CN101345141A - Electrical contact material with Ti3SiC2 three-layer compound structure and preparation technique - Google Patents
Electrical contact material with Ti3SiC2 three-layer compound structure and preparation technique Download PDFInfo
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- CN101345141A CN101345141A CNA2008101369963A CN200810136996A CN101345141A CN 101345141 A CN101345141 A CN 101345141A CN A2008101369963 A CNA2008101369963 A CN A2008101369963A CN 200810136996 A CN200810136996 A CN 200810136996A CN 101345141 A CN101345141 A CN 101345141A
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Abstract
The invention aims at providing an electric contact material Ti3SiC2 and a preparation method used for the electric contact material Ti3SiC2, wherein, the electric contact material Ti3SiC2 is provided with three-layer composite structure with self-lubrication performance and has the advantages of high-strength, high conductivity, high thermal conductivity, oxidation resistance, melt welding resistance and electric arc burning resistance. The electric contact material Ti3SiC2 with the three-layer composite structure is composed of three layers as follows: the first layer (surface layer) is Ti3SiC2 of 3 to 1000 microns thick, the second layer (substrate) is a copper-based or silver-based alloy and the third layer (welding layer) is solder of 0.03 to 0.10mm thick. The electric contact material Ti3SiC2 with three-layer composite structure adopts reasonable configuration of three layers of the Ti3SiC2/ copper (silver) based alloy/ solder, takes the TiSiC2 layer as the surface layer, and has the excellent characteristics such as high strength, good conductivity, good thermal conductivity, good melt welding resistance, good electric arc burning resistance, good corrosion resistance, good thermal-vibration resistance, good oxidation resistance and particularly good high-temperature oxidation resistance, etc.
Description
(1) technical field
The present invention relates to powder metallurgy technology, is exactly a kind of electrical contact material and preparation technology thereof of Ti3SiC2 three-layer composite structure specifically.
(2) background technology
In recent years, constantly release the novel mold cased circuit breaker and the small-sized high score circuit breaker of various series both at home and abroad, these novel circuit breaker volumes are littler, and breaking capacity but increases substantially.Novel breaker is except adopting a series of new current limiting techniques to improve the breaking capacity, and to the anti-melting welding of used electrical contact, anti-electrical arc erosion and electric life are all had higher requirement.
In present disclosed patent and the contact material used, a class is to be the Ag-based electrical contact material of principal component with silver, and another kind of is to be the Ag-based electrical contact material of principal component with copper.With silver is the Ag-based electrical contact material good electrical property of principal component, the cost height, but performance can not satisfy the specific (special) requirements of high-grade novel electric equipment products under some working condition.With copper be the copper-based electrical contact of principal component the cost of material is low, though electrical property can satisfy instructions for use, but still have much room for improvement.
(3) summary of the invention
The object of the present invention is to provide a kind of high-strength, high conduction, high heat conduction, resistance to oxidation, anti-melting welding, anti-electrical arc erosion, have the electrical contact material and the preparation technology thereof of the Ti3SiC2 three-layer composite structure of self-lubricating property.
The object of the present invention is achieved like this: the electrical contact material of described Ti3SiC2 three-layer composite structure is made of following three layers of material:
Ground floor (top layer) is the Ti3SiC2 of 3～1000 μ m for thickness;
The second layer (matrix) is copper base or silver-base alloy;
The 3rd layer (weld layer) is 0.03～0.10mm solder for thickness.
The present invention also has following technical characterictic:
(1) electrical contact material of a kind of Ti3SiC2 three-layer composite structure of the present invention, described Ti3SiC2 are to be made greater than 93% Ti3SiC2 powder by purity, and the Ti3SiC2 particle size is 0.01～50 μ m.
(2) electrical contact material of a kind of Ti3SiC2 three-layer composite structure of the present invention, described acid bronze alloy are fine copper or to contain percentage by weight be a kind of or wherein several mixing in 0.01～50% diamond, graphite, silver, lanthanum, cerium, dysprosium, samarium, yttrium, ytterbium, zirconium, aluminium, chromium, niobium, tin, zinc, tungsten, vanadium, tin oxide, cadmium oxide, the indium oxide.
(3) electrical contact material of a kind of Ti3SiC2 three-layer composite structure of the present invention, described silver-base alloy are fine silver or to contain percentage by weight be one or more mixing in 0.01～50% tungsten, molybdenum, copper, nickel, cadmium oxide, zinc oxide, tin oxide, indium oxide, tungsten carbide, diamond, the graphite.
