CN110981550B - Metallization preparation method of boron carbide ceramic - Google Patents
Metallization preparation method of boron carbide ceramic Download PDFInfo
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- C04B41/88—Metals
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5133—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the refractory metals
Abstract
A metallization preparation method of boron carbide ceramic comprises the steps of ball-milling and mixing three metal powders of 10-40wt% of Mo, 10-40wt% of W and 10-40wt% of Ni, adding an ethyl cellulose solution and a metal salt solution, mixing and ball-milling, wherein the metal salt solution is one or more of ammonium molybdate, ammonium tungstate or ammonium paratungstate solution, and obtaining metallization paste; printing the metallization paste on the part of the boron carbide ceramic part needing metallization, and drying; putting the dried boron carbide ceramic piece into a metallized sintering furnace, introducing hydrogen, preserving the temperature at 1650-1680 ℃ for 30-35 minutes, keeping the dew point at 0-10 ℃, and cooling along with the furnace. The formed Mo, W and Ni are matched with the thermal expansion system of the metallized layer alloy material to be close to that of boron carbide, and the metallized layer alloy material has high bonding strength and small metallization stress. Due to the submicron metal network structure, the brazing filler metal is not easy to fall off after brazing.
Description
Technical Field
The invention relates to the technical field of ceramic metallization, in particular to a preparation method of boron carbide ceramic metallization.
Background
Metallization is a special process, is suitable for metallization treatment of ceramic surfaces, and after the treatment, the ceramic surfaces have metal properties, and in order to obtain the metal properties of the ceramic, a layer of metal coating needs to be coated on the ceramic surfaces, and then the ceramic surfaces are placed on refractory materials and enter a high-temperature furnace for sintering.
Boron carbide is a non-metallic material of important physicochemical properties, and is the hardest boron compound following boron nitride. The boron carbide can be added into alumina and silicon carbide ceramics, so that the fracture toughness of the material can be improved, and the strength of the material is relatively improved; because boron carbide can also absorb a large amount of neutrons, the application of boron carbide is wider.
Boron carbide is a high-temperature P-type semiconductor material and has excellent properties of strong hardness, low density, high chemical inertness and the like. Can react with Fe, Ni, Ti, Zr and other metals at the high temperature of 1000 ℃. In addition, boron carbide has good application in atomic physics and medicine because of its strong neutron absorbing ability. In addition, boron carbide has wide applications in microelectronics, nuclear physics, military and space technology due to the properties.
Boron carbide is only a semiconductor, and needs to be metallized on the surface of a ceramic to be welded with a metal, and many metallization methods are used, but the boron carbide is easy to be detached when being brazed with other metals, and has a great influence on practical use.
Disclosure of Invention
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of boron carbide ceramic metallization comprises the following steps:
s1: mixing the powder; weighing three metal powders of Mo (10-40 wt%), W (10-40 wt%) and Ni (10-40 wt%) according to the weight ratio, and putting the metal powders into a ceramic ball-milling tank, wherein the material-ball ratio is 1: 2, ball milling for 100 hours, and sieving by a 300-mesh sieve to obtain mixed metal powder; the obtained metal particles with the diameter of about 50 microns are smaller, the leveling property is better, the mixing is more uniform, the roughness of the metallized surface after sintering is lower, and the metallized layer is more densely adhered to the surface of the ceramic.
S2: preparing paste; and (2) mixing the metal powder obtained from the S1 according to the weight ratio of 100-120: 30 percent of the mixture and 5 percent of ethyl cellulose solution by weight are mixed and ball-milled for 48 hours to obtain metallization paste; the metal particles are very fine after ball milling, the smaller the particle diameter is, the more spherical the surface of the metal particles is, the friction force is very small, and the metal particles are difficult to attach to the surface of the ceramic; the ethyl cellulose has the functions of adhesion, filling and film formation, and is used as an adhesive for bonding the metal particles and the ceramic surface to form a film.
S3: printing; printing the metallization paste obtained in the step S2 on a part of the boron carbide ceramic piece, which needs to be metallized, with the thickness of 20-30 μm, and drying; and brushing the metallization paste on the surface of the boron carbide ceramic part, leveling and drying to form a primary film and attach the primary film on the surface of the boron carbide ceramic part.
The drying method is further provided, the metallization paste is coated on the surface of the boron carbide ceramic part, because a process is needed for drying, the metallization paste coating layer is in a paste shape in the early stage, and slowly sinks towards the gravity direction under the influence of gravity in the drying process, so that the thickness of the dried metal layer is inconsistent, therefore, the boron carbide ceramic part coated with the metallization paste is placed on the substrate with the small holes, the boron carbide ceramic part is dried upwards from the substrate by adopting hot air, the influence of gravity on the metallization paste coating layer is reduced, the thickness of the dried metallization layer is more uniform, and excessive sinking of the metallization paste is avoided.
