CN113106413B - Pretreatment process for CVD diamond coating pre-substrate - Google Patents

Pretreatment process for CVD diamond coating pre-substrate Download PDF

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CN113106413B
CN113106413B CN202110417962.7A CN202110417962A CN113106413B CN 113106413 B CN113106413 B CN 113106413B CN 202110417962 A CN202110417962 A CN 202110417962A CN 113106413 B CN113106413 B CN 113106413B
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diamond
substrate
sand blasting
nano composite
composite powder
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CN113106413A (en
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王立峰
魏秋平
李秋燕
施应洁
花腾宇
王宝峰
周科朝
施帅
施振
施海平
夏鑫
余寒
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Hunan Xinfeng Technology Co ltd
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Hunan Xinfeng Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • B24C1/10—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for compacting surfaces, e.g. shot-peening
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions

Abstract

The invention discloses a pretreatment process of a CVD diamond coating pre-substrate, which comprises the following steps of carrying out alkaline etching treatment on a substrate, then carrying out acid etching treatment, then carrying out dry sand blasting on the acid etched substrate by using diamond micro-nano composite powder, then carrying out wet sand blasting by using mortar containing diamond micro-nano composite powder to obtain the sand blasted substrate, then placing the sand blasted substrate in turbid liquid containing diamond powder to plant seed crystals, and finally carrying out heat treatment. According to the invention, firstly, an acid-base two-step method is adopted to carry out primary cleaning and etching on the surface of the substrate, and then dry-wet mixed sand blasting is adopted to improve the surface roughness of the substrate, strengthen the mechanical locking effect between the coating and the diamond, eliminate stress concentration and relieve residual stress, thereby improving the film-substrate binding force.

Description

Pretreatment process for CVD diamond coating pre-substrate
Technical Field
The invention belongs to the technical field of diamond coatings, and particularly relates to a pretreatment process for a CVD diamond coating pre-substrate.
Background
The CVD diamond coating is a material with the best known mechanical property in the nature at present, has extremely high hardness, extremely high wear resistance, extremely high elastic modulus, extremely low friction coefficient and extremely good corrosion resistance, has high processing precision and is a coating material with the greatest prospect. However, the alloy substrate without any pretreatment operation has the problems of low nucleation rate, difficult guarantee of film quality, poor film-substrate bonding performance and the like when the diamond coating is deposited. At present, the most important and effective solutions are the etching method for treating the substrate and the transition layer method, but the latter method has the defects of complex process and high equipment requirement. Thus, the etching method is the most likely pretreatment means for large-scale industrialization. The pretreatment technology adopted at home and abroad is mostly strong acid and strong base etching. The method is simple and easy to operate, but has limited treatment effect, and the nucleation rate, the nucleation time and the membrane-base bonding strength need to be further improved.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a pretreatment process for a CVD diamond coating pre-substrate. According to the invention, the surface of the substrate is firstly preliminarily cleaned and etched by adopting an acid-base two-step method, and then mixed sand blasting treatment by adopting a dry method and a wet method is adopted, so that the surface roughness of the substrate is improved, the mechanical locking effect between the coating and the diamond is enhanced, the stress concentration is eliminated, the residual stress is relieved, and the film-substrate binding force is improved. Meanwhile, seed crystals can be planted and the nucleation density of the diamond can be improved through sand blasting.
The invention relates to a pretreatment process of a CVD diamond coating pre-matrix, which comprises the following steps:
the matrix is subjected to alkaline etching and acid etching, then the acid-etched matrix is subjected to dry sand blasting by using diamond micro-nano composite powder, then wet sand blasting is performed by using mortar containing diamond micro-nano composite powder to obtain the sand-blasted matrix, then the sand-blasted matrix is placed in turbid liquid containing diamond powder to plant seed crystals, and finally heat treatment is performed.
In the invention, the substrate is not limited too much, whether the substrate is an alloy substrate or a non-alloy substrate, the effect of the CVD diamond coating can be improved by adopting the pretreatment process of the invention, and the substrate is preferably a hard alloy substrate, but when the substrate is selected from hard alloy, the mass fraction of Co in the hard alloy substrate needs to be controlled to be less than or equal to 3 percent.
