CN101591741A - A kind of is the ceramic matric composite and the metal phase adding method thereof of metallographic phase with the copper alloy - Google Patents
A kind of is the ceramic matric composite and the metal phase adding method thereof of metallographic phase with the copper alloy Download PDFInfo
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- CN101591741A CN101591741A CNA200910043721XA CN200910043721A CN101591741A CN 101591741 A CN101591741 A CN 101591741A CN A200910043721X A CNA200910043721X A CN A200910043721XA CN 200910043721 A CN200910043721 A CN 200910043721A CN 101591741 A CN101591741 A CN 101591741A
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Abstract
The invention provides a kind of is the ceramic matric composite and the metal phase adding method thereof of metallographic phase with the copper alloy, solves the problem that the fine copper metallographic phase overflows in such matrix material sintering process, and improves density, specific conductivity and the toughness of material.The metal-powder of ceramic-metal composite material of the present invention is to coat one deck nickel cobalt (alloy) or one of them on Cu powder surface, perhaps coat one or more metals among Ag, Pd, Au, the Pt earlier on the copper powder surface, and then coating layer of metal nickel or cobalt, perhaps nickel cobalt (alloy) is made composite powder.Nickel or cobalt contents are 5%-40% in the composite powder; Other metal content is 0-20wt%.After composite metal powder and ceramic powder thorough mixing are even, go out ceramic-metal composite material by prepared such as compression moulding, degreasing, sintering.Solve the problem that current material system copper in preparation process is assembled mutually, overflowed, have greatly improved at aspects such as material density, electric conductivity, intensity and toughness simultaneously.
Description
Technical field
The invention belongs to technical field of composite materials, relating to a kind of is the ceramic matric composite and the metal phase adding method thereof of metallographic phase with the copper alloy.
Background technology
Stupalith has high fusing point, consistency and elasticity modulus, and its thermotolerance, solidity to corrosion and wear resistance are good, is widely used in fields such as military project, aerospace, automobile, electronics, metallurgy.Although stupalith has the property of excellence like this, fragility is its fatal shortcoming, has limited the performance and the application of its characteristic.Metallic substance has good ductility energy and machining property.Therefore, with pottery and metal composite together, can produce the high performance composite that have the good ductility of metallic substance and thermal conductivity and the good heat-resistant antifriction of stupalith etc. concurrently.And one of key for preparing this class matrix material is the wettability problem that solves between metallic substance and the stupalith, the wettability of ceramic matrix and metallographic phase and interfacial property, decision ceramic-metal composite material performance quality.For example, adopt powder metallurgy process to prepare NiFe
2O
4/ Cu, Ti (C, N)/during the ceramic-metal composite material of copper-bearing alloy metallographic phase such as Cu, because metallic copper is relatively poor with the wettability of pottery, be prone in the sintering process copper phase gathering, phenomenon such as overflow, and performances such as the density of matrix material, intensity and toughness all are difficult to reach the requirement of expection.For solving the problem that copper is assembled mutually, overflowed, usually copper mutually in other metal of adding improve the wettability of metallographic phase and ceramic phase, promptly in advance other metal is made powdered alloy with copper or directly mixes with ceramic powder with copper powder with the element powders form.The purpose of this invention is to provide a kind of new type of metal be added to method promptly thus the preparation be the ceramic matric composite of metallographic phase with the copper alloy, it coats other metals of one deck on the copper powder surface in advance and makes composite powder, improves the sintering character and the use properties of ceramic-metal composite material.
Summary of the invention
The invention provides a kind of is the ceramic-metal composite material and the metal phase adding method thereof of metallographic phase with the Cu alloy, solve current material system copper in preparation process and assemble mutually, overflow, and the relatively poor problem of material density, electric conductivity, intensity and toughness.
The objective of the invention is to realize in the following manner.