(4) it is copper that the electrical contact material of a kind of Ti3SiC2 three-layer composite structure of the present invention, described solder contain tin, the silver of 0-31%, the zinc of 1.5-17%, the phosphorus of 0-5.2%, the surplus that percentage by weight is 3.5-4.5%.
The electrical contact material and the preparation technology thereof of a kind of Ti3SiC2 three-layer composite structure of the present invention, its preparation technology is as follows:
(1) copper base or silver-base alloy are by powder metallurgic method, through mixing powder, compacting, sintering, pushing, be rolled into the sheet material of required specification.
(2) solder with smelting process, be rolled into the band that thickness is 0.05～0.15mm.
(3) copper base (or money base) sheet alloy is carried out single face and handle, making surface roughness is 2.5～13 μ m Ra.
(4) adopt brush to cover or the mode of plasma spraying sprays to Ti3SiC2 cermet powder on the sheet material of above-mentioned processing.
(5) with above-mentioned sheet material in vacuum degree 100～5 * 10
-4Pa, temperature are incubated 10～90min down for 800～900 ℃.Obtain Ti3SiC2/ copper (silver) alloy composite materials sheet material.
(6) with the basic composite board of above-mentioned Ti3SiC2/ copper (silver) after pickling, adopt hot application that copper (silver) basal plane and the solder band of the basic composite board of Ti3SiC2/ copper (silver) is compound, obtain Ti3SiC2/ copper (silver) alloy/solder composite sheet material.
(7) Ti3SiC2/ copper (silver) alloy/solder composite sheet material carries out Ageing Treatment under vacuum or protective atmosphere, 400～500 ℃ of treatment temperatures, 1～5 hour processing time.
(8) with the plate rolling after the Ageing Treatment to given size, and carry out machining by the contact size.
The electrical contact material of a kind of Ti3SiC2 three-layer composite structure of the present invention, reasonable disposition by the basic alloy of Ti3SiC2/ copper (silver)/solder three-decker, with Ti3SiC2 is the top layer, intensity height not only, and possess good electrical conductivity, thermal conductivity, good characteristic such as anti-melting welding, arc ablation resistance, corrosion-resistant, anti-thermal shock, anti-oxidant especially high-temperature oxidation resistance.Particularly the ultralow coefficient of friction and the self lubricity of this material are one of indispensable characteristics of contact material.The reasonable disposition of the basic alloy of copper (silver), solder then can reduce cost, and can be widely used in the low-voltage electrical apparatus contact material, as circuit breaker and probe of contactor.
(4) embodiment
Below the invention will be further described.
The electrical contact material of a kind of Ti3SiC2 three-layer composite structure of the present invention is made of following three layers of material:
Ground floor (top layer) is the Ti3SiC2 of 3～1000 μ m for thickness;
The second layer (matrix) is copper base or silver-base alloy;
The 3rd layer (weld layer) is 0.03～0.10mm solder for thickness.
This three-decker by brush cover, process such as sintering, Ageing Treatment is prepared from.
Ti3SiC2 belongs to hexagonal crystallographic texture, and the Si layer that the TiC octahedron of common rib is formed by the Si atom is separated, and forms special nanoscale layer laminated structure.This structure is given its image-stone China ink and is equally had lubrification and machinability, combines many premium properties of metal and pottery.The Ti3SiC2 fusing point has fabulous conductivity, thermal conductivity up to 3000 ℃, and its conductivity and simple metal are suitable, and conductance reaches 4.7 * 10 in the time of 25 ℃
6Sm
-1, thermal conductivity reaches 33.5Wm
-1K
-1In addition, the high strength that Ti3SiC2 possessed, anti-thermal shock, corrosion-resistant, anti-oxidant, especially high temperature oxidation resistance and anti-cyclic oxidation ability and characteristics such as self lubricity and ultralow coefficient of friction are the ideal material of low-voltage electrical apparatus with contact, therefore elect the top layer as.
Diamond is the highest material of occurring in nature thermal conductivity, and thermal conductivity reaches 138.16Wm
-1K
-1Have performances such as fusing point height (about 3700 ℃), hardness be big, wear-resistant simultaneously, adopt powder metallurgy process in copper, to add tiny diamond particles, not only can play dispersion-strengthened action, improve the effect of hardness and resistance to wear, also the heat that electric arc is produced conducts to crane span structure, reduces the contact surface temperature.The diamond particles of what is more important contact surface is burnt when beating arc, does not produce the deposit that causes resistance to increase in contact surface.Simultaneously, the contact that with copper is main composition is under the high-temperature electric arc effect, and it is metallic copper or cuprous oxide that the carbon monoxide that the diamond burning produces can make the copper oxide reduction of contact surface.Therefore, under the oxidized situation of contact surface, can change the structure of oxide layer by diamond and cuprous oxide.Cuprous oxide is the powdery film, helps guaranteeing that contact has sufficient rectified action.