In a preferable scheme, the mass fraction of Co in the matrix is less than or equal to 3%.
In a preferred embodiment, the alkaline etching agent is selected from NaOH solution, KOH solution, Na2CO3At least one of a solution and a Murakami reagent, wherein the time of the alkaline etching treatment is 10-20 min.
Further preferably, the agent for the alkaline etching treatment is a Murakami agent.
The Murakami reagent is K3[Fe(CN)]6、KOH、H2O is mixed with the solution according to the volume ratio of 1: 10.
In the invention, the substrate is firstly subjected to alkaline etching, and oil stains are removed through the alkaline etching.
In the actual operation process, after the alkali etching treatment, the substrate is placed in absolute ethyl alcohol for ultrasonic cleaning, then deionized water is used for ultrasonic cleaning, and finally the substrate is placed in an oven for drying, wherein the absolute ethyl alcohol cleaning time is 5-10 min, the deionized water cleaning time is 1-5 min, and the oven drying time is 1-2 min.
Preferably, the agent for acid etching treatment is selected from HNO3Solution, HCl solution, H2SO4Solution, HF solution, H2O2The acid etching time is 15-30 s.
In the present invention, the acid etching time is very short and limited control is required, and the inventors found that, in cooperation with the alkali etching treatment, the acid etching treatment for a very short time, i.e., the rust on the substrate surface can be completely removed and a roughened substrate surface can be obtained, whereas if the acid etching treatment time is prolonged, the substrate strength is rather impaired.
In the actual operation process, after acid etching treatment, the substrate is placed in absolute ethyl alcohol for ultrasonic cleaning, then deionized water is used for ultrasonic cleaning, and finally the substrate is placed in an oven for drying, wherein the absolute ethyl alcohol cleaning time is 5-10 min, the deionized water cleaning time is 1-5 min, and the oven drying time is 1-2 min.
In a preferred scheme, the granularity of the diamond micro-nano composite powder is 0.005-2 mu m.
In a preferred embodiment, the blasting pressure of the dry blasting is 1 × 106～3.5×106Pa, and the dry sand blasting time is 1-2 min.
According to the preferable scheme, in the mortar containing the diamond micro-nano composite powder, the mass fraction of the diamond micro-nano composite powder is 20-35%.
According to the preferable scheme, the particle size of the diamond micro-nano composite powder in the mortar containing the diamond micro-nano composite powder is 0.01-1 mu m.
In a preferred embodiment, the blasting pressure of the wet blasting is 1 × 106～3.5×106Pa, and the time of wet blasting is 1-2 min.
According to the invention, dry sand blasting is carried out on the surface of the alloy matrix by using diamond micro-nano composite powder, the micro-nano composite powder is filled in the pores of the matrix, the strength of the matrix is improved, more sites are provided for nucleation, then wet sand blasting is carried out on the surface of the alloy matrix by using mortar containing diamond micro-nano composite powder, the micro-nano composite powder is filled in the pores of the matrix, and meanwhile, under the combination of the sand blasting modes, the roughness of the surface of the matrix is further improved, the mechanical locking effect between a coating and diamond is enhanced, stress concentration is eliminated, residual stress is relieved, and the binding force of a film matrix is improved.
The inventors have found that the final coating effect can be improved better by using both the dry blasting and the wet blasting, but the order of the dry blasting and the wet blasting is very important, and the desired effect cannot be achieved by using the wet blasting and then using the dry blasting.
The inventor finds that the particle size of the diamond micro-nano composite powder used in dry sand blasting and wet sand blasting needs to be effectively controlled, if the particle size is too large, the surface of a base body can be scratched, the strength of the base body is reduced, the uniformity and the smoothness of the growth of a coating are not facilitated, and meanwhile, diamond particles are difficult to implant into the base body due to the too large particle size, are easy to fall off, have poor crystal implantation effect, and affect the quality of a subsequent deposition coating.
Preferably, in the suspension containing diamond powder, the solid-liquid mass-volume ratio of diamond powder to solvent is 2-6 g: 100 ml.
