CN114134504A - Hard alloy cutter pretreatment method for preparing diamond coating - Google Patents
Hard alloy cutter pretreatment method for preparing diamond coating Download PDFInfo
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- CN114134504A CN114134504A CN202111466320.2A CN202111466320A CN114134504A CN 114134504 A CN114134504 A CN 114134504A CN 202111466320 A CN202111466320 A CN 202111466320A CN 114134504 A CN114134504 A CN 114134504A
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- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- 238000002203 pretreatment Methods 0.000 title claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 69
- 239000010941 cobalt Substances 0.000 claims abstract description 69
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 64
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- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 20
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
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- 230000035484 reaction time Effects 0.000 claims description 6
- ZSPCEEBYANPQIX-UHFFFAOYSA-H chromium(3+) trisulfate pentahydrate Chemical group O.O.O.O.O.S(=O)(=O)([O-])[O-].[Cr+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[Cr+3] ZSPCEEBYANPQIX-UHFFFAOYSA-H 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical group O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 239000010949 copper Substances 0.000 abstract description 31
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
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Images
Classifications
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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
- 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
- C23F1/30—Acidic compositions for etching other metallic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to the technical field of metal processing, in particular to a pretreatment method of a hard alloy cutter for preparing a diamond coating, which comprises the following steps: etching the cemented carbide tool with Murakami reagent; etching the hard alloy cutter processed by the S1 by using acid solution; placing the hard alloy cutter processed by the S2 into a mixed solution of copper sulfate and chromium sulfate for replacement reaction until the subsurface cobalt is completely covered; and placing the cemented carbide tool subjected to replacement treatment into the suspension liquid to implant crystals in an ultrasonic environment, thereby completing pretreatment. The method adopts a solution replacement method, replaces partial subsurface cobalt by Cu and Cr ions in a cobalt-containing area, so that the Cu and Cr cover the surface of the subsurface cobalt, and removes a Cu/Cr layer covering the WC surface by planting crystals, thereby not only not changing the surface roughness of a WC phase, but also preventing the subsurface cobalt from overflowing and eliminating the adverse effect of the subsurface cobalt on the growth of diamond grains.
Description
Technical Field
The invention relates to the technical field of metal processing, in particular to a pretreatment method for preparing a hard alloy cutter with a diamond coating.
Background
The CVD diamond coating cutter has the advantages of high hardness, abrasion resistance, good heat conductivity, low thermal expansion coefficient and the like, and is very suitable for processing non-ferrous metals, alloys, non-metallic materials, composite materials and other materials which are difficult to process. Cemented carbide is a common substrate material for depositing CVD diamond films, of which the WC-Co system is most widely used, and the cobalt binder in such cemented carbide is very detrimental to diamond growth, so that the cemented carbide is pretreated before the diamond film is deposited.
A two-step cobalt removal method: developed in the middle of the nineties, the WC phase was etched away with Murakami reagent and then the Co phase was etched away with acid. Has been paid high attention by countries in the world at present and has achieved good effect in research and application. Removing WC phase by alkaline ferrate Murakami etching method, etching the surface of the substrate by various inorganic acids after removing WC phase to dissolve Co phase, and finally carrying out diamond suspension crystal planting treatment.
Intermediate transition layer or intermediate compound method: one or more transition layers with physical properties between the base material and the diamond or a diamond intermediate compound can be grown on the base by using the processes and methods such as CVD, PVD or P/CVD, and the like, and the interface transition layer or the diamond intermediate compound plays an important role in reducing the abrupt change of the physical properties of the interface, relieving stress concentration, improving the wettability between the base and the diamond film, improving the bonding strength and maintaining the mechanical stability of the interface. The intermediate transition layer materials studied at present mainly comprise amorphous carbide, SIC, WC, Cu, Mo, Nb, TiC/N, TiAlN, WC + 10% TiC and the like.
