CN115011917A - Diamond particle surface modification method based on vacuum thermal evaporation - Google Patents
Diamond particle surface modification method based on vacuum thermal evaporation Download PDFInfo
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- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0026—Activation or excitation of reactive gases outside the coating chamber
- C23C14/0031—Bombardment of substrates by reactive ion beams
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/26—Vacuum evaporation by resistance or inductive heating of the source
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/50—Substrate holders
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Abstract
The invention discloses a diamond particle surface modification method based on vacuum thermal evaporation, which comprises the following steps: firstly, carrying out surface pretreatment on diamond particles; then carrying out ion beam modification treatment on the pretreated diamond particles to obtain activated diamond particles; finally, the surface of the activated diamond particles is modified by a vacuum thermal evaporation method to obtain the diamond particles with the surface coated with the carbide coating. The invention can solve the problems of obvious graphitization tendency of the diamond, poor coating uniformity and the like in the existing diamond particle surface modification method. The method is simple to operate, convenient and easy to implement, low in cost and capable of meeting the requirement of industrial-grade diamond particle surface modification.
Description
Technical Field
The invention relates to the technical field of surface modification, in particular to a diamond particle surface modification method based on vacuum thermal evaporation.
Background
Power semiconductor chips are largely classified into silicon, gallium arsenide, silicon carbide, gallium nitride, and the like, depending on the material used. Silicon carbide and gallium nitride have wide bandgaps in excess of 3 electron volts (eV) and higher thermal conductivities than silicon, can achieve higher power efficiencies, smaller dimensions, lighter weight and lower overall costs, providing many attractive properties for high voltage power semiconductor devices. Along with the popularization and application of the novel power semiconductor chips, the power density of semiconductor devices is getting larger, the heating amount per unit area is rapidly increased, and the problem of heat dissipation is to be solved urgently.
The diamond particle reinforced copper-based composite material has the advantages of high heat conductivity, adjustable thermal expansion coefficient and the like, can be used as a new generation of high-performance heat management material, provides a high-efficiency stable heat dissipation function for silicon carbide and gallium nitride semiconductors, and ensures the working stability and safety and reliability of the silicon carbide and gallium nitride semiconductors. The diamond particle thermal conductivity at room temperature is 1500-2200W/(m.K), the copper thermal conductivity at room temperature is 400W/(m.K), theoretically, the thermal conductivity of the diamond particle reinforced copper-based composite material can reach 1000W/(m.K), but because the interface energy between diamond and a copper matrix is high, the copper matrix has poor wettability to diamond, the interface bonding is weak, and the interface thermal resistance is high. The actual thermal conductivity of the unmodified diamond particle reinforced copper-based composite material can only reach about 200W/(m.K), and the high thermal conductivity of the composite material cannot be fully exerted.
The diamond surface modification can effectively solve the problem of poor wettability of the diamond surface. Some strong carbide forming elements such as Ti, Cr, W, Mo and V are plated on the surface of the diamond by a physical or chemical method, and react with carbon atoms on the surface of the diamond to generate stable metal carbide, so that the wettability of the diamond and a matrix metal is improved, and the thermal conductivity of the composite material is improved. At present, the surface modification methods of diamond particles mainly comprise high-temperature thermal diffusion, salt bath plating, magnetron sputtering, chemical vapor deposition, sol-gel method and the like.
Patent CN 104651658A and patent CN104674208A Diamond particles with excess WO 3 Powder or MoO 3 Mixing the powders, and depositing a W or Mo coating on the surface of the diamond by high-temperature thermal diffusion in a vacuum environment. Due to the fact that the reaction temperature is high (950-1050 ℃), graphitization phenomena of different degrees appear on the surface of the diamond, and the bonding strength of a plating layer and the intrinsic thermal conductivity of the diamond are obviously reduced. In addition, the W or Mo coating prepared by the method is rough, and the thickness and uniformity are difficult to accurately control.
