CN115852189A - Preparation method of diamond copper composite material with high filling rate and high heat conductivity and double particle diameters - Google Patents
Preparation method of diamond copper composite material with high filling rate and high heat conductivity and double particle diameters Download PDFInfo
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 165
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000010949 copper Substances 0.000 title claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
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- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 239000011780 sodium chloride Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
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- 230000007704 transition Effects 0.000 abstract description 7
- 238000004100 electronic packaging Methods 0.000 abstract description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 abstract description 2
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Abstract
The invention relates to a preparation method of a diamond copper composite material with high filling rate and high heat conduction and double particle sizes, which comprises the following steps: preparing diamond with a metallized surface; and uniformly mixing the diamond and the copper with the two particle sizes, and placing the mixture into a hot pressing furnace for hot pressing and sintering. The invention plates tungsten carbide and tungsten metal transition layer on the surface of diamond by molten salt method, thereby effectively solving the problem of poor affinity between diamond and copper, and simultaneously adopts diamonds with particle size of 200 μm and 40 μm to maintain a proper proportion, so that the diamond with small particle size can be effectively filledFilled in the gaps among the large diamonds so as to further improve the total volume fraction of the diamonds in the composite material and finally prepare the diamond copper composite material with low density, high filling rate and high thermal conductivity, and is characterized in that the total volume fraction of the large diamonds and the small diamonds is up to 70 percent, and the density is lower than 5.4g/cm 3 The thermal conductivity reaches 639.53W/mK, and the preparation method has a good application prospect in the field of thermal management of modern electronic packaging.
Description
Technical Field
The invention relates to a preparation method of a high-filling-rate and high-heat-conduction double-particle-size diamond copper composite material, and belongs to the technical field of composite materials.
Background
Along with the continuous and rapid development of modern information technology, the integration density of electronic components is higher and higher, the power consumption in unit volume is also higher and higher, the heat dissipation requirement on electronic materials is higher and higher, meanwhile, the thermal expansion coefficient of the heat dissipation material also has certain requirements, and if the thermal expansion coefficient of the heat dissipation material is not matched with that of a chip, the chip can be cracked, and further the serious consequence that the electronic components are failed can be caused. Therefore, high thermal conductivity and low thermal expansion coefficient are essential requirements for the materials of modern electronic packages. Among the substances existing in nature known at present, the thermal conductivity of diamond is the highest, which can reach 1800W/mK and is far higher than that of electronic packaging materials such as silicon carbide, and the thermal expansion coefficient of diamond is only 2.3 multiplied by 10 -6 The temperature per degree centigrade is also very consistent with the requirements of modern thermal management materials. The metal Cu has high thermal conductivity, low price, easy processing and the like, is a packaging material commonly used in modern times, but the thermal expansion coefficient of the copper (17 multiplied by 10) -6 /° c) is too high and thus diamond copper composites are becoming one of the hottest thermal management materials currently under investigation.
But the hydrophilicity between diamond and copper is poor, so that a large number of holes exist on the surfaces of the two materials during compounding, the interface thermal resistance is obviously improved, and the thermal conductivity is obviously reduced. At present, a plurality of methods capable of improving the interface between diamond and copper exist, common methods include alloying of a metal matrix, metallization of the surface of diamond, preparation of a diamond-copper composite material and the like, and common methods also include hydraulic infiltration and powder metallurgy. At present, most researchers coat Ti, gr, mo, W, zr and other elements on the surface of the diamond to improve the problem of non-wettability between the diamond and a copper matrix.
Meanwhile, in order to improve the thermal conductivity of the diamond-copper composite material, one of the most important ways is to increase the volume content of the enhanced phase diamond in the matrix. Studies have shown that the highest volume fraction of particles of a single size that can be accommodated per unit volume is closely related to their shape, and spherical particles are added to a fixed volume by random close packing, giving a maximum volume content of 0.64. In order to further improve the volume fraction of the spherical particles, the method can be realized by a mode of mixing the sizes and the particle diameters, so that the small-particle-diameter diamond is filled in gaps formed by the large-particle-diameter diamond. Therefore, the experiment also introduces the diamond with small grain size, and simultaneously regulates and controls the volume ratio of the diamond with large grain size and the diamond with small grain size, thereby further improving the thermal performance of the composite material.