A heat treatment method: diamond coating boronizing pretreatment of hard alloy tool-Wangbang et al, carried out boronizing treatment on the surface of hard alloy by solid boronizing agent, and surface active B atoms and hard alloy surface Co phase formed stable CoB and Co2The B compounds are very stable under the condition of diamond deposition, so that Co is not evaporated during deposition to influence diamond nucleation, the adverse effect of CO on diamond deposition on the surface of the hard alloy can be obviously eliminated, and the diffusion of subsurface Co to the surface layer during the deposition process is prevented, thereby improving the diamond qualityQuality and adhesion of the stone film.
In the method for pretreating hard alloy, the method for removing or blocking cobalt on the surface layer in the solution is the simplest method, such as an acid solution corrosion method and a two-step method, and has the advantages of simple operation and low cost, however, the method has poor effect when treating high-cobalt hard alloy containing more than 8% of cobalt, and cannot prevent the subsurface Co from being driven by high temperature to diffuse to the surface layer during deposition, so that the nucleation growth of diamond grains is influenced, and certain limitations exist.
The surface of the hard alloy is subjected to boronizing treatment to prevent Co from diffusing to the interface layer and the diamond coating at high temperature, but the tool needs to be placed in a high-temperature environment during operation, so that the cohesiveness of the cobalt in the alloy is reduced, the alloy becomes brittle, the influence on alloy tools smaller than a certain size is great, and the hard alloy is only suitable for large-size alloy tools.
The method for preparing the intermediate transition layer or the intermediate compound has stronger bonding performance with two heterogeneous materials, namely the diamond film and the hard alloy substrate, can prevent Co from diffusing to the interface layer and the diamond coating direction at high temperature, and does not generate negative influence on nucleation and growth of the diamond film. However, the intermediate layer is generally prepared by processes such as CVD, PVD or PCVD, and the like, and the methods greatly increase the production cost, increase the operation steps and increase the difficulty, so that the method is difficult to be applied to actual production.
The document retrieval of the prior art finds that Chinese patent application No. 202010014014.4 discloses a method for preparing a diamond coating on the surface of a hard alloy with wide cobalt content and a tool and a die with the diamond coating, when the light rare earth mixture powder on the surface of an auxiliary anode is bombarded by plasma beams, a small amount of rare earth elements are volatilized into working gas, the cobalt phase in the surface layer of a hard alloy sample is subjected to rapid and efficient nitridation pretreatment and is converted into a nitride cobalt phase with high temperature stability, the nitride cobalt is not diffused in the preparation process of the diamond coating, and the outward diffusion of the unconverted cobalt phase at the deep layer of a sub-surface forms a barrier. The method has favorable effects on the hard alloy with low cobalt and high cobalt content, but has high preparation cost and high equipment requirement, is difficult to apply in actual production, and in addition, the intermediate transition layer completely covers the surface of the hard alloy, reduces the roughness and also influences the occlusion degree of diamond grains and the hard alloy.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a pretreatment method of a hard alloy cutter for preparing a diamond coating, which aims to prepare an intermediate compound, does not use high-cost means such as CVD/PVD and the like, adopts a solution replacement method, replaces part of subsurface cobalt by Cu and Cr ions in a cobalt-containing area, enables the Cu and Cr to cover the surface of the subsurface cobalt, and then removes a Cu/Cr layer covered on the WC surface through crystal implantation, so that the surface roughness of a WC phase is not changed, Cu and Cr can prevent the overflow of the subsurface cobalt in the process of depositing diamond and eliminate the adverse effect of the subsurface cobalt on the growth of diamond grains.
The invention provides a pretreatment method of a hard alloy cutter for preparing a diamond coating, which comprises the following specific steps:
s1, etching a hard alloy cutter by using a Murakami reagent, and then cleaning the hard alloy cutter by using clear water;
s2, etching the hard alloy cutter processed by the step S1 by using an acid solution to expose the cobalt on the subsurface, and then cleaning the hard alloy cutter by using clear water;
s3, preparing a mixed solution of copper sulfate and chromium sulfate for later use;
s4, placing the hard alloy cutter processed in the step S2 into the mixed solution of the step S3, then reacting in an ultrasonic environment, controlling the reaction time, and replacing until the subsurface cobalt is completely covered;
s5, preparing diamond powder suspension by using ethanol as a solvent, and placing the hard alloy cutter processed by the S4 into the suspension for crystal implantation in an ultrasonic environment to finish pretreatment.