Preferably, the solvent used in the suspension containing diamond powder is acetone or [2- (methacryloyloxy) ethyl group]Trimethyl ammonium chloride (TMAMEC) aqueous solution with concentration of 10-6～10-2mol/l。
In a preferable scheme, the time for planting the seed crystals is 10-30 min.
In the actual operation process, after the seed crystal is planted, the substrate is placed in absolute ethyl alcohol for ultrasonic cleaning, then deionized water is used for ultrasonic cleaning, and finally the substrate is placed in an oven for drying, wherein the absolute ethyl alcohol cleaning time is 5-10 min, the deionized water cleaning time is 1-5 min, and the drying time is 1-2 min.
Preferably, the heat treatment is performed in a mixed atmosphere containing hydrogen, and the volume fraction of hydrogen in the mixed atmosphere containing hydrogen is 6-50%.
In the preferable scheme, the temperature of the heat treatment is 400-600 ℃, the time of the heat treatment is 2-6 h, and the temperature is reduced at a cooling speed of 20-30 DEG/min after the heat treatment is finished.
In the actual operation process, the substrate with the seed crystals planted is placed in a vacuum furnace for roasting treatment, after gas replacement, mixed gas containing hydrogen is introduced to normal pressure, then the temperature is raised to the temperature of heat treatment, heat is preserved, the seed crystals are diffused, the seed crystals are more uniformly and more firmly embedded on the surface of the substrate, after the heat preservation is finished, the sample is rapidly cooled, and the gas source can be closed after the temperature is reduced to below 100 ℃ so as not to introduce mixed atmosphere containing hydrogen.
The inventor finds that after the heat treatment is finished, the cooling speed has the most influence on the final material performance, a rapid cooling mode is required, and if the cooling speed is too slow, the composition segregation is serious or the defects are concentrated.
Advantageous effects
The process of the invention firstly adopts an acid-base two-step method to carry out primary cleaning and etching on the surface of the substrate, and then adopts dry-wet mixed sand blasting treatment to improve the surface roughness of the substrate, strengthen the mechanical locking effect between the coating and the diamond, eliminate stress concentration and relieve residual stress, thereby improving the film-substrate binding force. Meanwhile, seed crystals can be planted and the nucleation density of the diamond can be improved through sand blasting.
The invention provides a pretreatment method with higher working efficiency, lower pollution emission and higher safety, and can better exert the excellent performance of the diamond coating in application.
Detailed Description
Example 1
In the tungsten-titanium-cobalt hard alloy used in the present example, the mass fraction of cobalt is 1.8%.
1) Murakami reagent (K) was used3[Fe(CN)]6∶KOH∶H2Carrying out alkaline etching treatment on the YG3 tungsten-cobalt matrix for 20min, then carrying out ultrasonic cleaning in absolute ethyl alcohol for 10min, then carrying out ultrasonic cleaning with deionized water for 5min, and finally baking in an oven for 2 min;
2) acid etching the tungsten-titanium-cobalt hard alloy matrix for 30s by using aqua regia, ultrasonically cleaning the tungsten-titanium-cobalt hard alloy matrix in absolute ethyl alcohol for 10min, ultrasonically cleaning the tungsten-titanium-cobalt hard alloy matrix for 5min by using deionized water, and finally baking the tungsten-titanium-cobalt hard alloy matrix in an oven for 2 min;
3) performing dry sand blasting treatment on the surface of the alloy matrix for 2min by using diamond micro-nano composite powder with the particle size of 1 mu m, wherein the sand blasting pressure is 3.5 multiplied by 106Pa；
4) Performing wet sand blasting treatment on the surface of the alloy matrix for 2min by using 35% by mass of diamond powder and 0.5 mu m diamond micro-nano composite powder mortar, wherein the sand blasting pressure is 3.5 multiplied by 106Pa；
5) Putting the alloy matrix into suspension with the mixture ratio concentration of 2g diamond powder/100 mlPerforming ultrasonic oscillation in liquid, performing seed crystal planting treatment for 30min, and suspending liquid solvent of diamond powder with concentration of 10-6mol/l of [2- (methacryloyloxy) ethyl group]Deionized water solution of trimethyl ammonium chloride (TMAMEMC) with diamond powder particle size of 1 μm, ultrasonic cleaning with anhydrous ethanol for 10min, ultrasonic cleaning with plasma water for 5min, and oven baking for 2 min;
