN 102051496 B CN102051496 B CN 102051496B
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- wolfram varbide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 22
- 239000010439 graphite Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- UYKQQBUWKSHMIM-UHFFFAOYSA-N silver tungsten Chemical compound [Ag][W][W] UYKQQBUWKSHMIM-UHFFFAOYSA-N 0.000 title abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910026551 ZrC Inorganic materials 0.000 claims abstract description 24
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 4
- -1 add element Chemical compound 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000003466 welding Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000010891 electric arc Methods 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 239000010937 tungsten Substances 0.000 abstract description 2
- 239000006104 solid solution Substances 0.000 abstract 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 230000003628 erosive effect Effects 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910052845 zircon Inorganic materials 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an electric contact material made of silver-tungsten carbide graphite and a preparation method thereof. The electric contact material comprises the following main components in percentage by weight: 11%-14% of tungsten carbide-zirconium carbide solid solution, 2%-6% of graphite, 0.3%-0.6% of additive and the balance of silver, wherein the added element is one or the combination of Ti, Co and Cr. The tungsten carbide and the zirconium carbide are added in form of solid solution with the ratio of (6:4)-(9:1). Compared with the traditional electric contact made of silver-tungsten carbide graphite, the electric contact material has higher welding resistance, electric arc burning resistance and high-temperature oxidation resistance. A low-voltage electric appliance adopting the electric contact material has lower contact resistance, longer electric service life and high reliability. Therefore, the novel electric contact material with high reliability is more suitable for being applied in various different plastic-shell circuit breakers, small high-interruption circuit breakers and alternating-current contactors.
Description
Technical field
The invention belongs to electrical contact material, specifically be meant a kind of high silver-colored wolfram varbide graphite electrical contact material of high-temperature oxidation resistance, resistance fusion welding and anti-electrical arc erosion property and preparation method thereof that has.
Background technology
Electrical contact is the core integral part in the low-voltage apparatus, in all kinds of trip switchs, bears the task of make-and-break contact, is widely used in fields such as military affairs, aerospace and Industry Control.The electric property of silver based contact material has fundamental influence to the long lifetime and the high reliability of all kinds of electrical control systems.
The silver-tungsten carbide-carbon series electric contact materials has excellent resistance fusion welding as the contact material of new generation of the traditional AgC5 of replacement, is widely used for auto-switch; On large capcity breaker, breaker of plastic casing and the some other derailing switch; The Ag-WC-C series electric contact has mainly utilized good conductive, the thermal conductivity of Ag, and the characteristics that the HMP of WC, high firmness and wear resistance are good can stand the intensive arc erosion; Have good resistance fusion welding and erosion resistant, reached the effect of joint silver simultaneously.
At present, adopt the asymmetric reasonable counterpart contact of AgWC12C3 and AgW50 pairing Chang Zuowei isolating switch in the silver-tungsten carbide-carbon series electric contact materials.But the main drawback of electrical contact that contains the WC material is that oxidation-resistance is poor.In use owing to the effect of electric arc, contact surface oxidation meeting forms the oxide compound of tungsten or the surface film of tungstate to the AgWC12C3 electrical contact, and this film is non-conductive, makes contact resistance increase severely, and severe patient can reach more than ten times of initial value.Therefore existing silver-colored wolfram varbide graphite contact material exists in oxidation-resistance, resistance fusion welding and the relatively poor defective of anti-electrical arc erosion property; Overall performance is stable inadequately; Limited the Application Areas of this contact material, be difficult to satisfy the 4th generation low-voltage apparatus the requirement of having relatively high expectations of high reliability and electromagnetic compatibility.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, and a kind of high silver-colored wolfram varbide graphite contact material of high-temperature oxidation resistance, resistance fusion welding and anti-electrical arc erosion property that has is provided.
Another object of the present invention has provided a kind of silver-colored wolfram varbide graphite contact preparation methods.
For realizing first purpose of the present invention, technical scheme of the present invention is
Wolfram varbide-zirconium carbide sosoloid 11%-14%, graphite 2%-6%, additive 0.3% ~ 0.8%, surplus is a silver; Wherein said interpolation element is the one or more combination in the following element: Ti, Co, Cr.Described wolfram varbide and zirconium carbide add with the sosoloid form, and wherein wolfram varbide is (6: 4) ~ (9: 1) with the ratio of zirconium carbide.