Add a spot of silver in the copper and, can improve its intensity, hardness, increase that electricity is led, thermal conductance and corrosion resistance, improve mobile and wettability is also improved the cold and hot working performance through excessive deformation process.An amount of alloying element that adds lanthanum, cerium, dysprosium, samarium, ytterbium, yttrium as copper in copper can improve the oxidation resistance of acid bronze alloy low temperature and high temperature, improves the intensity and the recrystallization temperature of acid bronze alloy, and conductivity is slightly improved.In copper, add zirconium, chromium, aluminium in right amount and can improve the medium and high temperature oxidation resistance of copper-based material, anti-ablation property and decay resistance.Aluminium, tin, zinc can reduce contact temperature and have the arc extinguishing effect as contact material the time by its vaporization.Chromium, niobium, tungsten, vanadium solid solubility in the copper matrix is extremely low, and the adding of these elements has certain effect to antioxygenic property, intensity and the anti-ablation property tool that improves matrix.The adding of such alloy also can improve recrystallization temperature.Can increase simultaneously the viscosity of contact surface formed metal bath under arcing, reduce the material damage of contact material, thereby increase the electric life of contact.
The effect that adds cadmium oxide, tin oxide and indium oxide in the copper matrix is: cadmium oxide, tin oxide and indium oxide flash to gas under arcing, play the arc extinguishing effect, and reduce the contact surface temperature.Can also increase simultaneously the viscosity of contact surface metal bath, reduce bath splash tendency, thereby reduce the material damage of contact surface, increase the contact life-span.
Based on above analysis, in copper, suitably add a kind of or wherein several mixing in diamond, graphite, silver, lanthanum, cerium, dysprosium, samarium, yttrium, ytterbium, zirconium, aluminium, chromium, niobium, tin, zinc, tungsten, vanadium, tin oxide, cadmium oxide, the indium oxide, can improve the correlated performance of copper base contact.As basis material, can guarantee under the excessive situation of top layer loss, still can guarantee the contact operate as normal.
Silver-base alloy of the present invention, can guarantee still can guarantee the contact operate as normal under the excessive situation of top layer loss as matrix for being in the silver based contact material of application state equally.
Weld layer has improved the contact welding efficiency, reduces cost of labor.
The preparation technology of the electrical contact material of a kind of Ti3SiC2 three-layer composite structure of the present invention is as follows:
(1) copper base or silver-base alloy are by powder metallurgic method, through mixing powder, compacting, sintering, pushing, be rolled into the sheet material of required specification.
(2) solder with smelting process, be rolled into the band that thickness is 0.05～0.15mm.
(3) copper base (or money base) sheet alloy is carried out single face and handle, making surface roughness is 2.5～13 μ m Ra.
(4) adopt brush to cover or the mode of plasma spraying sprays to Ti3SiC2 cermet powder on the sheet material of above-mentioned processing.
(5) with above-mentioned sheet material in vacuum degree 100～5 * 10
-4Pa, temperature are incubated 10～90min down for 800～900 ℃.Obtain Ti3SiC2/ copper (silver) alloy composite materials sheet material.
(6) with the basic composite board of above-mentioned Ti3SiC2/ copper (silver) after pickling, adopt hot application that copper (silver) basal plane and the solder band of the basic composite board of Ti3SiC2/ copper (silver) is compound, obtain Ti3SiC2/ copper (silver) alloy/solder composite sheet material.
(7) Ti3SiC2/ copper (silver) alloy/solder composite sheet material carries out Ageing Treatment under vacuum or protective atmosphere, 400～500 ℃ of treatment temperatures, 1～5 hour processing time.
(8) with the plate rolling after the Ageing Treatment to given size, and carry out machining by the contact size.
Embodiment 1
Top layer: Ti3SiC2, thickness 400 μ m;
Matrix: line copper, thickness 1.4mm;
Weld layer: tin 4.5%, silver 5.2%, zinc 2.0%, phosphorus 5.0%, copper surplus, thickness 0.1mm.
Embodiment 2
Top layer: Ti3SiC2, thickness 100 μ m;
Matrix: silver, thickness 1.1mm;
Weld layer: tin 4.5%, silver 30%, zinc 15%, copper surplus, thickness 0.1mm.