A kind of is that the ceramic matric composite of metallographic phase is made of the metallographic phase of ceramic phase and copper-bearing alloy with the copper alloy; The metallographic phase of described copper-bearing alloy is to coat one deck nickel, cobalt or nickel cobalt (alloy) on Cu powder surface, or has coated among Ag, Pd, Au, the Pt one or more earlier on Cu powder surface, and then has coated one deck nickel, cobalt or nickel cobalt (alloy).
Described ceramic phase comprises MFe
2O
4, MAl
2O
4, MMn
2O
4In one or more and MO type oxide compound in one or more, wherein M is selected from the metallic element of Zn, Co or Ni.
Described ceramic phase is the 70-95wt% of described ceramic-metal composite material, and described metallographic phase is the 5-30wt% of described ceramic-metal composite material.
Described a kind of be the metal phase adding method of the ceramic matric composite of metallographic phase with the copper alloy: coat one deck nickel, cobalt or nickel cobalt (alloy) on Cu powder surface, perhaps coat the metal level of one or more compositions among Ag, Pd, Au, the Pt earlier on Cu powder surface, and then coating one deck nickel, cobalt or nickel cobalt (alloy), make metallographic phase, behind composite metal powder and the ceramic powder mixing, get final product by compression moulding, degreasing, sintering.
Cu content is 60-95wt% in the described metallographic phase, and nickel or cobalt or nickel cobalt (alloy) content are 5-40wt%, and other metal content is 0-20wt%.
Copper powder coats Ag, Pd, composite metal powders such as Au, Pt prepare by chemical plating method; Copper powder coats composite metal powders such as Ni, Co or Ni-Co alloy can adopt electroless plating, hydro-thermal hydrogen reduction or carbonyl process preparation.
The metallographic phase of ceramic-metal composite material of the present invention adds mode and composite material and preparation method thereof, specifically may further comprise the steps:
The preparation of metal-powder (being the preparation of metallographic phase): adopt electroless plating method, hydro-thermal hydrogen reduction method or carbonyl process coat layer of metal nickel or cobalt on Cu powder surface, and perhaps nickel cobalt (alloy) is made composite powder; Perhaps coat one or more metal levels among Ag, Pd, Au, the Pt on the copper powder surface earlier, and then coat layer of metal nickel or cobalt, perhaps nickel cobalt (alloy) is made composite powder.Nickel or cobalt contents are 5%-40% in the composite powder;
Ceramic phase is synthetic: with NiO, Fe
2O
3After (/ or) additional metals oxide compound is proportionally prepared burden, be medium with water or alcohol, ball mill mixing 1-4 hour, dry back is the constant temperature 4-8 hour synthetic ceramic phase powder that obtains under 800-1400 ℃ of temperature;
Batch mixing: the composite metal powder and the second step synthetic ceramic powder of the first step preparation are prepared burden in proportion, and the organic binder bond and the dispersion agent that add 1%-3% carried out batch mixing 0.5-4 hour, till being dried to moisture and dispersion agent then and volatilizing fully;
Composite Preparation: adopt and to cold pressing or powder pressing forming that the method for isostatic cool pressing obtained for the 3rd step, the compacting sample is at 400-600 ℃ N
2Degreasing under the atmosphere, degreasing time are 2-6 hour, and temperature rise rate is 10-100 ℃/hour, carry out sintering then under 1200 ℃ of-1450 ℃ of temperature, nitrogen atmosphere, temperature rise rate 50-150 ℃/h, are incubated 2-10 hour, O in the sintering atmosphere
2Content is 10-2000ppm.
With adopting fine copper powder or copper powder and other metal mixed powder is that metallographic phase prepares ceramic base (ceramic phase is MFe
2O
4, MAl
2O
4, MMn
2O
4Deng, M is for being selected from Zn, Co or Ni metallic element) method of matrix material compares, the present invention adopts the copper powder surface to coat the composite powder of one deck nickel, cobalt or nickel cobalt (alloy) as metallographic phase, prevent that metallic copper is oxidized in the Composite Preparation process, and can strengthen the wettability of metallographic phase and ceramic phase, copper is assembled and spillover mutually in the elimination material sintering process, and metallographic phase is evenly distributed in material, and improves sintered density, bending strength and the conductivity of matrix material.