Based on the above background and needs, the present invention provides a method for preparing a dual-particle-size diamond copper composite material with low density, high filling rate and high thermal conductivity. The method comprises the steps of plating a metal transition layer on the surfaces of large and small diamonds through a molten salt method, so that the problem of poor affinity between the diamonds and copper is solved, then placing the diamonds with double particle sizes and copper powder into a hot pressing furnace for vacuum hot pressing sintering, and effectively filling the diamonds with small particle sizes among the diamonds with large particle sizes through regulating and controlling the proportion of the diamonds with large particle sizes and the volume ratio of the diamonds with double particle sizes in a composite material, so that the advantage of high diamond volume fraction is exerted. It is characterized in that the volume fraction is up to 70 percent, and the density is 5.4g/cm 3 The thermal conductivity is 639.53W/mK.
Disclosure of Invention
In order to overcome the requirements of the existing modern electronic packaging components and heat management materials on heat dissipation materials with high heat conductivity and low density, the invention provides a preparation method of a diamond copper composite material with the characteristics of low density, high filling rate and high heat conductivity, wherein a tungsten carbide and tungsten metal transition layer is plated on the surface of a diamond by a molten salt method, so that the problem of poor affinity between the diamond and copper is effectively solved, and meanwhile, diamonds with the grain sizes of 200 mu m and 40 mu m are adopted to maintain one diamondThe proper proportion ensures that the small-grain-size diamond is effectively filled in the gaps among the large diamonds, thereby further improving the total volume fraction of the diamond in the composite material and finally preparing the diamond copper composite material with low density, high filling rate and high thermal conductivity, and is characterized in that the total volume fraction of the large diamond and the small diamond is up to 70 percent, and the density is lower than 5.4g/cm 3 The thermal conductivity reaches 639.53W/mK, and the preparation method has a good application prospect in the field of thermal management of modern electronic packaging.
A preparation method of a diamond copper composite material with high filling rate and high heat conductivity and double grain diameters comprises the following steps:
the method comprises the following steps: cleaning the diamond: putting diamonds with the grain sizes of 40 microns and 200 microns into a sodium hydroxide solution respectively, performing ultrasonic cleaning, then performing ultrasonic cleaning by using deionized water, putting the diamonds into dilute sulfuric acid for ultrasonic cleaning, then performing ultrasonic cleaning again by using the deionized water, and putting the diamonds into a vacuum drying oven for drying to obtain the diamonds with the grain sizes after surface cleaning;
step two: preparing diamond with metallized surface by a molten salt method: sequentially weighing diamond and nano tungsten powder with the particle sizes of 200 mu m and 40 mu m and the mass ratio of 0.75 to 0.25, putting the three into a ball mill for fully and uniformly mixing, putting the obtained mixed material into a graphite crucible after mixing, compacting the mixed material, then weighing NaCl and KCl particles with the mass ratio of 1:1, putting the particles into the ball mill for fully mixing, covering the obtained mixed material on the mixed material of the diamond tungsten powder, compacting the mixed material again, finally putting the graphite crucible into a tubular furnace, setting the heating rate to be 4 ℃/min, keeping the temperature at 1050 ℃ for 120 minutes, then reducing the temperature to 500 ℃ at the cooling rate of 5 ℃/min, then naturally cooling to room temperature, then taking out,
step three: preparing the diamond copper composite material by hot-pressing sintering: and D, placing the diamond mixture with the metalized surface obtained in the step II into deionized water for ultrasonic cleaning, removing the residual NaCl and KCl, then weighing the mixed diamond and copper powder with the particle size of 5 microns according to the mass ratio of 0.936.02, placing the mixture into a ball mill for fully mixing, placing the mixture into a graphite mold, placing the graphite mold into vacuum hot pressing, pumping, and performing ultrasonic cleaning on the mixture, wherein the mixed diamond mixture is obtained in the step IIVacuum, maintaining the degree of vacuum below 1X 10 -3 Pa, setting the heating rate to be 60 ℃/min, heating to 900 ℃, keeping the temperature for 60 minutes, applying pressure of 0.5T while heating, and naturally cooling to room temperature after keeping the temperature to obtain the double-particle-size diamond copper composite material with the diamond filling rate of up to 70%.