For realizing another object of the present invention, technical scheme of the present invention is may further comprise the steps
(1) with wolfram varbide-zirconium carbide sosoloid and graphite, add element, silver powder mixes in proportion, mix the powder mode for do mix or wet mixing in a kind of.Mixing the powder time is: 4 ~ 7 hours, ball-to-powder weight ratio was: (1: 1) ~ (5: 1);
(2) powder mix is granulated in protective atmosphere; The granulation of this step is 650 ~ 850 ℃ in high temperature sintering furnace, carrying out pelleting temperature, 0.5 ~ 5 hour time, carries out in the protective atmosphere;
(3) powder mix that will granulate carries out first pressing and obtains pressed compact; The first pressing pressing pressure of this step is 50MPa ~ 200Mpa;
(4) pressed compact is carried out sintering in protective atmosphere, the sintering temperature of this step pressed compact is 850 ~ 920 ℃, and the time is 3 ~ 5 hours, the hydrogen atmosphere protection;
(5) base substrate behind the sintering being carried out once multiple the pressure handles; This step sintered body once again pressure pressure be 100 ~ 300MPa;
(6) will answer the pressed compact body anneals; This step annealing temperature is 550 ~ 650 ℃, and the time is 2 ~ 4 hours;
(7) base substrate of will annealing carries out secondary and presses again and obtain the finished product; The multiple pressure pressure of this step secondary is 500 ~ 700MPa.
The present invention has adopted wolfram varbide-zirconium carbide sosoloid in the silver-colored wolfram varbide graphite contact materials process of preparation, in conjunction with wolfram varbide high firmness, HS and high elastic coefficient, good chemicalstability is with its zirconium carbide excellent high temperature oxidation resistance.In addition, interpolation element ti, Co, Cr form liquid sosoloid at low temperature, improve the wettability of silver and wolfram varbide-zirconium carbide, strengthen substrate combinating strength.This novel silver-colored wolfram varbide graphite contact material has higher high-temperature oxidation resistance, resistance fusion welding and anti-electrical arc erosion property.Adopt the low-voltage apparatus of this electrical contact material to have than low contact resistance, higher electric life and high reliability.Therefore this electrical contact material is more suitable for being applied on various mold cased circuit breaker, small-sized high score isolating switch and the alternating current contactor.
Below in conjunction with Figure of description and embodiment the present invention is done further introduction.
Description of drawings
Fig. 1 process flow sheet of the present invention.
Embodiment
Through embodiment the present invention is carried out concrete description below; Only be used for the present invention is further specified; Can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment:
Embodiment 1,, be that the AgWC9.6ZrC2.4C3 of 7.5 * 7.5 * 2.5mm is an example with the preparation specification with reference to Fig. 1.
(1) with Ag powder and wolfram varbide-zirconium carbide sosoloid, graphite ratio in 85: 12: 3; Carried out wet mixing 6 hours with 0.3%Ni, 0.7%B, ball-to-powder weight ratio is 1: 1, vacuum drying; In hydrogen atmosphere 700 ℃; Carried out a change granulation in 4 hours, obtain the mixed powder of good fluidity, wherein the ratio of wolfram varbide and zirconium carbide is 8:2 in wolfram varbide-zirconium carbide sosoloid;
(2) mixed powder that will granulate is pressed into 7.5 * 7.5 * 3.5mm pressed compact, and first pressure pressure is 150MPa;
(3) with pressed compact in hydrogen atmosphere in 880 ℃, carried out sintering in 4 hours;
(4) pressure with base substrate 250MPa behind the sintering carries out multiple pressure, and pressed compact thickness is 2.8mm;
(5) will press again the back base substrate in hydrogen atmosphere in 500 ℃, annealed in 2 hours;
(6) will be the annealed base substrate carry out multiple pressure with the pressure of 560MPa and obtain 7.5 * 7.5 * 2.5mm product;
(7) silver-colored wolfram varbide carbonization zircon China ink contact is handled through grinding, polish, drying.
The AgWC9.6ZrC2.4C3 contact physicals of this examples preparation is following: density 9.69g/cm
3, resistivity 3.05 μ Ω .cm, hardness 626MPa.
Embodiment 2, be that the AgWC9.8ZrC4.2C2 of 6 * 6 * 2mm is an example with the preparation specification.