Description of drawings
Fig. 1 is 17 (Cu-Ni)/(NiFe
2O
4-7NiO-3CoO) ceramic-metal composite material metallographic phase region S EM line sweep photo
Embodiment
Below in conjunction with the metal phase adding method and the composite material and preparation method thereof of specific embodiment explanation ceramic-metal composite material, embodiment does not limit the present invention.
Embodiment 1:17 (Cu-Ni)/(NiFe
2O
4-7NiO-3CoO) the preparation of ceramic-metal composite material
The first step: the preparation of copper nickel composite powder (nickel content 20wt%)
Adopt chemically coated nickel method at copper powder (electrolytic copper powder, granularity is-325 orders) the uniform nickel of surface coating thickness, preparation copper nickel composite powder, detailed process is: take by weighing copper powder 35.40g, dilution heat of sulfuric acid with 10ml/L soaks the zone of oxidation of removing the surface in about 1 minute, till filtering and repeatedly cleaning copper powder to water and be neutrality with distilled water, then copper powder is added chemical nickel-plating solution (2L) and carry out till nickel plating to the nickel ion in the solution all consumes, the processing condition of chemical nickel plating are: NiSO
46H
2O20g/L; NaH
2PO
2H
2O 25g/L; Lactic acid 35ml/L; Sodium lauryl sulphate 0.2g/L; Thiocarbamide 2mg/L; Potassiumiodide 20mg/L; NaOH 10g/L; PH 4.3～4.5 (ammoniacal liquor adjusting); 70～75 ℃ of temperature; The copper nickel composite powder that chemical nickel plating obtains tap water washes clean final vacuum drying for standby;
Second step: the NiFe
2O
4Synthesizing of-7NiO-3CoO ceramic phase
With NiO, Fe
2O
3With CoO according to 35.5: 61.5: 3 mass ratio batching after, put into the roller ball mill jar, with the deionized water is medium, ball mill mixing (ratio of grinding media to material is 4: 1) 4 hours, till in 90 ℃ loft drier, being dried to moisture and evaporating fully, constant temperature 6 hours in the retort furnace under 1200 ℃ of temperature then, the synthetic NiFe that obtains
2O
4-7NiO-3CoO ceramic phase;
The 3rd step: batch mixing
The copper nickel composite powder and the second step synthetic ceramic phase powder of the first step preparation are prepared burden by 17: 83 mass ratio, and add 1%～2% polyvinyl alcohol (4%) aqueous solution and industrial spirit and carried out ball mill mixing 2 hours, till being dried to moisture and alcohol then and volatilizing fully;
The 4th step: Composite Preparation
The employing method of colding pressing, the powder that the 3rd step was obtained is pressed into the strip sample that sheet, cylindric sample and bending strength test are used under 200MPa pressure; The compacting sample is at 600 ℃ N
2Degreasing under the atmosphere, soaking time are 4 hours, and temperature rise rate is 50 ℃/h, carry out sintering then under 1350 ℃ of temperature, nitrogen atmosphere, and 100 ℃/h of temperature rise rate is incubated 6 hours, O in the sintering atmosphere
2Content is controlled at 230～250ppm.
Compare with nickel powder with the copper powder of the same ratio of direct adding, adopt the material of the method preparation that adds nickel copper-clad composite powder the phenomenon that metallographic phase overflows not occur, performance index such as density, electric conductivity and intensity all have clear improvement, and sheet, column and strip sample density all reach more than 96%; In room temperature to 900 ℃ temperature range, electric conductivity increases along with the rising of temperature, and the electric conductivity in the time of 900 ℃ reaches 85Scm
-1Room temperature bending strength is 185MPa, is that bending strength is 110MPa after 300 ℃ the thermal shock test through the temperature difference; Fig. 1 is the metallographic phase region S EM line sweep photo of this material cylindrical sample, and by this figure as can be seen, metallographic phase still exists with the form of nickel coating copper in the sample after through degreasing, sintering, can prevent that copper is oxidized in preparation process; Because outer field nickel of metallographic phase and ceramic phase be wettability preferably, has solved the problem that copper is assembled mutually and overflowed.
