CN1435503A - Carbide coating of enhancing carbon/copper interface binding characteristic, and process thereof - Google Patents
Carbide coating of enhancing carbon/copper interface binding characteristic, and process thereof Download PDFInfo
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- CN1435503A CN1435503A CN 02114427 CN02114427A CN1435503A CN 1435503 A CN1435503 A CN 1435503A CN 02114427 CN02114427 CN 02114427 CN 02114427 A CN02114427 A CN 02114427A CN 1435503 A CN1435503 A CN 1435503A
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Abstract
A coated carbide layer for improving the binding characteristics of C/Cu interface, that is, better wetting angle and electric conductivity, is prepared through generating uniform oxide layer on the surface of carbon material by use of the soluble inorganic salt of the elements chosen from groups IV, V and VI and sol-gel method, and preparing carbide layer on the surface of carbon material in protective atmosphere. Its advantages are low reaction temp and cost, simple operation and no pollution.
Description
Technical field: the present invention relates to a kind of carbide coating and technology thereof that improves carbon/copper interface binding characteristic, be mainly used in carbon coating cellulosic material (comprising homoatomic obform bodies such as diamond, graphite, decolorizing carbon, soccerballene) surface, make carbon/copper interface formation and copper or the carbide coating copper alloy good wet, that have electroconductibility.This carbide coating is based on the high-melting-point conductive carbide; utilize sol-gel method to obtain uniform coating on different shape, dissimilar carbon materials surfaces; then in protective atmosphere under certain temperature, utilize carbon reduction reaction to obtain the very good coating of electroconductibility on carbon materials surface.
Background technology: the application of carbon/carbon/carbon-copper composite material is very extensive, diamond/carbon/carbon-copper composite material wherein is used to make diamond tool for a long time, and graphite/carbon/carbon-copper composite material is widely used in the current collection brush, and novel graphite fibre/carbon/carbon-copper composite material also is expected to be used as novel heat sink material in electronic package.But, since about 136～170 ° of the wetting angle of various types of carbon elements and copper and molten alloyed copper under the high temperature, the wettability extreme difference.Thereby cause carbon/carbon/carbon-copper composite material interface compatibility poor, had a strong impact on performance of composites.This point is particularly outstanding on carbon/carbon/carbon-copper composite material made from powder metallurgic method, visible nonwetting just because of carbon and copper, and the application of carbon/carbon/carbon-copper composite material in electro-conductive material is subjected to its compound interface Effect on Performance.At present, in order to satisfy demand, also studied some and made the method for carbon/carbon/carbon-copper composite material carbon/carbon/carbon-copper composite material.The first has adopted the method for impregnation of high-pressure impregnation technology to make carbon/carbon/carbon-copper composite material, the huge heaviness of equipment used, complex process, material cost height, poor electric conductivity.Its two, for improving the angle of wetting of carbon/carbon/carbon-copper composite material, also carbon material surface is carried out coating usually and handles.Method at present commonly used has 1. chemical vapour deposition (CVD method), but this method is to the equipment requirements height, complex process, easily oxidation; 2. alloy such as Electroless Plating Ni-W, Co-W, Ni alloy heat treated wherein can cause carbon fiber to produce the amorphous graphite damage, also oxidation easily; 3. the Cr powder bury cover ooze, 4. vacuum plating and 5. magnetron sputtering Ti, W, Cr etc. and heat treated.Vacuum plating and magnetron sputtering method is with high costs, efficient is low in the aforesaid method; CVD method, electroless plating and Cr powder bury to cover to ooze also there are pollution in environment.In addition because the influence of coating, adopt the conductivity of carbon/carbon/carbon-copper composite material that these methods make poor, use is very restricted.Aforesaid method can carry out the coating carbon fiber except that CVD method, electroless plating simultaneously, and all the other methods all can not be implemented even applying coating on carbon fiber.
In sum: in the manufacturing of carbon/carbon/carbon-copper composite material, be badly in need of a kind ofly, and provide a kind of easy to operate, with low cost, pollution-free, safe and reliable processing method that obtains this coating for carbon/carbon/carbon-copper composite material interface provides a kind of effectively reliably new non-carbide wettability coating.This method can be easily on different shape (carbon granule, carbon fiber, carbon nanotube etc.), dissimilar carbon materials (homoatomic obform bodies such as diamond, graphite, decolorizing carbon, soccerballene) apply above-mentioned wetting coating, for produce specific conductivity, thermal conductivity and density height, the measured carbon/carbon/carbon-copper composite material of matter creates conditions.