Embodiment 3
Top layer: Ti3SiC2, thickness 200 μ m;
Matrix: diamond 1.3%, copper surplus, thickness 1.1mm;
Weld layer: tin 4.5%, silver 5.2%, zinc 2.0%, phosphorus 5.0%, Cu surplus, thickness 0.1mm.
Embodiment 4
Top layer: Ti3SiC2, thickness 250 μ m;
Matrix: diamond 1.3%, aluminium 0.12%, lanthanum 0.34%, zirconium 0.05, copper surplus, thickness 1.1mm;
Weld layer: tin 3.5%, silver 5.0%, zinc 2.0%, phosphorus 5.0%, Cu surplus, thickness 0.08mm.
Embodiment 5
Top layer: Ti3SiC2, thickness 30 μ m;
Matrix: diamond 0.8%, silver-colored surplus, thickness 1.1mm;
Weld layer: tin 4.5%, silver 31%, zinc 15%, copper surplus, thickness 0.05mm.
Embodiment 6
To implement 3 is example, and its preparation technology is:
(1) be the diadust 0.8kg of 2.0 μ m and granularity with particle mean size for-200 order electrolytic copper powder 99.2kg by powder metallurgic method, through mixing powder, compacting, sintering, pushing, be rolled into the sheet material that thickness is 1.21mm.
(2) solder with smelting process, be rolled into the band that thickness is 0.11mm.
(3) sheet material is carried out single face and handle, making surface roughness is 5 μ m Ra.
(4) adopt the mode of plasma spraying that Ti3SiC2 cermet powder is sprayed on the sheet material of above-mentioned processing, thickness is 220 μ m.
(5) with above-mentioned sheet material in vacuum degree 100 * 10
-4Pa, temperature are incubated 60min down for 900 ℃.
(6) after the sheet material pickling, adopt hot application that the copper basal plane and the solder band of sheet material is compound.
(7) under vacuum condition, carry out Ageing Treatment, 450 ℃ of treatment temperatures, 2 hours processing times.
(8) carry out machining with the rolling 1.3mm of composite board, and by the contact size.
Claims (6)
1. the electrical contact material of a Ti3SiC2 three-layer composite structure and preparation technology thereof, its electrical contact material is made of following three layers of material:
Ground floor (top layer) is the Ti3SiC2 of thickness 3～1000 μ m;
The second layer (matrix) is copper base (or money base) alloy;
The 3rd layer (weld layer) is thickness 0.03～0.10mm solder.
2. the electrical contact material of a kind of Ti3SiC2 three-layer composite structure according to claim 1 is characterized in that: described Ti3SiC2 is made greater than 93% Ti3SiC2 powder by purity, and the Ti3SiC2 particle size is 0.01～50 μ m.
3. the electrical contact material of a kind of Ti3SiC2 three-layer composite structure according to claim 1 is characterized in that: described acid bronze alloy is a fine copper or to contain percentage by weight be a kind of or wherein several mixing in 0.01～50% diamond, graphite, silver, lanthanum, cerium, dysprosium, samarium, yttrium, ytterbium, zirconium, aluminium, chromium, niobium, tin, zinc, tungsten, vanadium, tin oxide, cadmium oxide, the indium oxide.
4. the electrical contact material of a kind of Ti3SiC2 three-layer composite structure according to claim 1 is characterized in that: described silver-base alloy is a fine silver or to contain percentage by weight be one or more mixing in 0.01～50% tungsten, molybdenum, copper, nickel, cadmium oxide, zinc oxide, tin oxide, indium oxide, tungsten carbide, diamond, the graphite.
5. the electrical contact material of a kind of Ti3SiC2 three-layer composite structure according to claim 1 is characterized in that: it is copper that described solder contains tin, the silver of 0-31%, the zinc of 1.5-17%, the phosphorus of 0-5.2%, the surplus that percentage by weight is 3.5-4.5%.
