CN110699566B - CaMn7O12Reinforced low-expansion high-thermal-conductivity copper-based composite material and preparation method thereof - Google Patents
CaMn7O12Reinforced low-expansion high-thermal-conductivity copper-based composite material and preparation method thereof Download PDFInfo
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C22C—ALLOYS
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- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
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Abstract
The invention discloses CaMn7O12A reinforced low-expansion high-thermal-conductivity copper-based composite material and a preparation method thereof belong to the technical field of copper-based composite materials. The invention aims to solve the problem that metal materials and ceramic materials cannot simultaneously meet the requirements of low thermal expansion coefficient, high thermal conductivity, high electrical conductivity and good processability. The copper-based composite material is prepared from a metal matrix and a reinforcement, wherein the metal matrix is pure copper powder or copper alloy powder; the reinforcement is CaMn7O12Ceramic powder, or CaMn coated with interface coating of copper, copper oxide, silver, nickel oxide or zirconium oxide7O12Ceramic powder; the method comprises the following steps: and performing ball milling and powder mixing on the metal matrix and the reinforcement, and then sintering after cold pressing. The invention has the performances of low thermal expansion coefficient, high thermal conductivity and high electrical conductivity under the condition of low ceramic volume fraction.
Description
Technical Field
The invention belongs to the technical field of copper-based composite materials; in particular to CaMn7O12Reinforced copper-based composite material with low expansion and high thermal conductivity and a preparation method thereof.
Background
The low-expansion high-thermal-conductivity material has wide application in the technical fields of aviation, aerospace, semiconductors and the like, and people have higher and higher requirements on electronic packaging, heat sink materials, precision instrument part materials and the like. Such as the precision optical system frame and parts, part connectors and the like loaded on the spacecraft, because the spacecraft can experience large temperature differences during operation, and the local stress concentration caused by the thermal expansion coefficient of the material can affect the service performance of the material and even cause the material to fail, and the heat generated during the operation of the functional components needs to be dissipated through the connecting component, so that the thermal conductivity of the material is required. Traditional ceramic or metal materials often have difficulty in meeting the requirements of low expansion and high thermal conductivity. The addition of low expansion ceramics to high thermal conductivity metal matrix to obtain composite materials with both high thermal conductivity and low expansion is an important approach to solve this problem.
Although many studies have been made on low-expansion metal matrix composites, many problems still remain to be solved. On one hand, along with the development of electronic information technology, the performance of the materials is more and more required, and on the other hand, the existing ceramic reinforcement such as SiC and Al2O3And because the thermal expansion coefficient is not low enough, a large amount of ceramic reinforcements are often required to be added into the composite material to meet the requirement of the composite material on low thermal expansion performance, and the volume fraction even reaches more than 60 percent, so that the thermal conductivity and the electric conductivity of the composite material are seriously reduced, the plasticity is greatly reduced, and the processing and forming difficulty is improved.
Disclosure of Invention
The invention aims to solve the problem that metal materials and ceramic materials cannot simultaneously meet the requirements of low thermal expansion coefficient, high thermal conductivity, high electrical conductivity and good processability, and provides CaMn7O12A reinforced low-expansion high-thermal-conductivity copper-based composite material and a preparation method thereof.
To solve the above technical problems, the present invention provides CaMn7O12The reinforced copper-based composite material with low expansion and high heat conductivity is prepared from 30-95% of metal matrix and the balance of reinforcement by volume percentage, wherein the metal matrix is pure copper powder or copper alloy powder; the reinforcement is CaMn7O12The ceramic powder or the reinforcement is CaMn coated with copper, silver, copper oxide, nickel oxide or zirconium oxide7O12Ceramic powder; the preparation method specifically comprises the following steps: ball-milling and mixing the metal matrix and the reinforcement, cold-pressing and sintering to obtain CaMn7O12The reinforced low-expansion high-thermal-conductivity copper-based composite material.
When the metal matrix is pure copper powder or copper alloy powder, the pure copper powder or copper alloy powder is mixed according to any ratio.
Further defined, the copper alloy powder has a thermal conductivity greater than 200W/m K.
Further, the metal matrix has a particle size of 0.1 to 300 μm, and the reinforcement has a particle size of 0.1 to 100 μm.
Further limit, coating CaMn7O12The coating amount of the ceramic powder is 5-20% (volume).
Further defined, the CaMn7O12The ceramic powder is high-purity CaCO in stoichiometric ratio3And high purity MnO2The raw material is prepared by a solid phase synthesis method.