S4: metallization; and (3) putting the dried boron carbide ceramic piece in the S3 into a metallization sintering furnace, introducing hydrogen, keeping the temperature at 1650-1680 ℃ for 30-35 minutes, keeping the dew point at 0-10 ℃, and cooling along with the furnace.
Wherein the melting point of boron carbide is 2350 deg.C, the melting point of Mo is 2610 deg.C, the melting point of W is 3410 + -20 deg.C, the melting point of Ni is 1453 deg.C, Ni is used as molten metal in a sintering furnace, and W and Mo are fused to form an alloy metal layer. Boron carbide is basically stable at the temperature below 800 ℃ in an air environment, transition metals of IV, V and VI groups in the periodic table of elements of the boron carbide react with boron carbide powder strongly to form metal boride at the temperature of 1000-1100 ℃, the boron carbide is easy to nitride or react with transition metal oxide at a higher reaction temperature to form corresponding boron nitride and boride, the boride is more in rare earth and alkaline earth hexaboride, the dried metallization paste coating can be well fused at the temperature of 1650-1680 ℃, and the stability of the boron carbide can be ensured.
As a further improvement of the above technical solution:
and (3) constructing an organic-inorganic network, adding 20-40 parts by weight of metal salt solution before ball milling in the step S3, and evaporating and dehydrating the mixed solution at 20-30 ℃ after the ball milling is finished to obtain the metallization paste with the water content of 25-40%. The sintering in the metallization sintering furnace adopts hydrogen atmosphere, and hydrogen has strong reducibility, and can reduce a part of metal salt into metal under the condition of high temperature. After the metal salt solution is mixed with the ethyl cellulose solution and ball-milled, the metal salt is fully mixed and dried, the metal salt is separated out along the ethyl cellulose to form an organic-inorganic network, Mo, W and Ni metal particles are distributed, the ethyl cellulose is decomposed after sintering, the metal salt distributed along the ethyl cellulose is also decomposed and reduced into metal to form a metal submicron network, so that the metallization layer is fused more tightly, and the internal stress of the metallization layer is reduced.
The metal salt solution is one or more of ammonium molybdate or ammonium tungstate and ammonium paratungstate solution. Decomposing ammonium molybdate to generate ammonia gas and MoO3 in the high-temperature heating process, and reducing MoO3 by hydrogen to generate molybdenum; the ammonium tungstate is mainly used for manufacturing metal tungsten powder made of tungsten trioxide or blue tungsten oxide, is decomposed to generate ammonia gas and tungsten trioxide in the high-temperature heating process, and is reduced by hydrogen to generate tungsten dioxide so as to finally form tungsten powder; heating ammonium paratungstate to above 600 ℃ to lose all ammonia and crystal water, completely converting the ammonium paratungstate into yellow tungsten trioxide, and reducing the tungsten trioxide into tungsten dioxide by hydrogen so as to finally form tungsten powder. The tungsten powder reduced by the tungsten trioxide has fine granularity and more uniform granularity distribution. The specific surface area of the tungsten powder is 0.269m2/g, the particle size of the tungsten powder is 90.36% of 1-7 μm, 0.71% of 0.8-1.0 μm and 8.93% of 7-10 μm. The specific surface area of molybdenum powder generated by reduction of molybdenum trioxide is 0.126m2/g, the particle size of tungsten powder is 91.43% of 1-6 μm, 0.93% of 0.8-1.0 μm and 7.64% of 6-9 μm. Therefore, after the metal salt is reduced, a submicron metal network arranged along the ethyl cellulose is generated, the metal network is uniformly dispersed along each direction and is fused with the Mo, the W and the Ni to form a metallized layer with a submicron structure, the stress of the metallized layer with the submicron structure is smaller, the expansion coefficient of the metallized layer with the submicron structure is closer to that of a ceramic material, and the bonding strength is high. When the brazing alloy is brazed with other metals, the special microstructure and the welding periphery of the brazing alloy are firmer.
The weight ratio of the metal salt solution is 10-15%. The metal salt is mainly used for constructing an organic-inorganic network to form a metal salt network arranged along the ethyl cellulose, the content of the metal salt is increased, the occupied volume is increased after drying, a large amount of ammonia gas and water vapor are generated after heating and decomposition, holes are easy to form, only Ni can be melted in Mo, W and Ni metals at 1650-1680 ℃, and more holes are difficult to level.