The first step specifically comprises: putting purchased diamonds with the grain sizes of 40 mu m and 200 mu m into 0.5mol/L sodium hydroxide solution, carrying out ultrasonic cleaning for 30 minutes, then carrying out ultrasonic cleaning for 30 minutes by using deionized water, putting the diamonds into 0.5mol/L dilute sulfuric acid, carrying out ultrasonic cleaning for 30 minutes, finally carrying out ultrasonic cleaning for 30 minutes by using the deionized water again, and putting the diamonds into a vacuum drying box for drying, thus obtaining the diamonds with the grain sizes after the surface cleaning is finished.
The second step specifically comprises: preparing diamond with metalized surface by a molten salt method: weighing diamond and nano tungsten powder with the particle size of 200 microns and 40 microns and the mass ratio of 0.75 to 0.25 in turn, putting the diamond and the nano tungsten powder into a ball mill, fully and uniformly mixing for 30 minutes, putting the obtained mixed material into a graphite crucible after mixing, compacting the graphite crucible, then weighing NaCl and KCl particles with the mass ratio of 1:1, putting the particles into the ball mill, fully mixing for 30 minutes, covering the obtained mixed material on the mixture of the diamond tungsten powder, compacting the mixture again, finally putting the graphite crucible into a tube furnace, setting the heating rate to be 4 ℃/min, keeping the temperature at 1050 ℃ for 120 minutes, then reducing the temperature to 500 ℃ at the cooling rate of 5 ℃/min, and then naturally cooling to room temperature and taking out. The thickness of the metal W and WC on the surfaces of the diamond with limited sizes is 100-300 nm.
The third step specifically comprises: preparing the diamond copper composite material by hot-pressing sintering: and D, placing the diamond mixture with the metalized surface obtained in the step II into deionized water, performing ultrasonic cleaning for 30 minutes, removing the residual NaCl and KCl, then weighing the mixed diamond and copper powder with the particle size of 5 mu m according to the mass ratio of 0.936.02, placing the mixture into a ball mill, fully mixing for 30 minutes, placing the mixture into a graphite mold, finally placing the graphite mold into a vacuum hot press, vacuumizing, and keeping the vacuum degree lower than 1 x 10 -3 Pa, setting the heating rate to be 60 ℃/min, and heating toAnd (3) preserving the heat at 900 ℃ for 60 minutes, applying 0.5T of pressure while heating, and naturally cooling to room temperature after heat preservation to obtain the double-particle-size diamond copper composite material with the diamond filling rate up to 70%.
The diamond filling rate of the double-grain-size diamond copper composite material reaches 70%, and the thermal conductivity is 639.53W/mK.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic view of the present invention;
fig. 2 is SEM images of diamonds produced in examples 1 and 2 of the present invention;
FIG. 3 is XRD and XPS plots of diamonds prepared in examples 1 and 2 of the present invention;
fig. 4 is SEM images of the surface and cross-section of the diamond copper composite materials prepared in examples 1 and 2 of the present invention, and EDS line scan images at the interface of the transition layer;
fig. 5 is a schematic diagram comparing the theoretical calculated thermal conductance and the experimental thermal conductance of the diamond copper composite material prepared in examples 1 and 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the method comprises the following steps: cleaning the diamond: putting purchased diamond with the particle size of 200 mu m into 0.5mol/L sodium hydroxide solution, carrying out ultrasonic cleaning for 30 minutes, then carrying out ultrasonic cleaning for 30 minutes by using deionized water, putting the diamond into 0.5mol/L dilute sulfuric acid, carrying out ultrasonic cleaning for 30 minutes, finally carrying out ultrasonic cleaning for 30 minutes by using the deionized water again, and putting the diamond into a vacuum drying oven for drying to obtain the diamond with the cleaned surface.