(1) with Ag powder and wolfram varbide-zirconium carbide sosoloid, graphite ratio in 84: 14: 2; Carried out wet mixing 4 hours with 0.4%Cr, ball-to-powder weight ratio is 3: 1, vacuum drying; In hydrogen atmosphere 750 ℃; Carried out a change granulation in 3 hours, obtain the mixed powder of good fluidity, wherein the ratio of wolfram varbide and zirconium carbide is 7: 3 in wolfram varbide-zirconium carbide sosoloid;
(2) mixed powder that will granulate is pressed into 6 * 6 * 2.8mm pressed compact, and first pressure pressure is 180MPa.
(3) with pressed compact in hydrogen atmosphere in 900 ℃, carried out sintering in 3 hours;
(4) pressure with base substrate 280MPa behind the sintering carries out multiple pressure, and pressed compact thickness is 2.2mm;
(5) will press again the back base substrate in hydrogen atmosphere in 600 ℃, annealed in 4 hours;
(6) will be the annealed base substrate carry out multiple pressure with the pressure of 600MPa and obtain 6 * 6 * 2mm;
(7) silver-colored wolfram varbide carbonization zircon China ink contact is handled through grinding, polish, drying.
The AgWC9.8ZrC4.2C2 contact physicals of this examples preparation is following: density 9.76g/cm
3, resistivity 3.12 μ Ω .cm, hardness 637MPa.
Embodiment 3, be that the AgWC10.8ZrC1.2C3 of 11 * 9 * 2mm is an example with the preparation specification.
(1) with Ag powder and wolfram varbide-zirconium carbide sosoloid, graphite ratio in 85: 12: 3; Carried out wet mixing 6 hours with 0.3%Ni, 0.7%B, ball-to-powder weight ratio is 1: 1, vacuum drying; In hydrogen atmosphere 700 ℃; Carried out a change granulation in 4 hours, obtain the mixed powder of good fluidity, wherein the ratio of wolfram varbide and zirconium carbide is 9:1 in wolfram varbide-zirconium carbide sosoloid;
(2) mixed powder that will granulate is pressed into 11 * 9 * 2.8mm pressed compact, and first pressure pressure is 150MPa;
(3) with pressed compact in hydrogen atmosphere in 880 ℃, carried out sintering in 4 hours;
(4) pressure with base substrate 250MPa behind the sintering carries out multiple pressure, and pressed compact thickness is 2.2mm;
(5) will press again the back base substrate in hydrogen atmosphere in 500 ℃, annealed in 2 hours;
(6) will be the annealed base substrate carry out multiple pressure with the pressure of 560MPa and obtain 11 * 9 * 2mm product;
(7) silver-colored wolfram varbide carbonization zircon China ink contact is handled through grinding, polish, drying.
The AgWC10.8ZrC1.2C3 contact physicals of this examples preparation is following: density 9.81g/cm
3, resistivity 2.97 μ Ω .cm, hardness 648MPa.
Embodiment 4, be that the AgWC8.4ZrC5.6C2 of 8 * 5.5 * 2mm is an example with the preparation specification.
(1) with Ag powder and wolfram varbide-zirconium carbide sosoloid, graphite ratio in 84: 14: 2; Carried out wet mixing 4 hours with 0.4%Cr, ball-to-powder weight ratio is 3: 1, vacuum drying; In hydrogen atmosphere 720 ℃; Carried out a change granulation in 4 hours, obtain the mixed powder of good fluidity, wherein the ratio of wolfram varbide and zirconium carbide is 6: 4 in wolfram varbide-zirconium carbide sosoloid;
(2) mixed powder that will granulate is pressed into 8 * 5.5 * 2.8mm pressed compact, and first pressure pressure is 180MPa.
(3) with pressed compact in hydrogen atmosphere in 900 ℃, carried out sintering in 3 hours;
(4) pressure with base substrate 280MPa behind the sintering carries out multiple pressure, and pressed compact thickness is 2.2mm;
(5) will press again the back base substrate in hydrogen atmosphere in 600 ℃, annealed in 4 hours;
(6) will be the annealed base substrate carry out multiple pressure with the pressure of 600MPa and obtain 8 * 5.5 * 2mm;
(7) silver-colored wolfram varbide carbonization zircon China ink contact is handled through grinding, polish, drying.