Summary of the invention: technical scheme of the present invention is for improving the angle of wetting of carbon/carbon/carbon-copper composite material, material surface being carried out coating handle.It is characterized in that: soluble inorganic salt and the organism of selecting IV, V, VI family element; utilize sol-gel method to obtain and the corresponding oxide compound uniform coating of element on different shape, dissimilar carbon materials surfaces; then in protective atmosphere under certain temperature, utilize carbon reduction reaction to obtain the carbide coating of above-mentioned element on carbon materials surface.Form because the formation of these carbide coatings is chemical reactions, not only firm attachment and has changed carbon and copper bonded angle of wetting on the carbon materials surface forever.Owing to the characteristic of IV, V, VI family element conduction, this carbide coating of formation has excellent conducting performance simultaneously.With carbon/carbon/carbon-copper composite material that this carbon material with carbide coating is made, because the wetting angle of high-melting-point conductive carbide coating and copper is very little, the coating interface bonding force is strong, and little to the influence of matrix material electrical property electroconductibility.
Can adopt the soluble inorganic salt of IV, V such as containing Mo, W, Cr, Ti, Ta, V, Nb, VI family element and organism at different shape, form and the wetting high-melting-point conductive carbide coating of copper, and equilibrium wetting angle and the resistivity such as the following table of copper on dissimilar carbon materials surfaces:
The wetting carbide of table 1 and copper under 1200 ℃ of vacuum with the equilibrium wetting angle and the resistivity Carbides Cr of copper
3C
2WC Mo
2C TaC NbC
0.97TiC
0.49VC
0.83Contact angle/ θ ° of 47 70 60 60 25 Electrical resistant/ Ω m * 10
-875 19.2 71～100 44～147 102
Technological process of the present invention is: the soluble inorganic salt and the organism that will contain IV, V, VI family element, be dissolved in the organic-inorganic solution, the oxyhydroxide precipitation pH value of control strength of solution and solution forms the sol solutions (sol-gel method) that contains IV, V, VI family element; The material that will belong to the allotropic substance of carbon is dipped in the colloidal sol or above-mentioned colloidal sol is coated on the allotropic substance material surface of carbon, the control reaction makes above-mentioned coating change gel into, through Temperature Treatment, gel decomposition is become contain the oxide compound and the water of IV, V, VI family element, and react at the allotropic substance material surface of carbon and to form the film of above-mentioned oxide compound; To apply the carbon allotrope material of the oxide coating that contains IV, V, VI family element at Ar
2Be heated to 700～800 ℃ of temperature under the protection, oxide compound forms firm, the conductivity excellence with the reaction of top layer carbon and can improve carbon combines angle of wetting with copper carbide coating.
This method can be carried out coating to different shape size, dissimilar carbon materials surfaces, and the bonding strength at interface is very high, and the resistivity of IV, V, VI family element is than the resistivity (1.25 * 10 of carbon
-3Ω cm) low, thus can improve at the interface conductive characteristic with its making coatings, to emphasize to conduct electricity, the Cu-base composites of heat conductivility is very favourable.Facts have proved that carbon/carbon/carbon-copper composite material specific conductivity, thermal conductivity and density height, the quality made with this coating are good.Because temperature of reaction is lower in this technology.And only need adopt the cheap protective gas protection of wide material sources, so need not adopt vacuum apparatus.The coating material requested is an industrial or agricultural industrial chemicals commonly used, wide material sources, cheapness.Therefore, this preparation technology of coating is simple, and is easy to operate, with low cost, and whole process of preparation is pollution-free, safe and reliable.
Description of drawings:
Fig. 1, technological process synoptic diagram
Fig. 2, embodiment synoptic diagram
Embodiment: to apply Mo
2The C+Mo coating is an example
The first, adopt sol-gel method at carbon materials surface-coated MoO
3Coating: adopt molybdenum ammonium solution [(NH
4)
6Mo
7O
244H
2O], when ammonium paramolybdate is dissolved in hot water and water generation hydrolysis reaction, the oxyhydroxide precipitation pH value of the concentration of control molybdenum salt and solution makes it produce polycondensation under certain acidity and temperature, forms H
2MoO
4Colloidal sol; The allotropic substance of carbon is dipped in H
2MoO
4In the colloidal sol or with H
2MoO
4Colloidal sol is coated on the allotropic substance material surface of carbon, and this has been applied H
2MoO
4After the allotropic substance material of the carbon of colloidal sol is dried certain temperature, cause H
2MoO
4Resolve into MoO
3And water, promptly obtain MoO
3Coating is at the allotropic substance material surface formation MoO of carbon
3Film.This coating liquid good film-forming property, the membrane structure densification that makes, coating is even.