Step two: preparing diamond with metalized surface by a molten salt method: weighing diamond and nano tungsten powder with the particle size of 200 mu m and the mass ratio of 1:1 in sequence, putting the diamond and the nano tungsten powder into a ball mill, fully and uniformly mixing for 30 minutes, putting the obtained mixed material into a graphite crucible after mixing, compacting the graphite crucible, then weighing NaCl and KCl particles with the mass ratio of 1:1, putting the NaCl and KCl particles into the ball mill, fully mixing for 30 minutes, covering the obtained mixed material on the mixed material of the diamond tungsten powder, compacting the mixed material again, finally putting the graphite crucible into a tubular furnace, setting the heating rate to be 4 ℃/min, keeping the temperature at 1050 ℃ for 120 minutes, then reducing the temperature to 500 ℃ at the cooling rate of 5 ℃/min, and then naturally cooling to room temperature and taking out. The thickness of the diamond surface metal W and WC is limited to 100-300 nm.
Step three: preparing the diamond copper composite material by hot-pressing sintering: and D, placing the diamond mixture with the metalized surface obtained in the step II into deionized water, performing ultrasonic cleaning for 30 minutes, removing the residual NaCl and KCl, then weighing the mixed diamond and copper powder with the particle size of 5 mu m according to the mass ratio of 0.936.02, placing the mixture into a ball mill, fully mixing for 30 minutes, placing the mixture into a graphite mold, finally placing the graphite mold into a vacuum hot press, vacuumizing, and keeping the vacuum degree lower than 1 x 10 - 3 Pa, setting the heating rate to be 60 ℃/min, heating to 900 ℃, keeping the temperature for 60 minutes, applying pressure of 0.5T while heating, and naturally cooling to room temperature after keeping the temperature to obtain the single-grain-diameter diamond copper composite material with the diamond filling rate of up to 70%.
Step four: and (4) performing morphology characterization and thermal performance test on the large diamond and the small diamond prepared in the second step and the composite material sample obtained in the third step.
Example 2:
the method comprises the following steps: cleaning the diamond: putting purchased diamonds with the grain sizes of 40 mu m and 200 mu m into 0.5mol/L sodium hydroxide solution, carrying out ultrasonic cleaning for 30 minutes, then carrying out ultrasonic cleaning for 30 minutes by using deionized water, putting the diamonds into 0.5mol/L dilute sulfuric acid, carrying out ultrasonic cleaning for 30 minutes, finally carrying out ultrasonic cleaning for 30 minutes by using the deionized water again, and putting the diamonds into a vacuum drying box for drying, thus obtaining the diamonds with the grain sizes after the surface cleaning is finished.
Step two: preparing diamond with metalized surface by a molten salt method: weighing diamond and nano tungsten powder with the particle size of 200 microns and 40 microns and the mass ratio of 0.75 to 0.25 in turn, putting the diamond and the nano tungsten powder into a ball mill, fully and uniformly mixing for 30 minutes, putting the obtained mixed material into a graphite crucible after mixing, compacting the graphite crucible, then weighing NaCl and KCl particles with the mass ratio of 1:1, putting the particles into the ball mill, fully mixing for 30 minutes, covering the obtained mixed material on the mixture of the diamond tungsten powder, compacting the mixture again, finally putting the graphite crucible into a tube furnace, setting the heating rate to be 4 ℃/min, keeping the temperature at 1050 ℃ for 120 minutes, then reducing the temperature to 500 ℃ at the cooling rate of 5 ℃/min, and then naturally cooling to room temperature and taking out. The thickness of the metal W and WC on the surfaces of the diamond with limited sizes is 100-300 nm.
Step three: preparing the diamond copper composite material by hot-pressing sintering: and D, placing the diamond mixture subjected to surface metallization obtained in the step II into deionized water for ultrasonic cleaning for 30 minutes, removing residual NaCl and KCl, then weighing the mixed diamond and copper powder with the particle size of 5 microns according to a mass ratio of 0.936.02, placing the mixed diamond and the copper powder into a ball mill for fully mixing for 30 minutes, placing the mixture into a graphite mold, finally placing the graphite mold into vacuum hot pressing, vacuumizing, and keeping the vacuum degree lower than 1 x 10 - 3 Pa, setting the heating rate to be 60 ℃/min, heating to 900 ℃, keeping the temperature for 60 minutes, applying pressure of 0.5T while heating, and naturally cooling to room temperature after keeping the temperature to obtain the double-particle-size diamond copper composite material with the diamond filling rate of up to 70%.