Further defined, the coated CaMn7O12The ceramic powder is prepared by a sol-gel method and a chemical plating method.
Further limiting, the pressure of the cold pressing is 5MPa-80MPa, and the time is 1min-30 min.
Further defined, the sintering adopts vacuum hot-pressing sintering and spark plasma sintering; wherein the vacuum hot-pressing sintering process parameters are as follows: the heating rate is 2 ℃ min-1-50℃·min-1Sintering temperature of 850-1050 ℃, sintering pressure of 10-80 MPa, heat preservation time of 5-240 min and vacuum degree of 10-5Pa-10-1Pa; the discharge plasma sintering process parameters are as follows: the heating rate is 10 ℃ min-1-100℃·min-1The sintering temperature is 550-950 ℃, the sintering pressure is 10-80 MPa, the heat preservation time is 1-30 min, and the vacuum degree is 10-5Pa-10-1Pa。
In the invention, CaMn is coated by copper, copper oxide, silver, nickel oxide or zirconium oxide7O12Ceramic powder coated with CaMn7O12The ceramic powder improves the interface bonding state, and further improves the thermal cycle stability of the performance of the composite material.
Extrinsic ferroelectric CaMn7O12Has obvious negative expansion phenomenon in a wider temperature range. CaMn7O12CaMn in rhombohedral phase (space group R-3) at room temperature, starting from about 122 deg.C7O12Gradually transform into cubic phase (space group Im-3), and the cubic phase CaMn increases with temperature7O12The ratio of (A) to (B) is gradually increased until the CaMn of rhombohedral phase is about 225 DEG C7O12Complete conversion to cubic phase. In a phase transition temperature range of about 100 ℃, CaMn7O12Always exhibit a negative expansion phenomenon in which the average coefficient of thermal expansion in the temperature range of 157 ℃ and 215 ℃ is as low as-28.64X 10-6V. C. Cubic phase CaMn7O12The phenomenon of negative expansion of ceramics is caused by negative expansion of flexible structure, MnO in crystal structure6The octahedron gradually becomes flat and twists in the phase change process to extrude eight MnO6The octahedral intermediate void region, resulting in a reduction in the lattice volume, exhibits negative expansion characteristics. The invention controls the interface combination structure, the interface thermal mismatch stress, the rhombohedral phase is converted into the cubic phase under the influence of the thermal mismatch stress, and the negative expansion characteristic is obvious, thereby obtaining the copper-based composite material with low expansion, high thermal conductivity, high electrical conductivity and good processing performance under the condition of low ceramic volume fraction.
The copper-based composite material has low thermal expansion coefficient, high thermal conductivity, high electrical conductivity and easy processing under the condition of lower volume fraction, has the performances of low thermal expansion coefficient, high thermal conductivity and high electrical conductivity besides the performances of plateability, weldability, corrosion resistance, good electromagnetic interference (EMI)/Radio Frequency Interference (RFI) shielding capability, excellent processability, formability and low price, and has the thermal expansion coefficient of 1 multiplied by 10 at the temperature of-100 to 300 DEG C-6～9×10-6The thermal conductivity is 70 to 380W/m.K.
Drawings
FIG. 1 shows the chemical synthesis method for preparing CaMn7O12Ceramic powder XRD atlas;
FIG. 2 shows CaMn7O12The bulk thermal expansion coefficient and the linear thermal expansion coefficient of the ceramic powder are obtained by (a) calculation by using HRSXRD data refined by Rietveld and (b) measurement by using a strain gauge in figure 2;
FIG. 3 shows CaMn prepared by the fourth process in accordance with the embodiment7O12Cu composite materialSurface topography under different times of materials, a)5 μm, b)15 μm;
FIG. 4 shows CaMn prepared by the fourth process in accordance with the embodiment7O12Thermal expansion coefficient of the/Cu composite material.
Detailed Description
The first embodiment is as follows: in this embodiment, CaMn is prepared by solid phase synthesis7O12The ceramic powder is prepared by the following steps: MnO of a purity of 99.99 mass%2And CaCO with a purity of 99.99 mass%3Mixing according to stoichiometric ratio, fully grinding, placing into a box-type resistance furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the air atmosphere, carrying out heat preservation roasting for 24h, cooling to room temperature along with the furnace at a cooling rate of 3 ℃/min, grinding, placing the powder into a tabletting steel die with the diameter of 10mm, pressurizing for 40MPa (pressurizing for 10min) for forming, placing into the box-type resistance furnace, and carrying out pressureless sintering at the temperature of 930 ℃ in the air for 48h to obtain CaMn with compact structure and high purity7O12Grinding and sieving the polycrystalline block to obtain CaMn7O12The ceramic powder has obvious negative expansion effect during phase change.