And in the step S3, drying, namely, putting the printed boron carbide ceramic part into a drying furnace, heating up to 30 ℃ every 10 minutes by hot dry air of 1-2m/S from the antigravity direction until the temperature is raised to 120 ℃ and is preserved for 10 minutes, then heating up to 600 ℃ by an electric furnace and preserving the temperature for 10 minutes, and cooling along with the furnace. And decomposing ammonia gas in the ammonium molybdate, the ammonium tungstate or the ammonium paratungstate in the drying process to form metal oxide. Ammonium tungstate and ammonium paratungstate are heated to above 600 ℃ to lose all ammonia and crystal water, and ammonium molybdate is heated to above 540 ℃ to lose all ammonia and crystal water.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, by adding ammonium molybdate, ammonium tungstate or ammonium paratungstate metal salt into the metallization paste, metal salt crystals or metal oxides arranged along the ethyl cellulose are formed in the drying process, and then a submicron metal network arranged along the ethyl cellulose is formed after high-temperature reduction, so that the metallization layer has a submicron metal network structure, the internal stress is smaller, and the adhesion is stronger.
2. The Mo, W and Ni ratio of the metallized layer alloy material formed by the method is close to the thermal expansion system of boron carbide, the bonding strength is high, and the metallization stress is small.
3. The boron carbide ceramic part can be brazed with other metals without electroplating after metallization, and is not easy to fall off after brazing due to the submicron metal network structure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
the preparation method of the boron carbide ceramic by metallization comprises the following steps:
s1: mixing the powder; weighing three metal powders of Mo (10 wt%), W (10 wt%) and Ni (10 wt%) according to a ratio, and putting the metal powders into a ceramic ball-milling tank, wherein the ratio of material balls to material balls is 1: 2, ball milling for 100 hours, and sieving by a 300-mesh sieve to obtain mixed metal powder;
s2: preparing paste; and (3) mixing the metal powder obtained in the step (S1) according to the weight ratio of 100: 30 percent of the mixture and 5 percent of ethyl cellulose solution by weight are mixed and ball-milled for 48 hours to obtain metallization paste;
s3: printing; printing the metallization paste obtained in the step S2 on a part of the boron carbide ceramic piece, which needs to be metallized, with the thickness of 20 mu m, and drying;
s4: metallization; and (3) putting the dried boron carbide ceramic piece in the S3 into a metallization sintering furnace, introducing hydrogen, keeping the temperature at 1650 ℃ for 30 minutes, keeping the dew point at 0-10 ℃, and cooling along with the furnace.
Example 2:
the preparation method of the boron carbide ceramic by metallization comprises the following steps:
s1: mixing the powder; weighing three metal powders of Mo (10 wt%), W (10 wt%) and Ni (10 wt%) according to a ratio, and putting the metal powders into a ceramic ball-milling tank, wherein the ratio of material balls to material balls is 1: 2, ball milling for 100 hours, and sieving by a 300-mesh sieve to obtain mixed metal powder;
s2: preparing paste; and (3) mixing the metal powder obtained in the step (S1) according to the weight ratio of 100: 30 parts of the metal salt solution and 5% of ethyl cellulose solution, adding 20 parts of the metal salt solution, and performing ball milling for 48 hours to obtain a metallization paste; after the ball milling is finished, evaporating the mixed solution at 20 ℃ to remove water to obtain metallization paste with the water content of 25%;
s3: printing; printing the metallization paste obtained in the step S2 on the positions of the boron carbide ceramic piece needing metallization, wherein the thickness of the metallization paste is 20 microns; placing the printed boron carbide ceramic part into a drying furnace, heating up to 30 ℃ every 10 minutes by passing 1m/s hot dry air from the antigravity direction, keeping the temperature for 10 minutes when the temperature is raised to 120 ℃, then heating up to 600 ℃ by adopting an electric furnace, keeping the temperature for 10 minutes, and cooling along with the furnace;
s4: metallization; and (3) putting the dried boron carbide ceramic piece in the S3 into a metallization sintering furnace, introducing hydrogen, keeping the temperature at 1650 ℃ for 30 minutes, keeping the dew point at 0-10 ℃, and cooling along with the furnace.
The metal salt solution is ammonium molybdate.
The weight ratio of the ammonium molybdate solution is 10 percent.