Step four: and (4) performing morphology characterization and thermal performance test on the large diamond and the small diamond prepared in the second step and the composite material sample obtained in the third step.
FIG. 2 is SEM images of the surface topography of large and small diamonds after molten salt tungsten plating of examples 1 and 2, wherein (a) and (b) are the topography of diamonds having a particle size of 200 μm and (c) and (d) are the surface topography of small diamonds having a particle size of 40 μm. It can be seen that no matter how large the diamond grain size, a smooth and dense metal film is formed on the diamond surface, further proving the uniformity and integrity of the diamond surface coating. The thickness of the tungsten layer is about 200nm as can also be obtained from the upper right hand corner of the graph in fig. 2 (a).
Fig. 3 is XRD and XPS graphs of the surface morphologies of the large and small diamonds after the fused salt tungsten plating of examples 1 and 2, wherein (a) in fig. 3 shows an X-ray diffraction pattern of an uncoated diamond having a particle size of 200 μm and a diamond coated with a tungsten metal layer, and a standard card of WC and W. As can be seen from the figure, the diamond surface coating consists of WC and W without intermediate product W 2 And C, indicating that the metal tungsten completely reacts with carbon atoms on the surface of the diamond in the molten salt process. In addition, the diffraction peak of WC is sharp, indicating that the crystallinity of W is high. In fig. 3, (b), (C) and (d) are graphs in which the chemical state of the diamond surface coating is investigated by XPS analysis, and XPS full spectrum, C1s and W4f peak of the diamond surface are fitted to the graphs, respectively. WO is observed at 37.8eV, 35.7eV, 33.2eV, and 31.1eV in FIG. 3 (d) as four fitting peaks, respectively 3 (4f 5/2 )、WO 3 (4f 7/2 )、W(4f 5/2 )、W(4f 7/2 ) The existence of the W-O bond is because the sample adsorbs oxygen in the air during detection, and cannot be detected in the X-ray diffraction spectrum of the graph (a) in FIG. 3, which shows that the bond is weak and cannot influence the subsequent sintering of the sample. In FIG. 3 (C), the W4f doublet of 31.1eV and 33.2eV in the graph is very consistent with metallic W0, the C1s core layer spectrum is also shown as 284.6eV, consistent with the standard results, demonstrating the presence of W-C and C-C, confirming that the composition of such coatings includes WC.
Fig. 4 is an SEM image of the surface and cross-section of the diamond copper composite prepared in example 1 and example 2, both of which have a total diamond volume fraction of 70%. The single grain diamond copper composite consisted of only 70% 200 μm diamond, and the dual grain diamond copper composite consisted of 52% 200 μm large diamond and 18% 40 μm small diamond, this grain size ratio being calculated by the Funas model. As can be seen from the graphs (a) and (b) in fig. 4, compared with the single-grain-diameter diamond, the diamond particles in the dual-grain-diameter composite material are tightly combined with the copper matrix, and the small diamond particles are also uniformly distributed in the gaps of the large diamond, thereby increasing the packing density of the diamond-copper composite material. In FIG. 4, (c) to (f) are SEM images of the cross-sectional structure of the diamond copper composite, wherein (c) and (e) are single-particle-size diamond copper composites having a particle size of 200 μm, and (d) and (f) are double-particle-size diamond copper composites having a particle size of 40 μm and 200 μm. It can be seen from the figure that when the volume fraction of the single-particle-size diamond is 70%, the single-particle-size diamond is poor in adhesion with the copper matrix, the number of pores therein is large, and there are also cases where the diamond is crushed due to mutual compression of the diamonds, but the dual-particle-size diamond is better bonded with the copper matrix at the volume fraction. In fig. 4, (g) and (h) are EDS line scans of the interface between diamond and copper in the composite material, which proves that the composite material has a continuous interface, the thickness of the transition layer between diamond and copper is about 200nm, and the EDS line scans also show that the transition layer on the diamond surface can enhance the interface adhesion, thereby improving the interface heat transfer between the matrix and the reinforcing phase.