According to the technical scheme, firstly, the hard alloy cutter is etched and corroded on surface WC particles through a Murakami reagent, then the surface cobalt layer is etched and corroded through an acid solution, the subsurface cobalt is exposed, then a mixed solution of copper sulfate and chromium sulfate is used for soaking for replacement reaction, the hard alloy cutter with the subsurface cobalt covered with a copper-chromium layer is obtained, and finally crystal planting is carried out. According to the method, the subsurface cobalt is replaced by copper and chromium until the copper and chromium cover the surface of the subsurface cobalt, the Cu/Cr layer covering the surface of WC is removed by crystal implantation, so that WC particles cannot be covered, the rough appearance of the surface of a cutter can be kept, the diamond particles and the surface of the cutter can be tightly engaged, meanwhile, the Cu/Cr layer which is not firmly attached to the substrate can be peeled off in the crystal implantation process, only the Cu/Cr layer with good adhesive force is left, and the quality of the Cu-Cr layer prepared by the replacement method can be greatly improved.
Further, in the above scheme S1, the Murakami reagent is etched for 20 to 30 min. Wherein the Murakami reagent is 10g K3[Fe(CN)]6And 10g KOH/NaOH in 100mL water.
Further, in the above scheme S2, the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide, and a volume ratio of the sulfuric acid to the hydrogen peroxide in the mixed solution is 2-4:6-8, preferably 3: 7.
Further, in the above scheme S2, the acid solution is used for etching the tool for 4-7S. In the technical scheme, the etching time of the acid solution is short, is obviously shorter than that of a normal two-step method, and the corrosion of the cobalt layer is less.
Further, in the above scheme S3, the mass fraction of copper sulfate in the mixed solution is 1.4 to 2.2%, and the copper sulfate is copper sulfate pentahydrate; the mass fraction of the chromium sulfate is 0.3-0.6%, and the chromium sulfate is chromium sulfate pentahydrate. In the technical scheme, the mixed solution of copper sulfate and chromium sulfate is used for covering the subsurface cobalt of the hard alloy cutter and completely covering the subsurface cobalt, so that the overflow of the subsurface cobalt can be prevented in the process of depositing diamond, and the adverse effect on the growth of diamond grains is eliminated.
Further, in the above scheme S4, the power of the ultrasonic wave is 40 to 60W, and the reaction time is 9 to 14 min.
Further, in the above scheme S5, the power of the ultrasonic wave is 40 to 60W, and the treatment time is 20 to 30 min.
The invention also provides an application of the hard alloy cutter pretreatment method in a low-cobalt hard alloy cutter or a high-cobalt hard alloy cutter.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, Cu and Cr cover the surface of the subsurface cobalt, and the Cu and Cr can prevent the subsurface cobalt from overflowing in the process of depositing diamond, so that the adverse effect of the subsurface cobalt on the growth of diamond grains is eliminated;
2. compared with the method that the surface of the hard alloy cutter is completely covered with a layer of intermediate transition layer or intermediate compound by a PVD/CVD method, the method only needs to replace the subsurface cobalt into Cu and Cr, the Cu and the Cr only cover the surface of the subsurface cobalt, and the Cu/Cr covering the surface of WC particles is removed through the crystal implanting process, so that the rough appearance of the surface of the cutter can be kept, the surface has higher roughness, and the occlusion tightness of the diamond particles and the surface of the cutter can be ensured;
3. according to the method, through the crystal planting process, the copper/chromium layer which is not firmly attached can be peeled off, only the copper/chromium with good adhesive force is left, and the quality of the copper-chromium layer prepared by the replacement method can be greatly improved;
4. the method has reliable process and low cost, and can be suitable for low-cobalt hard alloy cutters or high-cobalt hard alloy cutters.