Embodiment 2:12 (Cu-Ag-Ni)/(NiFe
2O
4-10NiO) the preparation of ceramic-metal composite material
The preparation of the first step: copper-Yin-nickel composite powder
Adopting glucose is that reductive agent is earlier at copper powder (electrolytic copper powder, granularity is-325 orders) surface coats layer of metal silver and makes cuprum argentum composite powder, be that the reductive agent chemically coated nickel method coats the uniform nickel of thickness on the cuprum argentum composite powder surface with the diamine then, preparation copper silver nickel composite powder, detailed process is: take by weighing copper powder 35.2g, soak the zone of oxidation of removing the surface in about 1 minute with the dilution heat of sulfuric acid of 10ml/L, till filtering and repeatedly cleaning copper powder to water and be neutrality with distilled water; Get the 6.93g Silver Nitrate and add the 400ml deionized water, add ammoniacal liquor 40ml, stirring obtains clear solution, adds 2g sodium hydroxide, stirs back adding 10ml ammoniacal liquor and obtains transparent argentamine liquid; Add 30g glucose, 20ml ethanol, 6g polyoxyethylene glycol in the 400ml deionized water, stirring obtains silver-colored reduced liquid; The copper powder that to handle then adds in the reduced liquid, stirs the back and adds argentamine liquid, stirs 50 minutes, filters the back washed with de-ionized water more than three times, filters and obtains the cuprum argentum composite powder end; Then the cuprum argentum composite powder end that obtains is added to chemical nickel-plating solution (1L) and carries out till nickel plating to the nickel ion in the solution all consumes, the processing condition of chemical nickel plating are: NiSO
46H
2O 20g/L; Diamine 100ml/L; EDTA disodium 25g/L; Seignette salt 10g/L; Sodium lauryl sulphate 0.1g/L; PbAc 0.05g/L; PH 12～12.5 (NaOH adjusting); 82～85 ℃ of T; The copper silver nickel composite powder (silver and nickel content are 10wt% in the powder) that obtains cleans up the final vacuum drying for standby with deionized water;
Second step: the NiFe
2O
4Synthesizing of-10NiO ceramic phase
With NiO and Fe
2O
3Mass ratio batching according to 38.5: 61.5, put into the roller ball mill jar, with the pure water is medium, ball mill mixing in the roller ball grinding machine (ratio of grinding media to material is 4: 1) 4 hours, till in 90 ℃ loft drier, being dried to moisture and evaporating fully, constant temperature 6 hours in the retort furnace under 1200 ℃ of temperature then, the synthetic NiFe that obtains
2O
4-10NiO ceramic phase;
The 3rd step: batch mixing
With the copper nickel of the first step preparation, silver-colored nickel composite powder and the second step synthetic ceramic phase powder mass ratio batching by 12: 88, and add 1%～2% polyvinyl alcohol (4%) aqueous solution and an amount of industrial spirit carried out ball mill mixing 2 hours, then till being dried to moisture and alcohol under 70 ℃ of temperature and volatilizing fully;
The 4th step: Composite Preparation
The employing method of colding pressing, the powder that the 3rd step was obtained is pressed into the strip sample that sheet, cylindric sample and bending strength test are used under 200MPa pressure; The compacting sample is at 600 ℃ N
2Degreasing under the atmosphere, soaking time are 4 hours, and temperature rise rate is 50 ℃/h, sintering under 1300 ℃ of temperature, nitrogen atmosphere then, and 60 ℃/h of temperature rise rate is incubated 6 hours, O in the sintering atmosphere
2Content is controlled at 230～250ppm.