6) finally, baking the substrate by adopting a vacuum tube furnace, introducing mixed gas of hydrogen and nitrogen into a quartz tube, wherein the proportion of the hydrogen is 50 percent, leading the air pressure to reach normal pressure, heating to 600 ℃, then preserving heat for 2 hours, then stopping heating, rapidly cooling the sample, leading the cooling rate to be 30 DEG/min, finally turning off a vacuum pump, reducing the temperature to be below 100 ℃, turning on a piston, introducing pressure to normal pressure, taking out the pretreated substrate
The application effect is achieved;
placing the pretreated substrate in hot wire chemical vapor deposition equipment, controlling the temperature of a hot wire to be 2100 ℃, the distance between the hot wire and the substrate to be 10 mu m, the temperature of the substrate to be 700 ℃, and the composition of atmosphere to be CH4、H2And Ar with the flow rate of 36sccm, 4sccm and 60sccm respectively, the gas pressure of 3kpa and the deposition time of 6h, so as to obtain the matrix containing the diamond coating.
Detecting the film-substrate bonding performance of the obtained matrix containing the diamond coating by using a Rockwell indentation method, and observing that the failure load of the matrix is 20N through a scanning electron microscope; another sample and Si3N4The ball is subjected to a ball face-to-face grinding experiment, the applied load is 2N, the result shows that the friction coefficient is stabilized at 0.04, and the wear rate of the coating is 2 multiplied by 10-8mm3N-1m-1，Si3N4The wear rate of the ball was 7X 10-6mm3N-1m-1。
Example 2
In the WC-Co matrix used in this example, the mass fraction of cobalt was 3%.
1) Murakami reagent (K) was used3[Fe(CN)]6∶KOH∶H2O1: 10 (volume ratio)) is subjected to alkali etching treatment on a WC-Ni matrix for 15min, and then ultrasonic cleaning is carried out in absolute ethyl alcoholWashing for 8min, then ultrasonically cleaning for 3min by using deionized water, and finally baking for 2min in an oven;
2) using v (HNO)3):v(H2O2) Carrying out acid etching treatment on a WC-Co substrate for 25s by using a solution with a ratio of 3:7, carrying out ultrasonic cleaning in absolute ethyl alcohol for 8min, carrying out ultrasonic cleaning with deionized water for 3min, and finally baking in an oven for 2 min;
3) performing dry sand blasting treatment on the surface of the alloy matrix for 2min by using diamond micro-nano composite powder with the particle size of 1 mu m, wherein the sand blasting pressure is 2 multiplied by 106Pa；
4) Carrying out wet sand blasting treatment on the surface of the alloy matrix for 2min by using 30 mass percent of diamond powder and mortar of diamond micro-nano composite powder with the particle size of 75nm, wherein the sand blasting pressure is 2 multiplied by 106Pa；
5) Placing the alloy matrix into suspension with a concentration of 4g diamond powder/100 ml for ultrasonic oscillation, and performing seed crystal implantation for 20min, wherein the concentration of diamond powder suspension is 10-4mol/l of [2- (methacryloyloxy) ethyl group]Deionized water solution of trimethyl ammonium chloride (TMAMEMC) with diamond powder particle size of 75nm, ultrasonic cleaning with anhydrous ethanol for 8min, ultrasonic cleaning with plasma water for 3min, and oven baking for 2 min;
6) finally, baking the substrate by adopting a vacuum tube furnace, introducing mixed gas of hydrogen and argon into a quartz tube, wherein the proportion of the hydrogen is 25 percent, leading the air pressure to reach normal pressure, heating to 500 ℃, then preserving heat for 4 hours, then stopping heating, leading the sample to be rapidly cooled, leading the cooling rate to be 25 DEG/min, finally closing a vacuum pump, reducing the temperature to be below 100 ℃, closing an air source, opening a piston, leading the pressure to be normal pressure, and taking out the pretreated substrate;
the application effect is achieved;
placing the pretreated substrate in hot wire chemical vapor deposition equipment, controlling the temperature of a hot wire to be 2100 ℃, the distance between the hot wire and the substrate to be 10 mu m, the temperature of a substrate to be 700 ℃, and the composition of atmosphere to be CH4、H2And Ar with the flow rate of 36sccm, 4sccm and 60sccm respectively, the gas pressure of 3kpa and the deposition time of 6h, so as to obtain the matrix containing the diamond coating.