The patent CN 111575700A adopts a chemical vapor deposition method to plate W on the surface of diamond particles. The method comprises mixing blue tungsten or purple tungsten (WO) 3 ) Uniformly mixing the plating material and the diamond particles, heating to 700-800 ℃ in a hydrogen atmosphere, preserving heat for 1-2 h, and carrying out reduction and carbonization reactions to obtain the tungsten plating layer-coated diamond particles with different shapes. Although the plating temperature is slightly reduced compared to the high temperature thermal diffusion method, the hydrogen cost is high and cannot meet the requirement of single large-batch plating of industrial-grade diamond particles.
In patent CN 110373660 a, diamond particles and tungsten powder are put into chloride salt, and under a high temperature environment, the diamond particles coated with different coatings are obtained by being driven by the chloride molten salt. Because the reaction temperature is high (900-1200 ℃), the diamond is difficult to avoid graphitization; meanwhile, at a higher reaction temperature, the fused salt is seriously volatilized, equipment is easy to corrode, and the fused salt is difficult to clean and separate. In addition, because the density difference between the diamond particles and the tungsten powder is large, the tungsten powder is easy to precipitate, and a uniform tungsten coating is difficult to obtain.
Patent CN 111039675A combines diamond particles with Mo and MoO 3 Mixing with halide, and disproportionating with high-temperature molten salt to obtain diamond surfaceIn-situ preparation of compact continuous Mo 2 And C, layer. The method also has the problems of obvious graphitization tendency of diamond, equipment corrosion caused by high-temperature salt steam, difficult cleaning of molten salt residues and poor uniformity of a plating layer.
Disclosure of Invention
The invention provides a diamond particle surface modification method based on vacuum thermal evaporation, which is used for solving the problems that the graphitization tendency of diamond is obvious, the uniformity of a plating layer is poor, the industrial-grade plating requirement is difficult to meet and the like in the existing surface modification method.
In order to achieve the purpose, the invention provides a diamond particle surface modification method based on vacuum thermal evaporation, which comprises the following steps:
s1: pretreating the surface of the diamond particles;
s2: carrying out ion beam modification on the pretreated diamond particles to obtain activated diamond particles;
s3: placing the reaction material and the activated diamond particles in a high-temperature area and a low-temperature area in a double-temperature-area thermal evaporation tube furnace in sequence, vacuumizing, heating under the condition of furnace tube rotation, keeping the temperature of the high-temperature area at 850-1250 ℃ and the temperature of the low-temperature area at 550-750 ℃ for a period of time, and cooling to obtain diamond particles with surfaces coated with 100-200 nm carbide coatings;
the reaction material is composed of a metal simple substance M and a metal oxide MO 3 And a catalyst composition, wherein M is W or Mo, MO 3 Is WO 3 Or MoO 3 The catalyst is NH 4 Cl or NH 4 F。
In order to ensure that the surfaces of the diamond particles are uniformly plated, the furnace tube is driven to rotate ceaselessly by the rotary driving belts at the two ends of the furnace tube and the rolling bearing, so that the diamond particles in the furnace tube are driven to turn ceaselessly.
If tungsten powder or molybdenum powder is directly adopted to react with diamond particles in a solid phase to prepare the carbide coating, the carbide coating is generally prepared at the high temperature of 1400-1600 ℃. And metal tungsten and molybdenum steam or tungsten oxide and molybdenum oxide steam is adopted to react with the diamond particles, and the gas phase atoms have higher activity and are more fully contacted with the diamond particles, so that the reaction temperature can be reduced to 550-750 ℃, and the prepared carbide coating has better uniformity and finer coating particles. According to the invention, metal tungsten, tungsten oxide steam or metal molybdenum and molybdenum oxide steam is used for reacting with diamond particles, so that the heating temperature of the diamond is preferably 550-750 ℃.
M O O 3 Starting to sublime at a temperature above 520 ℃, WO 3 Sublimation begins at temperatures above 850 ℃ and the vapor pressure increases with increasing temperature. Considering the vapor pressure value, the dosage of the reaction materials in the actual deposition process and influencing factors, the heating temperature of the reaction materials is preferably 850-1250 ℃.
Preferably, in step S1, the preprocessing specifically includes:
firstly, placing diamond particles in acetone, ultrasonically cleaning for 10-20 min, removing residual acetone by using alcohol, and cleaning by using distilled water; then placing the diamond particles in 10% NaOH solution, continuously stirring and boiling for 10-20 min, taking out, and washing with distilled water to be neutral; finally, placing the diamond particles in a 30% dilute nitric acid solution, boiling for 10-30 min, taking out, washing with distilled water to be neutral, and placing in an oven for drying.