The second, applied MoO
3After the coating, at argon gas (Ar
2) protection under carry out 700～900 ℃ of high-temperature heat treatment, make MoO
3Coating is by the CO reduction of the C on carbon materials surface and generation therefrom.Detect through χ-X-ray analysis X, principal phase is α-Mo in the coating
2C also contains the metal M o that is reduced out on a small quantity in addition.Promptly directly generate uniform Mo on the carbon materials surface
2The C+Mo coating.About 0.2～0.3 μ m of coat-thickness.Its mechanism is: MoO
3Diffusion at high temperature, or directly with the carbon materials reaction, or shift to reductive agent-carbon materials surface with steam condition, adsorb thereon, and further reduction reaction take place herein.The intermidate oxide that generates is diffused in reductive agent-carbon materials, and gaseous product CO, CO
2From reductive agent-carbon materials surface desorption.Also just because of there is the migration of gas, so this method can be carried out coating to different shape size, dissimilar carbon materials surfaces,
Mo
2Wetting angle between C+Mo coating and copper and copper alloy melt is best with the copper wettability in all carbide, drips through actual seat to experiment showed, Mo
2Wetting angle between C+Mo coating and copper and copper alloy melt is between 0～30 °.Simultaneously, because Mo, Mo
2The hardness of C is very high, and is reaction coating, so the bonding strength at interface is very high, this point is particularly conducive to diamond tool.Simultaneously, Mo, Mo
2The resistivity of C is than the resistivity (1.25 * 10 of carbon
-3Ω cm) also little, as Mo
2C is 4.9 * 10
-5Ω cm, thus can improve at the interface conductive characteristic with its making coatings, to emphasize to conduct electricity, the Cu-base composites of heat conductivility is very favourable.Facts have proved that carbon/carbon/carbon-copper composite material specific conductivity, thermal conductivity and density height, the quality made with this coating are good.Practice is proof also, and the Infiltration Technics with low pressure as the vacuum infiltration method, can successfully be infiltrated up to copper melt by in coating carbon materials particle or the fibrous porous insert, can obtain carbon/carbon/carbon-copper composite material after solidifying.
In a word, apply Mo
2The C+Mo coating can make the wettability of carbon/copper interface and bonding force be improved significantly, is that the ideal at carbon/carbon/carbon-copper composite material interface is selected.
At MoO
3Obtain Mo with the C reaction
2In the process of C+Mo coating, temperature of reaction is lower, and only need adopt the cheap protective gas protection of wide material sources, and need not adopt vacuum apparatus, and the coating material requested is an industrial or agricultural industrial chemicals commonly used, wide material sources, cheapness.Therefore, this preparation technology of coating is simple, and is easy to operate, with low cost, and whole process of preparation is pollution-free, safe and reliable.
In addition, utilize this coating process can be easily on different shape (as: carbon granule, carbon fiber, carbon nanotube etc.), dissimilar carbon materials (homoatomic isomer such as diamond, graphite, carbon, soccerballene) apply multiple carbide coating, specifically have: Mo
2C, MoC, W
2C, WC, Cr
3C
2, Cr
7C
3, TiC
x, TaC, VC, NbC etc.
Claims (3)
1, a kind of carbide coating and technology thereof that improves carbon/copper interface binding characteristic is carried out coating to material surface and is handled.It is characterized in that: soluble inorganic salt and the organism of selecting IV, V, VI family element; utilize sol-gel method to obtain and the corresponding oxide compound uniform coating of element on different shape, dissimilar carbon materials surfaces; then in protective atmosphere under certain temperature, utilize carbon reduction reaction to obtain the carbide coating of above-mentioned element on carbon materials surface.
2, a kind of carbide coating and technology thereof that improves carbon/copper interface binding characteristic as claimed in claim 1 is characterized in that: can adopt IV, V such as containing Mo, W, Cr, Ti, Ta, V, Nb, VI family element to form Cr
3C
2, WC, Mo
2C, TaC, NbC, VC, TiC
0.49, coating.
3, a kind of technology that realizes claim 1, it is characterized in that: the soluble inorganic salt and the organism that will contain IV, V, VI family element, be dissolved in the organic and inorganic solution, the oxyhydroxide of control strength of solution and solution precipitation pH value forms the sol solutions (sol-gel method) that contains IV, V, VI family element; The material that will belong to the allotropic substance of carbon is dipped in the colloidal sol or above-mentioned colloidal sol is coated on the allotropic substance material surface of carbon, the control reaction makes above-mentioned coating change gel into, through Temperature Treatment, gel decomposition is become contain the oxide compound and the water of IV, V, VI family element, and react at the allotropic substance material surface of carbon and to form the film of above-mentioned oxide compound; To apply the carbon allotrope material of the oxide coating that contains IV, V, VI family element at Ar
2Be heated to 700～800 ℃ of temperature under the protection, oxide compound forms firm, the conductivity excellence with the reaction of top layer carbon and can improve carbon combines angle of wetting with copper carbide coating.