Adopt the ceramic-metal composite material of this method and prepared copper spillover mutually not occur, density reaches more than 97%, and in room temperature to 900 ℃ temperature range, electric conductivity increases along with the rising of temperature, and the electric conductivity in the time of 900 ℃ is about 75Scm
-1, room temperature bending strength is 155MPa, is that bending strength becomes 94MPa after 300 ℃ the thermal shock test through the temperature difference.
Embodiment 3:8 (Cu-Co)/(NiFe
2O
4-10CoO) the preparation of ceramic-metal composite material
The first step: the preparation of copper Co composite powder (cobalt contents 20wt%)
Adopt the electroless cobalt plating method at copper powder (electrolytic copper powder, granularity is-325 orders) the uniform cobalt of surface coating thickness, preparation copper Co composite powder, detailed process is: take by weighing copper powder 35.40g, dilution heat of sulfuric acid with 10ml/L soaks the zone of oxidation of removing the surface in about 1 minute, till filtering and repeatedly cleaning copper powder to water and be neutrality with distilled water, then copper powder is added electroless cobalt plating solution (2L) and carry out till cobalt plating to the cobalt ion in the solution all consumes, the processing condition of electroless cobalt plating are: CoSO
46H
2O20g/L; Diamine 80ml/L; EDTA disodium 60ml/L; Cetyl trimethylammonium bromide 0.1g/L; Thiocarbamide 2mg/L; NaOH 12g/L; PH 11.3～11.5 (ammoniacal liquor adjusting); 80～85 ℃ of temperature; The copper Co composite powder that electroless cobalt plating obtains tap water washes clean final vacuum drying for standby;
Second step: the NiFe
2O
4Synthesizing of-10CoO ceramic phase
With NiO, Fe
2O
3With CoO according to 28.5: 61.5: 10 mass ratio batching after, put into the roller ball mill jar, with the deionized water is medium, ball mill mixing (ratio of grinding media to material is 4: 1) 4 hours, till in 90 ℃ loft drier, being dried to moisture and evaporating fully, constant temperature 6 hours in the retort furnace under 1250 ℃ of temperature then, the synthetic NiFe that obtains
2O
4-10CoO ceramic phase;
The 3rd step: batch mixing
The copper Co composite powder and the second step synthetic ceramic phase powder of the first step preparation are prepared burden by 8: 92 mass ratio, and add 1%～2% polyvinyl alcohol (4%) aqueous solution and industrial spirit and carried out ball mill mixing 2 hours, till being dried to moisture and alcohol then and volatilizing fully;
The 4th step: Composite Preparation
The employing method of colding pressing, the powder that the 3rd step was obtained is pressed into the strip sample that sheet, cylindric sample and bending strength test are used under 200MPa pressure; The compacting sample is at 600 ℃ N
2Degreasing under the atmosphere, soaking time are 4 hours, and temperature rise rate is 50 ℃/h, carry out sintering then under 1350 ℃ of temperature, nitrogen atmosphere, and 100 ℃/h of temperature rise rate is incubated 6 hours, O in the sintering atmosphere
2Content is controlled at 230～250ppm.
Adopt the ceramic-metal composite material of this method and prepared copper spillover mutually not occur, density reaches more than 96%, and in room temperature to 900 ℃ temperature range, electric conductivity increases along with the rising of temperature, and the electric conductivity in the time of 900 ℃ is about 35Scm
-1, room temperature bending strength is 121MPa, is that bending strength becomes 76MPa after 300 ℃ the thermal shock test through the temperature difference.