The AgWC9.8ZrC4.2C2 contact physicals of this examples preparation is following: density 9.52g/cm
3, resistivity 3.29 μ Ω .cm, hardness 613MPa.
Claims (3)
1. a silver-colored wolfram varbide graphite contact material is characterized in that comprising following component, in massfraction:
Wolfram varbide-zirconium carbide sosoloid 11%-14%, graphite 2%-6% adds element 0.3% ~ 0.8%, and surplus is a silver; Wherein, described interpolation element is the one or more combination in the following element: Ti, Co, B, Cr, and wherein wolfram varbide is (6:4) ~ (9:1) with the ratio of zirconium carbide.
2. one kind prepares silver-colored wolfram varbide graphite contact preparation methods as claimed in claim 1, it is characterized in that may further comprise the steps:
(1) with wolfram varbide-zirconium carbide sosoloid and graphite, add element, silver powder mixes in proportion, mix the powder mode for do mix or wet mixing in a kind of, its mixed powder time is: 4 ~ 7 hours, ball-to-powder weight ratio was: (1:1) ~ (5:1);
(2) powder mix is granulated in protective atmosphere, granulate and in high temperature sintering furnace, carry out, pelleting temperature is 650 ~ 850 ℃, 0.5 ~ 5 hour time;
(3) powder mix that will granulate carries out first pressing and obtains pressed compact, and the first pressing pressing pressure is 50MPa ~ 200MPa;
(4) pressed compact is carried out sintering in protective atmosphere, the sintering temperature of pressed compact is 850 ~ 920 ℃, and the time is 3 ~ 5 hours;
(5) base substrate behind the sintering is carried out once multiple the pressure and handle, it once answers pressure pressure is 100 ~ 300MPa;
(6) will answer the pressed compact body and in protective atmosphere, anneal, its annealing temperature is 550 ~ 650 ℃, and the time is 2 ~ 4 hours;
(7) base substrate of will annealing carries out secondary and presses again and obtain the finished product, and the multiple pressure pressure of its secondary is 500 ~ 700MPa.
3. a kind of silver-colored wolfram varbide graphite contact preparation methods according to claim 2, it is characterized in that: described protective atmosphere is hydrogen or rare gas element.
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| CN102354543B (en) * | 2011-07-28 | 2013-06-19 | 攀枝花学院 | TiCr2-based electrical contact material and its preparation method and application |
| CN103586470B (en) * | 2013-11-22 | 2016-02-17 | 福达合金材料股份有限公司 | Preparation method of siluer metal oxide graphite composite electric contact material and products thereof |
| CN105886813A (en) * | 2016-04-23 | 2016-08-24 | 东莞市华诺合金有限公司 | Silver tin oxide-wolfram electrical contact material and preparation method thereof |
| CN106024432A (en) * | 2016-06-20 | 2016-10-12 | 仙居县南大合金科技有限公司 | Zirconium carbide copper-based contact material for low-voltage electric appliances and processing method thereof |
| CN112126810A (en) * | 2020-09-03 | 2020-12-25 | 大都克电接触科技（中国）有限公司 | Preparation method of silver tungsten carbide graphite electrical contact material |
| CN115491669A (en) * | 2021-06-19 | 2022-12-20 | 浙江帕特尼触头有限公司 | A silver/copper-based composite contact material and its preparation process |
| CN114182126A (en) * | 2021-12-01 | 2022-03-15 | 苏州市希尔孚新材料股份有限公司 | Preparation method of high-performance silver tungsten carbide graphite contact material |
| CN115522093B (en) * | 2022-08-24 | 2023-07-18 | 苏州银孚新材料有限公司 | Composite reinforced silver tungsten carbide graphite electric shock material and preparation method thereof |
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| CN101831571B (en) * | 2010-05-31 | 2012-03-28 | 福达合金材料股份有限公司 | A kind of silver-nickel base electric contact material and preparation method thereof |
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Effective date of registration: 20220130 Address after: 325025 No. 308, Binhai fifth road, Wenzhou Economic and Technological Development Zone, Wenzhou City, Zhejiang Province Patentee after: Zhejiang Fuda alloy material technology Co.,Ltd. Address before: No. 518, Binhai 4th Road, Binhai Park, Wenzhou Economic and Technological Development Zone, Zhejiang Province, 325000 Patentee before: FUDA ALLOY MATERIALS Co.,Ltd. |