Detecting the film-substrate bonding performance of the obtained matrix containing the diamond coating by using a Rockwell indentation method, and observing that the failure load of the matrix is 22N through a scanning electron microscope; another sample and Si3N4The ball is subjected to a ball face-to-face grinding experiment, the applied load is 2N, the result shows that the friction coefficient is stabilized at 0.04, and the wear rate of the coating is 4 multiplied by 10-8mm3N-1m-1，Si3N4The ball has a wear rate of 5X 10-6mm3N-1m-1。
Example 3
1) Murakami reagent (K) was used3[Fe(CN)]6∶KOH∶H2Carrying out alkali etching treatment on the WC-Cr matrix for 10min by using O (volume ratio) of 1: 10), then carrying out ultrasonic cleaning for 5min in absolute ethyl alcohol, then carrying out ultrasonic cleaning for 1min by using deionized water, and finally baking for 1min in an oven;
2) using H2SO4Solution (v (H)2SO4)︰v(H2O) ═ 1: 10) acid etching the WC-Co substrate for 30s, then ultrasonically cleaning in absolute ethyl alcohol for 5min, then ultrasonically cleaning with deionized water for 1min, and finally baking in an oven for 1 min;
3) performing dry sand blasting treatment on the surface of the alloy matrix for 1min by using diamond micro-nano composite powder with the particle size of 2 mu m, wherein the sand blasting pressure is 1 multiplied by 106Pa；
4) Performing wet sand blasting treatment on the surface of the alloy matrix for 1min by using the mortar of diamond micro-nano composite powder with the diamond powder mass accounting for 20% and the particle size of 15nm, wherein the sand blasting pressure is 1 multiplied by 106Pa；
5) Placing the alloy matrix into suspension with a concentration of 2g diamond powder/100 ml for ultrasonic oscillation, and performing seed crystal implantation for 10min, wherein the concentration of diamond powder suspension is 10-6mol/l of [2- (methacryloyloxy) ethyl group]Trimethyl ammonium chloride (TMAMEMC) solution with diamond powder particle size of 10nm, ultrasonic cleaning with anhydrous ethanol for 5min, ultrasonic cleaning with plasma water for 1min, and oven drying for 1 min;
6) finally, baking the substrate by adopting a vacuum tube furnace, introducing mixed gas of hydrogen and nitrogen into a quartz tube, wherein the proportion of the hydrogen is 6 percent, leading the air pressure to reach the normal pressure, heating to 400 ℃, then preserving the heat for 2 hours, then stopping heating, leading the sample to be rapidly cooled, leading the cooling rate to be 20 DEG/min, finally closing a vacuum pump, reducing the temperature to be below 100 ℃, closing an air source, opening a piston, leading the pressure to the normal pressure, and taking out the pretreated substrate;
the application effect is achieved;
placing the pretreated substrate in hot wire chemical vapor deposition equipment, controlling the temperature of a hot wire to be 2100 ℃, the distance between the hot wire and the substrate to be 10 mu m, the temperature of the substrate to be 700 ℃, and the composition of atmosphere to be CH4、H2And Ar with the flow rate of 36sccm, 4sccm and 60sccm respectively, the gas pressure of 3kpa and the deposition time of 6h, so as to obtain the matrix containing the diamond coating.