The impurities such as graphitized elements, oil stains and the like on the surfaces of diamond particles can be effectively removed through pretreatment, the surface roughness of the diamond is increased, the contact area with a reaction material is increased, and the interface bonding force of a plating layer is improved.
Preferably, in step S1, the diamond particles have a particle size of 25 to 425 mesh.
Preferably, step S2 is specifically:
and placing the pretreated diamond particles in a powder roller plasma surface treatment machine, vacuumizing to 5-10 Pa, introducing argon, performing plasma activation for 5-15 min, and taking out to obtain activated diamond particles.
Through the bombardment effect of the plasma beam on the surface of the diamond particles, pollutants can be separated from the surface and are sucked away by a vacuum pump, so that the aim of thorough cleaning is fulfilled; in addition, the bombardment of the active particles can improve the surface energy of the diamond particles and increase the surface adsorption force and the adsorption uniformity of the diamond particles.
Preferably, in step S3, the mass ratio of the activated diamond particles to the reaction materials is 1: 5-15.
Preferably, in step S3, M and MO in the reaction mass 3 In a mass ratio of 1: 2.5-4, and metal oxide MO 3 The vapor pressure is higher, and the diamond surface is seriously corroded due to the violent reaction of the diamond when the adding amount is more. Therefore, to properly reduce MO 3 The steam concentration of the catalyst does not influence the generation of metal carbide, and part of metal simple substance M with lower steam pressure is added into the reaction material.
The mass ratio of the activated diamond particles to the catalyst is 5-10: 1.
The reactions specifically involved in the modification are as follows:
M+C→MC (1-1)
MO 3 +C→MC+CO (1-2)
M+M i+ →M j+ (1-3)
M j+ +C→M i+ +MC (1-4)
wherein M is i+ Represents a higher valent ion of M, M j+ Represents the ion of M in the middle valence state, and i is more than j.
As shown by the reaction formulas (1-1) and (1-2), the simple metal M and the metal oxide MO are present in a high-temperature vacuum environment 3 Evaporating to form a large amount of gas phase metal atoms, diffusing to the surface of the diamond particles through a vacuum pumping system, and reacting with the C atoms on the surface of the diamond to generate a metal carbide coating. In addition, high-temperature disproportionation reaction is involved in the whole modification process, such as the combination of chloride ions and fluoride ions in the catalyst with the simple metal M to generate high-valence M i+ Ion, M i+ The ions react with M simple substance to generate low valence state M j+ Ions; m j+ The ions further react with carbon atoms on the surface of the diamond to generate a metal carbide coating. M produced by the disproportionation reaction at a high temperature, as compared with the reaction formulas (1-1) and (1-2) j+ The activity is higher, and the reaction with C atoms is easier to carry out. Therefore, the addition of the catalyst can improve the plating efficiency and enhance the plating effect.
Preferably, in step S3, the high temperature region is heated by induction heating, and the heating rate is 200 to 300 ℃/min; the low-temperature area adopts resistance heating, and the heating rate is 20 ℃/min. The reaction materials are heated rapidly by induction heating, so that on one hand, the oxidation of metal tungsten powder or molybdenum powder can be avoided, on the other hand, gas-phase W or Mo atoms can be evaporated rapidly in a high-temperature vacuum environment, and are driven by a vacuum pump to diffuse to the surface of the diamond in a low-temperature area for deposition, and the diamond particles with metal carbide plated on the surface can be obtained efficiently.
Preferably, in step S3, the reaction material has a particle size of 1000 to 1500 mesh and a purity of 99.99 wt%.
Preferably, in the step S3, the heat preservation time is 0.5-1.5 h.
Preferably, in step S3, the vacuum degree of the vacuum pumping is 0.1-200 Pa.