Fig. 5 is a comparative graph of theoretical calculation experiment test thermal conductance of the diamond copper composite prepared in examples 1 and 2. The dashed line in the graph represents the thermal conductivity versus volume fraction curve for the dual-grained diamond copper composite calculated by the DEM model. Because some pores exist between diamond and copper in the composite material, and the interface bonding between diamond and copper is insufficient, the thermal conductivity of an actual experimental value is lower than that of a theoretical calculated value. As can be seen from the figure, when the volume fraction is less than or equal to 60%, the thermal interface between diamond and copper is more due to the small diamond doped in the dual-particle size composite material, and the thermal conductivity of the dual-particle size composite material is lower than that of the single-particle size composite material. However, due to the dense distribution of single-grain diamond at high volume fractions (70%), copper powder does not completely fill the interstices between the diamonds, and the thermal properties of the composite deteriorate. In the double-particle-size diamond copper composite material, the large-particle-size diamondThe volume proportion of the stone is low (the diamond with the particle size of 200 mu m accounts for 52 percent, the diamond with the particle size of 40 mu m accounts for 18 percent), the diamond with small particle size and the copper powder effectively fill the gaps between the large diamond, so that the thermal conductivity of the double-particle-size diamond copper composite material is not reduced under the volume fraction of 70 percent, and the thermal conductivity of the composite material reaches 639.53Wm -1 K -1 . However, since the range in which the packing density of the composite material can be increased is limited, when the volume fraction of diamond reaches 80%, the thermal conductivity of the composite material is significantly reduced. This problem can be solved by further increasing the grain size ratio of the large and small diamonds.
In conclusion, the tungsten metal transition layer is plated on the surface of the diamond by a molten salt method, meanwhile, the diamond with two different particle sizes is introduced into the prepared composite material, and the vacuum degree is kept to be lower than 1 x 10 in the vacuum hot-pressing sintering process -3 Pa, setting the heating rate to be 60 ℃/min, heating to 900 ℃, keeping the temperature for 60 minutes, applying pressure of 0.5T while heating, naturally cooling to room temperature after keeping the temperature, and finally obtaining the density of 5.4g/cm 3 The diamond volume fraction reaches 70 percent, and the thermal conductivity is 639.53W/mK, namely the diamond copper composite material with low density, high filling rate and high thermal conductivity.
The embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (6)
1. A preparation method of a diamond copper composite material with high filling rate and high heat conductivity and double grain diameters is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: cleaning the diamond: putting diamonds with the grain sizes of 40 micrometers and 200 micrometers into a sodium hydroxide solution, performing ultrasonic cleaning, then performing ultrasonic cleaning by using deionized water, putting the diamonds into dilute sulfuric acid, performing ultrasonic cleaning, then cleaning again by using the deionized water, and putting the diamonds into a vacuum drying oven for drying to obtain the diamonds with the grain sizes after the surfaces are cleaned;
step two: preparing diamond with metalized surface by a molten salt method: sequentially weighing diamond and nano tungsten powder with the particle sizes of 200 microns and 40 microns in a mass ratio of 0.75 to 0.25, putting the diamond, the nano tungsten powder and the nano tungsten powder into a ball mill, fully and uniformly mixing, putting the obtained mixed material into a graphite crucible after mixing is finished, compacting the graphite crucible, then weighing NaCl and KCl particles with the mass ratio of 1:1, putting the particles into the ball mill for fully mixing, covering the obtained mixed material on the mixed material of the diamond tungsten powder, compacting the mixed material again, finally putting the graphite crucible into a tubular furnace, setting the heating rate to be 4 ℃/min, keeping the temperature at 1050 ℃ for 120 minutes, then reducing the temperature to 500 ℃ at the cooling rate of 5 ℃/min, naturally cooling to room temperature, and then taking out;
step three: preparing the diamond copper composite material by hot-pressing sintering: putting the diamond mixture subjected to surface metallization obtained in the second step into deionized water for ultrasonic cleaning, removing residual NaCl and KCl, then weighing the mixed diamond and copper powder with the particle size of 5 microns according to the mass ratio of 0.936.02, putting the mixed diamond and the copper powder into a ball mill for fully mixing, putting the mixture into a graphite die, putting the graphite die into vacuum hot pressing, vacuumizing, and keeping the vacuum degree to be lower than 1 x 10 -3 Pa, setting the heating rate to be 60 ℃/min, heating to 900 ℃, keeping the temperature for 60 minutes, applying pressure of 0.5T while heating, and naturally cooling to room temperature after keeping the temperature to obtain the double-particle-size diamond copper composite material with the diamond filling rate of up to 70%.