Detecting the film-substrate binding performance of the obtained matrix containing the diamond coating by using a Rockwell indentation method, and observing that the failure load of the matrix is 18N through a scanning electron microscope; another sample and Si3N4The ball is subjected to a ball face-to-face grinding experiment, the applied load is 2N, the result shows that the friction coefficient is stabilized at 0.04, and the wear rate of the coating is 6 multiplied by 10-8mm3N-1m-1，Si3N4The ball has a wear rate of 3X 10-6mm3N-1m-1。
Comparative example 1
The other conditions were the same as in example 1, except that the etching treatment was carried out for 5 minutes, and the diamond coating-containing substrate was examined for film-substrate bonding properties by the Rockwell indentation method, and the failure load was 14N as observed by a scanning electron microscope.
Comparative example 2
The diamond coated substrates obtained without wet blasting were tested for film-to-substrate bonding using the Rockwell indentation method and observed to have a failure load of 16N by scanning electron microscopy, all under the same conditions as in example 1.
Comparative example 3
The other conditions were the same as in example 1 except that wet blasting was performed first and then dry blasting was performed, the film-substrate bonding properties of the diamond-coated substrate obtained were examined by the rockwell indentation method, and the failure load was 15N as observed by a scanning electron microscope.
Comparative example 4
The other conditions were the same as in example 1 except that the sample was rapidly cooled at a cooling rate of 15 deg./min, and the resulting diamond coating-containing substrate was examined for film-substrate bonding properties by the Rockwell indentation method and was observed to have a failure load of 14N by a scanning electron microscope.

Claims (10)

1. A pretreatment process for a CVD diamond coating pre-substrate is characterized by comprising the following steps: comprises the following steps of (a) preparing a solution,
the matrix is subjected to alkaline etching and acid etching, then the acid-etched matrix is subjected to dry sand blasting by using diamond micro-nano composite powder, then wet sand blasting is performed by using mortar containing diamond micro-nano composite powder to obtain the sand-blasted matrix, then the sand-blasted matrix is placed in turbid liquid containing diamond powder to plant seed crystals, and finally heat treatment is performed.
2. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, characterised in that: in the matrix, the mass fraction of Co is less than or equal to 3%.
3. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, characterised in that: the alkaline etching agent is selected from NaOH solution, KOH solution and Na2CO3At least one of a solution and a Murakami reagent, wherein the time of the alkaline etching treatment is 10-20 min.
4. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, characterised in that: the agent for acid etching treatment is selected from HNO3Solution, HCl solution, H2SO4Solution, HF solution, H2O2The acid etching time is 15-30 s.
5. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, characterised in that: when the dry sand blasting is carried out, the granularity of the diamond micro-nano composite powder is 0.005-2 mu m, and the sand blasting pressure of the dry sand blasting is 1 multiplied by 106～3.5×106Pa, and the dry sand blasting time is 1-2 min.
6. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, characterised in that: in the mortar containing the diamond micro-nano composite powder, the mass fraction of the diamond micro-nano composite powder is 20-35%;
the particle size of the diamond micro-nano composite powder in the mortar containing the diamond micro-nano composite powder is 0.01-1 mu m;
the sand blasting air pressure of the wet sand blasting is 1 multiplied by 106～3.5×106Pa, and the time of wet blasting is 1-2 min.
7. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, characterised in that: in the suspension containing the diamond powder, the solid-liquid mass volume ratio of the diamond powder to a solvent is 2-6 g: 100 ml;
in the suspension containing the diamond powder, the solvent is acetone or TMAMEC aqueous solution, and the concentration of the TMAMEC aqueous solution is 10-6～10-2mol/l。
8. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, characterised in that: the time for planting the seed crystals is 10-30 min.
9. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, wherein: the heat treatment is carried out in a hydrogen-containing mixed atmosphere, wherein the volume fraction of hydrogen in the hydrogen-containing mixed atmosphere is 6-50%.
10. A CVD diamond pre-coating substrate pre-treatment process according to claim 1, characterised in that: the temperature of the heat treatment is 400-600 ℃, the time of the heat treatment is 2-6 h, and the temperature is reduced at a cooling speed of 20-30 DEG/min after the heat treatment is finished.
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