Example 3:
the preparation method of the boron carbide ceramic by metallization comprises the following steps:
s1: mixing the powder; weighing three metal powders of Mo (40 wt%), W (40 wt%) and Ni (40 wt%) according to the weight ratio, and putting the metal powders into a ceramic ball-milling tank, wherein the material-ball ratio is 1: 2, ball milling for 100 hours, and sieving by a 300-mesh sieve to obtain mixed metal powder;
s2: preparing paste; and (3) mixing the metal powder obtained in the step (S1) according to the weight ratio of 120: mixing the mixture with ethyl cellulose solution of which the weight ratio is 5% in a proportion of 30, adding metal salt solution of which the weight ratio is 40, performing ball milling for 48 hours, and evaporating the mixed solution at 30 ℃ to remove water to obtain metallization paste with the water content of 40% to obtain metallization paste;
s3: printing; printing the metallization paste obtained in the step S2 on a part of a boron carbide ceramic piece to be metallized, wherein the thickness of the metallization paste is 30 microns, putting the printed boron carbide ceramic piece into a drying furnace, heating the boron carbide ceramic piece to 30 ℃ per 10 minutes by hot dry air of 2m/S in the antigravity direction, keeping the temperature of the boron carbide ceramic piece at 120 ℃ for 10 minutes, heating the boron carbide ceramic piece to 600 ℃ by using an electric furnace, keeping the temperature of the boron carbide ceramic piece at 10 minutes, and cooling the boron carbide ceramic piece along with the furnace;
s4: metallization; and (3) putting the dried boron carbide ceramic piece in the S3 into a metallization sintering furnace, introducing hydrogen, keeping the temperature at 1680 ℃ for 35 minutes, keeping the dew point at 0-10 ℃, and cooling along with the furnace.
The metal salt solution is a mixed solution of ammonium molybdate, ammonium tungstate and ammonium paratungstate.
The weight ratio of the mixed solution is 15%.
Example 4:
the preparation method of the boron carbide ceramic by metallization comprises the following steps:
s1: mixing the powder; weighing three metal powders of Mo (10 wt%), W (25 wt%) and Ni (30 wt%) according to a ratio, and putting the metal powders into a ceramic ball-milling tank, wherein the ratio of material balls to material balls is 1: 2, ball milling for 100 hours, and sieving by a 300-mesh sieve to obtain mixed metal powder;
s2: preparing paste; and (2) mixing the metal powder obtained in the step (S1) according to the weight ratio of 110: 30 parts of the metal salt solution is added, and after ball milling for 48 hours, evaporation is carried out on the mixed solution at 25 ℃ to remove water, so as to obtain metallization paste with the water content of 30%;
s3: printing; printing the metallization paste obtained in the step S2 on a part, needing metallization, of the boron carbide ceramic part, wherein the thickness of the metallization paste is 25 microns, putting the printed boron carbide ceramic part into a drying furnace, heating the boron carbide ceramic part to 30 ℃ per 10 minutes through 1.5m/S of hot dry air in the antigravity direction, keeping the temperature for 10 minutes when the temperature is raised to 120 ℃, then heating the boron carbide ceramic part to 600 ℃ by using an electric furnace, keeping the temperature for 10 minutes, and cooling the boron carbide ceramic part along with the furnace;
s4: metallization; and (3) putting the dried boron carbide ceramic part in the S3 into a metallization sintering furnace, introducing hydrogen, keeping the temperature at 1660 ℃ for 32 minutes, keeping the dew point at 0-10 ℃, and cooling along with the furnace.
And (4) constructing an organic-inorganic network, and before ball milling in the step S3.
The metal salt solution is a mixed solution of ammonium molybdate and ammonium tungstate.
The weight ratio of the mixed solution is 12%.
Example 5:
the preparation method of the boron carbide ceramic by metallization comprises the following steps:
s1: mixing the powder; weighing three metal powders of Mo (15 wt%), W (20 wt%) and Ni (30 wt%) according to a ratio, and putting the metal powders into a ceramic ball-milling tank, wherein the ratio of material balls to material balls is 1: 2, ball milling for 100 hours, and sieving by a 300-mesh sieve to obtain mixed metal powder;
s2: preparing paste; and (3) mixing the metal powder obtained in the step (S1) according to the weight ratio of 120: 30 percent of the mixture and 5 percent of ethyl cellulose solution by weight are mixed and ball-milled for 48 hours to obtain metallization paste;
s3: printing; printing the metallization paste obtained in the step S2 on a part, needing metallization, of the boron carbide ceramic part, wherein the thickness of the metallization paste is 25 microns, putting the printed boron carbide ceramic part into a drying furnace, heating the boron carbide ceramic part to 30 ℃ per 10 minutes by 1m/S of hot dry air from the antigravity direction, keeping the temperature of the boron carbide ceramic part at 120 ℃ for 10 minutes, heating the boron carbide ceramic part to 600 ℃ by using an electric furnace, keeping the temperature of the boron carbide ceramic part at 10 minutes, and cooling the boron carbide ceramic part along with the furnace;
s4: metallization; and (3) putting the dried boron carbide ceramic piece in the S3 into a metallization sintering furnace, introducing hydrogen, keeping the temperature at 1650 ℃ for 30 minutes, keeping the dew point at 0-10 ℃, and cooling along with the furnace.