6. the electrical contact material of a Ti3SiC2 three-layer composite structure and preparation technology thereof, its preparation technology is as follows:
(1) described copper base or silver-base alloy are by powder metallurgic method, through mixing powder, compacting, sintering, pushing, be rolled into the sheet material of required specification;
(2) solder with smelting process, be rolled into the band that thickness is 0.05～0.15mm;
(3) copper base (or money base) sheet alloy is carried out single face and handle, making surface roughness is 2.5～13 μ m Ra;
(4) adopt brush to cover or the mode of plasma spraying sprays to Ti3SiC2 cermet powder on the sheet material of above-mentioned processing;
(5) with above-mentioned sheet material in vacuum degree 100～5 * 10
-4Pa, temperature are incubated 10～90min down for 800～900 ℃; Obtain Ti3SiC2/ copper (silver) alloy composite materials sheet material;
(6) with above-mentioned Ti3SiC2/ copper (silver) alloy composite plate material after pickling, adopt hot application that copper (silver) basal plane and the solder band of Ti3SiC2/ copper (silver) alloy composite plate material is compound, obtain Ti3SiC2/ copper (silver) alloy/solder composite sheet material;
(7) Ti3SiC2/ copper (silver) alloy/solder composite sheet material carries out Ageing Treatment under vacuum or protective atmosphere, 400～500 ℃ of treatment temperatures, 1～5 hour processing time;
(8) with the plate rolling after the Ageing Treatment to given size, and carry out machining by the contact size.
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| CN102231348A (en) * | 2011-06-23 | 2011-11-02 | 江苏省如高高压电器有限公司 | Method for improving surface roughness of silver coating layer of cylindrical contact terminal of breaker |
| CN102290116A (en) * | 2011-08-15 | 2011-12-21 | 上海中希合金有限公司 | Ag-Cu-Ni ceramic composite for micromotor commutator and manufacturing technology thereof |
| CN105047459A (en) * | 2015-08-25 | 2015-11-11 | 旌德县华丰电子元件有限公司 | Double control switch touch control sheet |
| CN105393349A (en) * | 2013-08-26 | 2016-03-09 | 三菱综合材料株式会社 | Assembly and power-module substrate |
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| CN106282641A (en) * | 2016-08-29 | 2017-01-04 | 江苏大学 | A kind of silver chromio electrical contact self-lubricating composite and its production and use |
| CN107487055A (en) * | 2016-06-12 | 2017-12-19 | 中国科学院宁波材料技术与工程研究所 | The application of multilayer complex films, its preparation method and the connecting material as carbon fibre-reinforced carbon composite material |
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| CN102231348A (en) * | 2011-06-23 | 2011-11-02 | 江苏省如高高压电器有限公司 | Method for improving surface roughness of silver coating layer of cylindrical contact terminal of breaker |
| CN102290116A (en) * | 2011-08-15 | 2011-12-21 | 上海中希合金有限公司 | Ag-Cu-Ni ceramic composite for micromotor commutator and manufacturing technology thereof |
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| CN105393349B (en) * | 2013-08-26 | 2017-06-09 | 三菱综合材料株式会社 | Conjugant and power module substrate |
| CN105047459B (en) * | 2015-08-25 | 2018-01-23 | 旌德县华丰电子元件有限公司 | A kind of double control switch touch control sheet |
| CN105047459A (en) * | 2015-08-25 | 2015-11-11 | 旌德县华丰电子元件有限公司 | Double control switch touch control sheet |
| CN107487055A (en) * | 2016-06-12 | 2017-12-19 | 中国科学院宁波材料技术与工程研究所 | The application of multilayer complex films, its preparation method and the connecting material as carbon fibre-reinforced carbon composite material |
| CN107487055B (en) * | 2016-06-12 | 2019-08-20 | 中国科学院宁波材料技术与工程研究所 | The application of multilayer complex films, preparation method and the connecting material as carbon fibre-reinforced carbon composite material |
| CN106057526A (en) * | 2016-06-27 | 2016-10-26 | 温州中希电工合金有限公司 | Laminated silver-copper-brazing-filler-metal three-composite electrical contact material manufactured by coating and sleeving method and manufacturing method thereof |
| CN106282641A (en) * | 2016-08-29 | 2017-01-04 | 江苏大学 | A kind of silver chromio electrical contact self-lubricating composite and its production and use |
| CN108899199A (en) * | 2018-06-20 | 2018-11-27 | 宿迁市覆盆子信息科技有限公司 | Transcalent capacitor |
| CN108899199B (en) * | 2018-06-20 | 2020-07-31 | 宿迁市覆盆子信息科技有限公司 | Capacitor easy to conduct heat |
| CN110976887A (en) * | 2019-12-17 | 2020-04-10 | 哈尔滨东大高新材料股份有限公司 | AgWC (T)/CuC (X) contact material and preparation method thereof |
| CN110976887B (en) * | 2019-12-17 | 2022-02-11 | 哈尔滨东大高新材料股份有限公司 | AgWC (T)/CuC (X) contact material and preparation method thereof |
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