Compared with the prior art, the invention has the beneficial effects that:
the method for modifying the surface of the diamond particles based on vacuum thermal evaporation provided by the invention comprises the following steps of pretreating the surface of the diamond particles; ion beam modification is carried out on the pretreated diamond particles to obtain activated diamond particles; and carrying out vacuum thermal evaporation on the activated diamond particles, rapidly heating the reaction material by utilizing induction heating, evaporating out gas phase W or Mo atoms in a high-temperature vacuum environment, and then diffusing the gas phase W or Mo atoms to the surface of the diamond in a low-temperature area by driving of a vacuum pump for deposition to obtain the diamond particles with the surface coated with the carbide coating. Compared with other vacuum thermal evaporation methods, the invention realizes organic unification of high-temperature evaporation and low-temperature plating, the diamond plating temperature is low, the plating time is short, and the graphitization problem can be completely avoided.
In the coating process, the furnace tube rotates to drive the diamond particles inside to turn over, so that the diamond particles can be in all-dimensional contact and reaction with gas atoms of a reactant, and uniform coating of the diamond particles is facilitated. The method is simple to operate, convenient and easy to implement, low in cost and has excellent performance advantages for industrial grade diamond particle surface modification requirements.
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 description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic diagram of a dual-temperature zone thermal evaporation tube furnace employed in the present invention:
FIG. 2a is a surface SEM image of a surface modified diamond particle of example 1;
FIG. 2b is an enlarged view at box of FIG. 2 a;
FIG. 2c is an enlarged view at box of FIG. 2 b;
fig. 3 is an XRD pattern of the surface modified diamond particles of example 1.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all 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 embodiment provides a diamond particle surface modification method based on vacuum thermal evaporation, which comprises the following steps:
s1: weighing 5kg of diamond single crystal particles with the particle size of 25 meshes, putting the diamond single crystal particles into an acetone solution, ultrasonically cleaning for 15min, removing residual acetone by using alcohol, and cleaning by using distilled water; putting the cleaned diamond particles into 10% NaOH solution, continuously stirring and boiling for 15min, taking out, and cleaning with distilled water to neutrality; the diamond particles are placed in a 30% dilute nitric acid solution to be boiled for 20min, taken out, washed to be neutral by distilled water, and placed in an oven to be dried.
S2: and putting the dried diamond particles into a powder roller plasma surface treatment machine, vacuumizing to 8Pa, introducing argon, starting a power supply, operating a cleaning program for 15min, and taking out to obtain the activated diamond particles.
S3: weighing 11kgW powder and 35kgWO 3 Placing powder and 1kg of ammonium chloride (reaction material) in a porous tungsten skeleton cylinder, weighing 5kg of activated diamond particles, placing the activated diamond particles in a dual-temperature-zone thermal evaporation tubular furnace, wherein the reaction material is located in a high-temperature zone, and the activated diamond particles are located in a low-temperature zone; vacuumizing an alumina ceramic tube to 0.5Pa, starting resistance heating, and raising the temperature of diamond particles to 680 ℃; starting induction heating to make W powder and WO powder 3 Rapidly heating the powder and ammonium chloride to 1150 ℃ within 5min, keeping the temperature for 1h, closing a heating power supply, cooling to obtain the diamond particles with the WC coated on the surface, wherein the thickness of the WC coating is about 150 nm. In the reaction process, the furnace tube is driven to rotate ceaselessly by the rotary driving belts at the two ends of the alumina ceramic tube and the rolling bearings, so that diamond particles in the furnace tube are driven to turn over, and uniform plating is realized.
In this example, the schematic diagram of the equipment used for modifying the surface of diamond particles is shown in fig. 2: the device mainly comprises 1-a left side furnace tube support, 2-an alumina ceramic tube, 3-an equipment platform, 4-a high temperature zone, 5-an induction coil, 6-a reaction material, 7-a porous metal framework cylinder, 8-a low temperature zone, 9-a resistance wire, 10-diamond particles, 11-a right side furnace tube support, 12-a rolling bearing, 13-a dynamic rotating shaft sealing device, 14-a vacuum pressure gauge, 15-a vacuum pump and 16-a rotating driving belt.