And (3) constructing an organic-inorganic network, adding a metal salt solution with weight proportion of 40 before ball milling in the step S3, and evaporating and dehydrating the mixed solution at 30 ℃ after the ball milling is finished to obtain the metallization paste with the water content of 25%.
The metal salt solution is a mixed solution of ammonium molybdate, ammonium tungstate and ammonium paratungstate.
The weight ratio of the mixed solution is 10-15%.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (2)
1. The metallization preparation method of the boron carbide ceramic is characterized by comprising the following steps:
s1: mixing the powder; weighing three metal powders of 10-40wt% of Mo, 10-40wt% of W and 10-40wt% of Ni according to the weight ratio, and putting the metal powders into a ceramic ball milling tank, wherein the ratio of material balls to material balls is 1: 2, ball milling for 100 hours, and sieving by a 300-mesh sieve to obtain mixed metal powder;
s2: preparing paste; and (2) mixing the metal powder obtained from the S1 according to the weight ratio of 100-120: 30 parts of the mixture is mixed with 5% of ethyl cellulose solution by weight, then 20-40 parts of metal salt solution by weight is added for mixing, after ball milling is carried out for 48 hours, evaporation and dehydration are carried out on the mixed solution at 20-30 ℃, and metallization paste with the water content of 25-40% is obtained;
the metal salt solution is one or more of ammonium molybdate, ammonium tungstate or ammonium paratungstate solution;
s3: printing; printing the metallization paste obtained in the step S2 on a part of the boron carbide ceramic piece to be metallized, wherein the thickness of the metallization paste is 20-30 mu m, and drying;
s4: metallization; and (3) putting the dried boron carbide ceramic piece in the S3 into a metallization sintering furnace, introducing hydrogen, keeping the temperature at 1650-1680 ℃ for 30-35 minutes, keeping the dew point at 0-10 ℃, and cooling along with the furnace.
2. The method for preparing boron carbide ceramic by metallization according to claim 1, wherein: and in the step S3, drying, namely, putting the printed boron carbide ceramic part into a drying furnace, heating up to 30 ℃ every 10 minutes by hot dry air of 1-2m/S from the antigravity direction until the temperature is raised to 120 ℃ and is preserved for 10 minutes, then heating up to 600 ℃ by an electric furnace and preserving the temperature for 10 minutes, and cooling along with the furnace.
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| CN1800096A (en) * | 2005-11-15 | 2006-07-12 | 山东大学 | Boron carbide base ceramic sand jet material |
| CN101353264A (en) * | 2008-09-26 | 2009-01-28 | 北京科技大学 | Method for improving ceramic metallized layer microstructure |
| CN102700192A (en) * | 2012-06-21 | 2012-10-03 | 北京理工大学 | Metal and ceramic composite material and preparation method of metal and ceramic composite material |
| CN103373860A (en) * | 2012-04-27 | 2013-10-30 | 比亚迪股份有限公司 | Surface metalized coating composition of ceramic matrix, surface metalizing method of ceramic matrix, and coating and ceramic prepared from ceramic matrix |
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| US20110227259A1 (en) * | 2009-07-24 | 2011-09-22 | Saint-Gobain Ceramics & Plastics, Inc. | Methods of forming sintered boron carbide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800096A (en) * | 2005-11-15 | 2006-07-12 | 山东大学 | Boron carbide base ceramic sand jet material |
| CN101353264A (en) * | 2008-09-26 | 2009-01-28 | 北京科技大学 | Method for improving ceramic metallized layer microstructure |
| CN103373860A (en) * | 2012-04-27 | 2013-10-30 | 比亚迪股份有限公司 | Surface metalized coating composition of ceramic matrix, surface metalizing method of ceramic matrix, and coating and ceramic prepared from ceramic matrix |
| CN102700192A (en) * | 2012-06-21 | 2012-10-03 | 北京理工大学 | Metal and ceramic composite material and preparation method of metal and ceramic composite material |
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