Embodiment 4:17 (Cu-Pd-Ni-Co)/(NiFe
2O
4-10NiO) the preparation of ceramic-metal composite material
The first step: the preparation of Cu-Pd-Ni-Co composite powder
Adopt the chemical palladium-plating method earlier at copper powder (electrolytic copper powder, granularity is-325 orders) the uniform palladium layer of surface coating thickness, the chemical nickel plating cobalt-base alloy prepares the Cu-Pd-Ni-Co composite powder on palladium copper-clad powder then, detailed process is: take by weighing copper powder 40g, dilution heat of sulfuric acid with 10ml/L soaks the zone of oxidation of removing the surface in about 1 minute, till filtering and repeatedly cleaning copper powder to water and be neutrality with distilled water, then copper powder is added till chemical palladium-plating solution (1L) plates the palladium ion of palladium to the solution and all consume, the processing condition of chemical palladium-plating are: PdCl
22.5g/L; NaH
2PO
2H
2O 6.4g/L; EDTA disodium 19g/L; Quadrol 25g/L; PH 6～7 (ammoniacal liquor adjusting); 40～45 ℃ of temperature; The copper palladium composite powder that obtains filters the back and, filters and obtain the cuprum argentum composite powder end more than three times with washed with de-ionized water; Till then copper palladium composite powder being added in the solution (2L) of chemical nickel plating cobalt-base alloy electroless plating to nickel and cobalt ion and all consuming, processing condition are: NiSO
46H
2O 13.5g/L; CoSO
46H
2O 5.7g/L; NaH
2PO
2H
2O 25g/L; Lactic acid 40ml/L; Sodium lauryl sulphate 0.2g/L; Thiocarbamide 2mg/L; NaOH 10g/L; PH 4.3～4.5 (ammoniacal liquor adjusting); 70～75 ℃ of temperature; The Cu-Pd-Ni-Co composite powder that the chemical nickel plating cobalt obtains tap water washes clean final vacuum drying for standby;
Second step: the NiFe
2O
4Synthesizing of-10NiO ceramic phase
With NiO, Fe
2O
3After 38.5: 61.5 mass ratio batching, put into the roller ball mill jar, with the deionized water is medium, ball mill mixing (ratio of grinding media to material is 4: 1) 4 hours, till in 90 ℃ loft drier, being dried to moisture and evaporating fully, constant temperature 6 hours in the retort furnace under 1200 ℃ of temperature then, the synthetic NiFe that obtains
2O
4-10NiO ceramic phase;
The 3rd step: batch mixing
The Cu-Pd-Ni-Co composite powder and the second step synthetic ceramic phase powder of the first step preparation are prepared burden by 17: 83 mass ratio, and add 1%～2% polyvinyl alcohol (4%) aqueous solution and industrial spirit and carried out ball mill mixing 2 hours, till being dried to moisture and alcohol then and volatilizing fully;
The 4th step: Composite Preparation
The employing method of colding pressing, the powder that the 3rd step was obtained is pressed into the strip sample that sheet, cylindric sample and bending strength test are used under 200MPa pressure; The compacting sample is at 600 ℃ N
2Degreasing under the atmosphere, soaking time are 4 hours, and temperature rise rate is 50 ℃/h, carry out sintering then under 1300 ℃ of temperature, nitrogen atmosphere, and 120 ℃/h of temperature rise rate is incubated 8 hours, O in the sintering atmosphere
2Content is controlled at 230～250ppm.
Adopt the performance index such as material density, electric conductivity and intensity of this method preparation all to have clear improvement, sheet, column and strip sample density all reach more than 96.5%; In room temperature to 900 ℃ temperature range, electric conductivity increases along with the rising of temperature, and the electric conductivity in the time of 900 ℃ reaches 88Scm
-1Room temperature bending strength reaches 193MPa, is that bending strength is 112MPa after 300 ℃ the thermal shock test through the temperature difference.
Claims (5)
1, a kind of is the ceramic matric composite of metallographic phase with the copper alloy, it is characterized in that, described matrix material is made of the metallographic phase of ceramic phase and copper-bearing alloy; The metallographic phase of described copper-bearing alloy is to coat one deck nickel, cobalt or nickel cobalt (alloy) on Cu powder surface, or has coated among Ag, Pd, Au, the Pt one or more earlier on Cu powder surface, and then has coated one deck nickel, cobalt or nickel cobalt (alloy).