2. The method for preparing the diamond copper composite material with high filling rate and high thermal conductivity according to claim 1, wherein the method comprises the following steps: the first step specifically comprises: putting purchased diamonds with the grain sizes of 40 mu m and 200 mu m into 0.5mol/L sodium hydroxide solution, carrying out ultrasonic cleaning for 30 minutes, then carrying out ultrasonic cleaning for 30 minutes by using deionized water, putting the diamonds into 0.5mol/L dilute sulfuric acid, carrying out ultrasonic cleaning for 30 minutes, finally carrying out ultrasonic cleaning for 30 minutes by using the deionized water again, and putting the diamonds into a vacuum drying box for drying, thus obtaining the diamonds with the grain sizes after the surface cleaning is finished.
3. The method for preparing the diamond copper composite material with high filling rate and high thermal conductivity according to claim 2, wherein the method comprises the following steps: the second step specifically comprises: preparing diamond with metalized surface by a molten salt method: weighing diamond and nano tungsten powder with the particle size of 200 microns and 40 microns and the mass ratio of 0.75 to 0.25 in sequence, putting the diamond and the nano tungsten powder into a ball mill, fully and uniformly mixing for 30 minutes, putting the obtained mixed material into a graphite crucible after mixing, compacting the graphite crucible, then weighing NaCl and KCl particles with the mass ratio of 1:1, putting the particles into the ball mill, fully mixing for 30 minutes, covering the obtained mixed material on the mixture of the diamond tungsten powder, compacting the mixture again, finally putting the graphite crucible into a tube furnace, setting the heating rate to be 4 ℃/min, preserving the temperature at 1050 ℃ for 120 minutes, then reducing the temperature to 500 ℃ at the cooling rate of 5 ℃/min, naturally cooling to room temperature, and taking out, wherein the thickness of metal W and WC on the surfaces of the diamond with the limited size is 100-300 nm.
4. The preparation method of the diamond copper composite material with high filling rate and high heat conductivity and double particle sizes as claimed in claim 3, wherein the preparation method comprises the following steps: the third step specifically comprises: preparing the diamond copper composite material by hot-pressing sintering: and D, placing the diamond mixture with the metalized surface obtained in the step II into deionized water, performing ultrasonic cleaning for 30 minutes, removing the residual NaCl and KCl, then weighing the mixed diamond and copper powder with the particle size of 5 mu m according to the mass ratio of 0.936.02, placing the mixture into a ball mill, fully mixing for 30 minutes, placing the mixture into a graphite mold, finally placing the graphite mold into a vacuum hot press, vacuumizing, and keeping the vacuum degree lower than 1 x 10 -3 Pa, setting the heating rate to be 60 ℃/min, heating to 900 ℃, keeping the temperature for 60 minutes, applying pressure of 0.5T while heating, and naturally cooling to room temperature after keeping the temperature to obtain the double-particle-size diamond copper composite material with the diamond filling rate of up to 70%.
5. The method for preparing the diamond copper composite material with high filling rate and high thermal conductivity according to claim 1, wherein the method comprises the following steps: the double-grain diamondThe density of the copper composite material is 5.4g/cm 3 The thermal conductance is 639.53W/mK.
6. A high-filling-rate high-thermal-conductivity dual-particle-size diamond copper composite material prepared based on the preparation method of any one of claims 1 to 5.
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| CN116550975A (en) * | 2023-07-04 | 2023-08-08 | 赣州金顺科技有限公司 | Preparation method of diamond/copper composite material |
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