The reaction chemical equation is:
14MnO2+2CaCO3＝2CaMn7O12+2CO2↑+3O2↑
the solid phase synthesis method in this example prepares CaMn7O12The ceramic powder XRD physical phase diagram 1 shows that in FIG. 2, DeltaV/V is the respective phase fraction weighted value of two phases, [ (DeltaV)Cubic phase/VCubic phase) (cubic phase fraction) + (Δ V)Rhombus phase/VRhombus phase) 'xi' (diamond square phase fraction)]/100。
CaMn in the present embodiment7O12The preparation method of the copper-based composite material with enhanced low expansion and high thermal conductivity is realized by the following steps:
(1) ball milling and powder mixing: the raw material is CaMn with the average grain diameter of 10 mu m7O12Powder and copper powder with average particle size of 5 μm, and reinforcement CaMn7O12Is 20% by volumeMixing powder by a planetary ball milling method, and adopting absolute ethyl alcohol as a medium to prevent Cu powder from being oxidized due to temperature rise in the ball milling process, wherein the ball milling process parameters are as follows: the ball material ratio is 2: 1; the ball milling rotating speed is 300 r/min; the ball milling time is 12 h.
The ball mill equipment was a planetary ball mill of type QM-1SP (ZL) manufactured by Nanjing university instruments works. The ball milling tank is a corundum tank, and the grinding ball is ZrO2A ball.
(2) Cold pressing: and (2) putting the mixed powder obtained in the step (1) into a graphite die, and pressurizing the powder in the die in a uniaxial direction at the pressure of 20Mpa for 10 min. The cold pressing can help to discharge the gas adsorbed in the powder, the pressure of the cold pressing does not need to be too large, and partial gas is prevented from being sealed and locked in the powder and cannot be discharged, and finally becomes air holes in the composite material to influence the performance of the composite material.
(3) And (3) sintering: sintering is carried out by adopting a discharge plasma sintering method or a vacuum hot pressing sintering method, and the technological parameters of sintering are shown in table 1.
TABLE 1 composite sintering Process
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the volume fraction of reinforcement is 40%. Other steps and parameters are the same as in the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the volume fraction of reinforcement is 60%. Other reaction steps and parameters are the same as in the first embodiment.
The fourth concrete implementation mode: the second embodiment is different from the first embodiment in that: coating CaMn with CuO7O12Ceramic powder is used as reinforcement, wherein, CuO coats CaMn7O12The ceramic powder is prepared by adopting a heterogeneous precipitation method, and the specific process is as follows:
1) dissolving 5g of PVP reagent in 400ml of deionized water by using a magnetic stirring method;
2) into the dispersion30g of CaMn are added7O12Continuously stirring the powder for 2 hours to ensure that the CaMn is obtained7O12The powder is uniformly dispersed without sedimentation;
3) adding proper amount of Cu (NO) into the suspension according to the coating amount3)2·3H2O reagent, continuously stirring for 1h to ensure that Cu (NO)3)2Completely dissolved in the suspension;
4) to dissolve Cu (NO)3)2Slowly dripping NaOH solution with the concentration of 1mol/L into the suspension, keeping magnetic stirring in the dripping process, and stopping dripping until the pH value of the suspension reaches 12;
5) the stirring was stopped and after a period of standing the suspension settled. And washing the precipitated substances with deionized water and absolute ethyl alcohol for multiple times until the pH value of the washing liquid reaches 7, and stopping washing. Then putting the precipitate into an oven for drying treatment to obtain Cu (OH)2Coated CaMn7O12Powder;
6) will be coated with Cu (OH)2CaMn of7O12Dehydrating the powder at 700 deg.C for 2 hr to make Cu (OH) on the surface of the powder2Decomposed to CuO at high temperature. Thereby obtaining CuO coated CaMn7O12The morphology of the ceramic particles, with a copper oxide coating amount of 5%, is shown in FIG. 3 (b). Other reaction steps and parameters are the same as those of the second embodiment.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: the copper oxide coating amount is 10%, and other reaction steps and parameters are the same as those of the fourth embodiment.
The sixth specific implementation mode: the fourth difference from the embodiment is that: the copper oxide coating amount is 20%, and other reaction steps and parameters are the same as those of the fourth embodiment.