Priority Applications (1)
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|---|---|---|---|
| CN 02114427 CN1435503A (en) | 2002-01-28 | 2002-01-28 | Carbide coating of enhancing carbon/copper interface binding characteristic, and process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02114427 CN1435503A (en) | 2002-01-28 | 2002-01-28 | Carbide coating of enhancing carbon/copper interface binding characteristic, and process thereof |
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ID=27628471
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248283B (en) * | 2005-08-01 | 2010-12-01 | Skf股份公司 | Bearing and method of producing the same |
| CN101768706B (en) * | 2010-01-05 | 2012-09-05 | 北京科技大学 | Preparation method of diamond particle reinforced copper-based composite material parts with high volume fraction |
| CN107176604A (en) * | 2016-03-10 | 2017-09-19 | 中国科学院金属研究所 | A kind of method that carbon materials surface in situ generates nano-carbide coating |
| CN109095939A (en) * | 2018-09-18 | 2018-12-28 | 航天特种材料及工艺技术研究所 | A kind of silicon carbide fiber reinforced silicon carbide composite material and preparation method thereof that tungsten carbide interface layer is modified |
| CN109095938A (en) * | 2018-09-18 | 2018-12-28 | 航天特种材料及工艺技术研究所 | A kind of silicon carbide fiber reinforced silicon carbide composite material and preparation method thereof that dimolybdenum carbide boundary layer is modified |
| CN110048125A (en) * | 2019-03-19 | 2019-07-23 | 长沙市秒冲电池技术与材料研究所 | Power battery, negative electrode tab, cathode composite foil and preparation method thereof |
| CN110157999A (en) * | 2019-05-09 | 2019-08-23 | 李纳 | A kind of pantograph pan graphite fibre enhancing Cu-base composites |
| CN111799621A (en) * | 2020-06-28 | 2020-10-20 | 东风博泽汽车系统有限公司 | High-current-resistant motor carbon brush composite material |
| CN112981299A (en) * | 2021-02-07 | 2021-06-18 | 哈尔滨工业大学 | Method for preparing high-bonding-strength carbide coating on diamond surface by using thermal plasma |
-
2002
- 2002-01-28 CN CN 02114427 patent/CN1435503A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248283B (en) * | 2005-08-01 | 2010-12-01 | Skf股份公司 | Bearing and method of producing the same |
| CN101768706B (en) * | 2010-01-05 | 2012-09-05 | 北京科技大学 | Preparation method of diamond particle reinforced copper-based composite material parts with high volume fraction |
| CN107176604B (en) * | 2016-03-10 | 2019-08-02 | 中国科学院金属研究所 | A kind of method that carbon materials surface in situ generates nano-carbide coating |
| CN107176604A (en) * | 2016-03-10 | 2017-09-19 | 中国科学院金属研究所 | A kind of method that carbon materials surface in situ generates nano-carbide coating |
| CN109095939A (en) * | 2018-09-18 | 2018-12-28 | 航天特种材料及工艺技术研究所 | A kind of silicon carbide fiber reinforced silicon carbide composite material and preparation method thereof that tungsten carbide interface layer is modified |
| CN109095938A (en) * | 2018-09-18 | 2018-12-28 | 航天特种材料及工艺技术研究所 | A kind of silicon carbide fiber reinforced silicon carbide composite material and preparation method thereof that dimolybdenum carbide boundary layer is modified |
| CN109095938B (en) * | 2018-09-18 | 2021-03-16 | 航天特种材料及工艺技术研究所 | Silicon carbide fiber reinforced silicon carbide composite material modified by dimolybdenum carbide interface layer and preparation method thereof |
| CN109095939B (en) * | 2018-09-18 | 2021-06-25 | 航天特种材料及工艺技术研究所 | Silicon carbide fiber reinforced silicon carbide composite material modified by tungsten carbide interface layer and preparation method thereof |
| CN110048125A (en) * | 2019-03-19 | 2019-07-23 | 长沙市秒冲电池技术与材料研究所 | Power battery, negative electrode tab, cathode composite foil and preparation method thereof |
| CN110157999A (en) * | 2019-05-09 | 2019-08-23 | 李纳 | A kind of pantograph pan graphite fibre enhancing Cu-base composites |
| CN111799621A (en) * | 2020-06-28 | 2020-10-20 | 东风博泽汽车系统有限公司 | High-current-resistant motor carbon brush composite material |
| CN112981299A (en) * | 2021-02-07 | 2021-06-18 | 哈尔滨工业大学 | Method for preparing high-bonding-strength carbide coating on diamond surface by using thermal plasma |
| CN112981299B (en) * | 2021-02-07 | 2022-03-04 | 哈尔滨工业大学 | Method for preparing high-bonding-strength carbide coating on diamond surface by using thermal plasma |
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