2, matrix material according to claim 1 is characterized in that, described ceramic phase comprises MFe
2O
4, MAl
2O
4, MMn
2O
4In one or more and MO type oxide compound in one or more, wherein M is selected from the metallic element of Zn, Co or Ni.
3, matrix material according to claim 1 and 2 is characterized in that, described ceramic phase is the 70-95wt% of described ceramic-metal composite material, and described metallographic phase is the 5-30wt% of described ceramic-metal composite material.
4, claim 1 described a kind of be the metal phase adding method of the ceramic matric composite of metallographic phase with the copper alloy, it is characterized in that: coat one deck nickel, cobalt or nickel cobalt (alloy) on Cu powder surface, perhaps coat the metal level of one or more compositions among Ag, Pd, Au, the Pt earlier on Cu powder surface, and then coating one deck nickel, cobalt or nickel cobalt (alloy), make metallographic phase, behind composite metal powder and the ceramic powder mixing, get final product by compression moulding, degreasing, sintering.
5, metal phase adding method according to claim 4 is characterized in that: Cu content is 60-95wt% in the described metallographic phase, and nickel or cobalt or nickel cobalt (alloy) content are 5-40wt%, and other metal content is 0-20wt%.
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| CN102248168A (en) * | 2011-03-28 | 2011-11-23 | 中南大学 | Manufacturing method of ceramic/copper composite material throat insert |
| CN104178652A (en) * | 2014-08-12 | 2014-12-03 | 天津大学 | Nickel-cobalt alloy/tetragonal zirconia polycrystalline composite ceramic material and preparation method thereof |
| CN104451237A (en) * | 2014-11-14 | 2015-03-25 | 北京科技大学 | Method for preparing three-dimensional continuous network Cr3C2-Cu composites by utilizing infiltration process |
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| CN107405683A (en) * | 2015-03-26 | 2017-11-28 | 住友金属矿山株式会社 | Copper powder and copper cream, conductive coating paint, the conductive sheet using the copper powder |
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| CN1101289C (en) * | 1999-07-08 | 2003-02-12 | 中国科学技术大学 | Chemicalpreparing method for nanometre metal iron powder |
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| CN102248168A (en) * | 2011-03-28 | 2011-11-23 | 中南大学 | Manufacturing method of ceramic/copper composite material throat insert |
| CN104178652A (en) * | 2014-08-12 | 2014-12-03 | 天津大学 | Nickel-cobalt alloy/tetragonal zirconia polycrystalline composite ceramic material and preparation method thereof |
| CN104178652B (en) * | 2014-08-12 | 2016-06-22 | 天津大学 | Nickel cobalt (alloy)/cubic polycrystal zirconia composite ceramic material and preparation method thereof |
| CN104451237A (en) * | 2014-11-14 | 2015-03-25 | 北京科技大学 | Method for preparing three-dimensional continuous network Cr3C2-Cu composites by utilizing infiltration process |
| CN107405683A (en) * | 2015-03-26 | 2017-11-28 | 住友金属矿山株式会社 | Copper powder and copper cream, conductive coating paint, the conductive sheet using the copper powder |
| CN106548822A (en) * | 2016-10-31 | 2017-03-29 | 上海新益电力线路器材有限公司 | A kind of high temperature resistant composite conductor and preparation method thereof |
| CN107604387A (en) * | 2017-08-10 | 2018-01-19 | 中国铝业股份有限公司 | A kind of ceramal anode material and preparation method thereof |
| CN113199024A (en) * | 2021-05-06 | 2021-08-03 | 西华大学 | Ternary layered compound, metal-based composite material, and preparation method and raw materials thereof |
| CN113199024B (en) * | 2021-05-06 | 2023-01-31 | 西华大学 | Ternary layered compound, metal-based composite material, and preparation method and raw materials thereof |
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| CN101591741B (en) | 2011-02-16 |
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