The surface modification of the diamond particles comprises the following specific steps: placing the 6-reaction material in a 7-porous metal framework cylinder, and placing the 6-reaction material and the 10-diamond particles in a double-temperature-zone thermal evaporation tubular furnace together, wherein the reaction material is located in a 4-high-temperature zone, and the diamond particles are located in an 8-low-temperature zone; vacuumizing the 2-alumina ceramic tube, heating the 10-diamond particles to a certain temperature by a 9-resistance wire, heating the reaction materials by a 5-induction coil to quickly raise the temperature to a certain temperature, and preserving the temperature for a period of time to ensure that the reaction materials evaporate out gas phase W atoms and gas phase WO under a high vacuum environment 3 Diffusing to the surface of the diamond particles; cooling to obtain surface modified diamond particlesAnd (4) granulating. In the heat preservation process, in order to ensure that the surfaces of the diamond particles are uniformly plated, the furnace tube is driven to rotate ceaselessly through 16-rotation driving belts and 12-rolling bearings at the two ends of the 2-alumina ceramic tube, so that the 10-diamond particles in the 2-alumina ceramic tube are driven to turn ceaselessly.
The microstructure and XRD pattern of the surface of the plated WC diamond particles obtained in this example are shown in fig. 2a, 2b, 2c and 3. As can be seen from the figures 2a, 2b and 2c, the edges and corners of the coated diamond particles are clear, the surface coating is uniform and complete, and the coating coverage rate reaches more than 95%. As can be seen from FIG. 3, the main component of the coating on the surface of the diamond particles is WC, indicating that gas phase W atoms adsorbed on the surface of the diamond at 680 ℃ and WO 3 Fully contacts with the C atoms on the surface of the diamond and completely reacts. The phase of ammonium chloride is not shown in the diffraction spectrum, indicating that the ammonium chloride has reacted completely and is not left on the surface of the diamond particles.
Example 2
The embodiment provides a diamond particle surface modification method based on vacuum thermal evaporation, which comprises the following steps:
s1: weighing 4kg of diamond single crystal particles with the granularity of 100 meshes, putting the diamond single crystal particles into an acetone solution, ultrasonically cleaning for 15min, removing residual acetone by using alcohol, and cleaning by using distilled water; putting the cleaned diamond particles into 10% NaOH solution, continuously stirring and boiling for 15min, taking out, and cleaning with distilled water to neutrality; then placing the diamond particles in a 30% dilute nitric acid solution, boiling for 10min, taking out, washing with distilled water to be neutral, and placing in an oven for drying.
S2: and putting the dried diamond particles into a powder roller plasma surface treatment machine, vacuumizing to 10Pa, introducing argon, starting a power supply, operating a cleaning program for 8min, and taking out to obtain the activated diamond particles.
S3: weighing 10kg of Mo powder and 30kg of MoO 3 Placing the powder and 0.4kg of ammonium fluoride (reaction material) in a porous molybdenum skeleton cylinder, weighing 4kg of activated diamond particles, placing the activated diamond particles together in a double-temperature-zone thermal evaporation tubular furnace, placing the reaction material in a high-temperature zone, and placing the activated diamond particles in a low-temperature zone; the alumina ceramic tube is vacuumized to 0.1Pa,starting resistance heating to heat the diamond particles to 700 ℃; starting induction heating to make Mo powder and MoO 3 Rapidly heating the powder and ammonium chloride to 900 deg.C within 4.5min, maintaining for 0.5h, turning off heating power supply, cooling to obtain Mo-coated surface 2 C, the coating thickness is about 100 nm. In the reaction process, the furnace tube is driven to rotate ceaselessly by the rotary driving belts at the two ends of the alumina ceramic tube and the rolling bearings, so that diamond particles in the furnace tube are driven to turn over, and uniform plating is realized.
Example 3
The embodiment provides a diamond particle surface modification method based on vacuum thermal evaporation, which comprises the following steps:
s1: weighing 2kg of diamond single crystal particles with the granularity of 425 meshes, putting the diamond single crystal particles into an acetone solution, ultrasonically cleaning for 15min, removing residual acetone by using alcohol, and cleaning by using distilled water; putting the cleaned diamond particles into a 10% NaOH solution, continuously stirring and boiling for 15min, taking out, and cleaning with distilled water to be neutral; then placing the diamond particles in a 30% dilute nitric acid solution to boil for 15min, taking out the diamond particles, washing the diamond particles to be neutral by using distilled water, and placing the diamond particles in an oven to dry.