The seventh embodiment: the second embodiment is different from the first embodiment in that: coating CaMn with NiO7O12Ceramic powder is used as reinforcement, wherein NiO coats CaMn7O12The ceramic powder is prepared by adopting a chemical coating method, and comprises the following specific steps:
1) mixing Ni (NO)3)2·6H2Dissolving O in anhydrous ethanol, adding CaMn7O12Ceramic powder;
2) heating at 80 deg.C while magnetically stirring until the solution volatilizes;
3) then drying for 12 hours at 120 ℃;
4) then calcining at 500 ℃ for 12 hours to make Ni (NO)3)2Formation of Ni (OH)2；
5) Then calcining at high temperature to obtain Ni (OH)2NiO is formed to obtain NiO-coated CaMn7O12Ceramic particles.
The nickel oxide coating amount in this embodiment is 5%. Other reaction steps and parameters are the same as those of the second embodiment.
The interfacial NiO coating is introduced in the embodiment to improve the wettability of the interface in the composite material.
The specific implementation mode is eight: the seventh embodiment is different from the seventh embodiment in that: the nickel oxide coating amount is 10%, and other reaction steps and parameters are the same as those of the seventh embodiment.
The specific implementation method nine: the seventh embodiment is different from the seventh embodiment in that: the nickel oxide coating amount is 20%, and other reaction steps and parameters are the same as those of the seventh embodiment.
TABLE 2
Claims (10)
1.CaMn7O12The reinforced copper-based composite material with low expansion and high heat conductivity is characterized in that the reinforced copper-based composite material is prepared from 30-95% of metal matrix and the balance of reinforcement according to volume fraction, wherein the metal matrix is pure copper powder or copper alloy powder; the reinforcement is CaMn7O12Ceramic powder, or reinforcementCoating CaMn for copper, silver, copper oxide, nickel oxide or zirconium oxide interface coating7O12Ceramic powder; the preparation method specifically comprises the following steps: ball-milling and mixing the metal matrix and the reinforcement, cold-pressing and sintering to obtain CaMn7O12The reinforced low-expansion high-thermal-conductivity copper-based composite material.
2. A reinforced copper-based composite material according to claim 1, characterized in that the thermal conductivity of said copper alloy powder is greater than 200W/m-K.
3. The reinforced copper-based composite material according to claim 2, wherein the metal matrix has a particle size of 0.1 to 300 μm and the reinforcement has a particle size of 0.1 to 100 μm.
4. The reinforced copper-based composite material according to claim 1, characterized in that the coating is CaMn7O12The coating volume fraction of the ceramic powder is 5-20%.
5. The reinforced copper-based composite material according to claim 1, characterized in that said CaMn7O12The ceramic powder is high-purity CaCO in stoichiometric ratio3And high purity MnO2The starting material is prepared by a solid phase synthesis method or a single crystal separation method.
6. The reinforced copper-based composite material according to claim 1, characterized in that said coating CaMn7O12The ceramic powder is prepared by a sol-gel method or a chemical plating method.
7. The CaMn of any one of claims 1-67O12The preparation method of the reinforced copper-based composite material with low expansion and high heat conductivity is characterized by comprising the following steps: ball-milling and mixing the metal matrix and the reinforcement, pre-cooling and pressing, and then performing pressure sintering to obtain CaMn7O12The reinforced low-expansion high-thermal-conductivity copper-based composite material.
8. The CaMn of claim 77O12The preparation method of the reinforced copper-based composite material with low expansion and high thermal conductivity is characterized in that the pressure of cold pressing is 5MPa-80MPa, and the time is 1min-30 min.
9. The CaMn of claim 7 or 87O12The preparation method of the reinforced copper-based composite material with low expansion and high thermal conductivity is characterized in that the sintering adopts vacuum hot-pressing sintering or spark plasma sintering.
10. The CaMn of claim 97O12The preparation method of the reinforced copper-based composite material with low expansion and high thermal conductivity is characterized in that the vacuum hot-pressing sintering process parameters are as follows: the heating rate is 2 ℃ min-1-50℃·min-1Sintering temperature of 850-1050 ℃, sintering pressure of 10-80 MPa, heat preservation time of 5-240 min and vacuum degree of 10-5Pa-10-1Pa; the discharge plasma sintering process parameters are as follows: the heating rate is 10 ℃ min-1-100℃·min-1The sintering temperature is 550-950 ℃, the sintering pressure is 10-80 MPa, the heat preservation time is 1-30 min, and the vacuum degree is 10-5Pa-10-1Pa。
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