S2: and putting the dried diamond particles into a powder roller plasma surface treatment machine, vacuumizing to 5Pa, introducing argon, starting a power supply, running a cleaning program for 5min, and taking out to obtain the activated diamond particles.
S3: weighing 4kg of Mo powder and 16kg of MoO 3 Powder and 0.4kg of ammonium chloride (reaction material) are placed in a porous molybdenum skeleton cylinder, 2kg of activated diamond particles are weighed and are placed in a double-temperature-zone thermal evaporation tubular furnace together, the reaction material is in a high-temperature zone, and the activated diamond particles are in a low-temperature zone; vacuumizing the alumina ceramic tube to 200Pa, starting resistance heating, and raising the temperature of diamond particles to 750 ℃; starting induction heating to make Mo powder and MoO 3 Rapidly heating the powder and ammonium chloride to 850 deg.C within 4min, maintaining for 0.5h, turning off heating power supply, cooling to obtain Mo-plated surface 2 C, the coating thickness is about 120 nm. In the reaction process, the furnace tube is driven by the rotary driving belts and the rolling bearings at the two ends of the alumina ceramic tubeThe continuous rotation drives the diamond particles in the furnace tube to turn over, and uniform plating is realized.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A diamond particle surface modification method based on vacuum thermal evaporation is characterized by comprising the following steps:
s1: pretreating the surfaces of the diamond particles;
s2: carrying out ion beam modification on the pretreated diamond particles to obtain activated diamond particles;
s3: placing the reaction material and the activated diamond particles in a high-temperature area and a low-temperature area in a double-temperature-area thermal evaporation tube furnace in sequence, vacuumizing, heating under the condition of rotating the furnace tube, keeping the temperature of the high-temperature area at 850-1250 ℃ and the temperature of the low-temperature area at 550-750 ℃, and cooling to obtain diamond particles with carbide coatings coated on the surfaces;
the reaction material is composed of a metal simple substance M and a metal oxide MO 3 And a catalyst, wherein M is W or Mo, MO 3 As WO 3 Or MoO 3 The catalyst is NH 4 Cl or NH 4 F。
2. The diamond particle surface modification method according to claim 1, wherein in step S1, the pretreatment is specifically:
firstly, placing diamond particles in acetone, ultrasonically cleaning for 10-20 min, removing residual acetone by using alcohol, and cleaning by using distilled water; then placing the diamond particles in a 10% NaOH solution, continuously stirring and boiling for 10-20 min, taking out, and washing with distilled water to be neutral; and finally, placing the diamond particles in a 30% dilute nitric acid solution, boiling for 10-30 min, taking out, washing with distilled water to be neutral, and placing in an oven for drying.
3. The method for modifying the surface of diamond particles according to claim 1, wherein the diamond particles have a particle size of 25 to 425 mesh in step S1.
4. The diamond particle surface modification method according to claim 1, wherein step S2 is specifically:
and placing the pretreated diamond particles in a powder roller plasma surface treatment machine, vacuumizing to 5-10 Pa, introducing argon, performing plasma activation for 5-15 min, and taking out to obtain activated diamond particles.
5. The diamond particle surface modification method according to claim 1, wherein in step S3, the mass ratio of the activated diamond particles to the reaction material is 1:5 to 15.
6. The method for modifying the surface of diamond particles according to claim 1 or 5, wherein in step S3, M and MO are contained in the reaction mixture 3 The mass ratio of (A) to (B) is 1: 2.5-4; the mass ratio of the activated diamond particles to the catalyst is 5-10: 1.
7. The method for modifying the surface of diamond particles according to claim 1, wherein in step S3, the high-temperature region is heated by induction heating at a heating rate of 200 to 300 ℃/min; the low-temperature area adopts resistance heating, and the heating rate is 20 ℃/min.
8. The method for modifying the surface of diamond particles according to claim 1, wherein the reaction material has a particle size of 1000 to 1500 mesh and a purity of 99.99 wt% in step S3.
9. The method for modifying the surface of diamond particles according to claim 1, wherein the heat-retaining time is 0.5 to 1.5 hours in step S3.
10. The method for modifying the surface of diamond particles according to claim 1, wherein the degree of vacuum of the vacuum applied in step S3 is 0.1 to 200 Pa.
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