Drawings
FIG. 1 is a schematic view of the structure of a non-pretreated cemented carbide tool according to the present invention;
FIG. 2 is a schematic view of a cemented carbide tool according to the present invention after being etched by Murakami reagent;
FIG. 3 is a schematic view of the structure of a hard metal tool etched with an acid solution according to the present invention;
FIG. 4 is a schematic structural diagram of a cemented carbide tool after reaction of a copper-chromium mixed solution according to the present invention;
FIG. 5 is a schematic structural diagram of a cemented carbide tool after reaction and crystal growth by a Cu-Cr mixed solution according to the present invention.
Number designations in the schematic drawings illustrate that:
1. non-corroded WC particles; 2. cobalt on the surface layer; 3. corroded WC particles; 4. cobalt on the subsurface layer; 5. a copper chromium layer covering the WC crystal grains; 6. a copper chromium layer overlying the subsurface cobalt.
Detailed Description
The invention is further explained with reference to the drawings and the embodiments. Other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and its several details are capable of modifications and variations in various respects, all without departing from the spirit of the invention.
In the description of the present application, it should be understood that the terms "first", "second", etc. are used to define the components, and are used only for the convenience of distinguishing the corresponding components, and if not otherwise stated, the terms have no special meaning, and thus, should not be construed as limiting the scope of the present application.
In the description of the present application, it is to be understood that the orientation or positional relationship indicated by the directional terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal" and "top, bottom", etc., are generally based on the orientation or positional relationship shown in the drawings, and are used for convenience of description and simplicity of description only, and in the case of not making a reverse description, these directional terms do not indicate and imply that the device or element being referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore, should not be considered as limiting the scope of the present application; the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.
Referring to fig. 1 to 4, it should be noted that the drawings provided in the present embodiment are only schematic illustrations of the basic idea of the present invention, and only the components related to the present invention are shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the shape, number and ratio of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
The invention aims to provide a pretreatment method for preparing a hard alloy cutter with a diamond coating, which comprises the following specific steps:
s1, etching a hard alloy cutter by using a Murakami reagent, and then cleaning the hard alloy cutter by using clear water; specifically, the Murakami reagent is 10g K3[Fe(CN)]6And 10g KOH/NaOH dissolved in 100mL water mixed solution, etching time is 20-30min, either standing etching or etching while using ultrasonic treatment;
s2, etching the hard alloy cutter processed by the step S1 by using an acid solution to expose the cobalt on the subsurface, and then cleaning the hard alloy cutter by using clear water; specifically, the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 2-4:6-8, preferably 3: 7; the etching time is 4-7S, which is obviously shorter than the etching time of 30S by a normal two-step method, the corrosion of the cobalt layer is less, and the cobalt layer is exposed, so that the later-stage cobalt replacement is facilitated; the acid solution etching can be static etching or ultrasonic treatment.
S3, preparing a mixed solution of copper sulfate and chromium sulfate for later use; specifically, the mass fraction of copper sulfate in the mixed solution is 1.4-2.2%, and the copper sulfate is copper sulfate pentahydrate; the mass fraction of the chromium sulfate is 0.3-0.6%, and the chromium sulfate is chromium sulfate pentahydrate.
S4, placing the hard alloy cutter processed in the step S2 into the mixed solution of the step S3, then reacting in an ultrasonic environment, controlling the reaction time, and replacing until the subsurface cobalt is completely covered; specifically, the reaction is carried out under the environment of 40-60W of ultrasonic power, the reaction time is 9-14min, and the reaction can be stopped when all the exposed cobalt on the subsurface layer is covered by copper and chromium by observing in the reaction process.
S5, preparing diamond powder suspension by using ethanol as a solvent, and placing the hard alloy cutter processed by the S4 into the suspension for crystal planting in an ultrasonic environment. Specifically, the diamond powder suspension is prepared by mixing a certain amount of nano diamond with an ethanol solvent, and adding a proper amount of dispersant or surfactant to improve the suspension property, wherein the ethanol can be 95% ethanol, the ultrasonic power is 40-60W, and the pretreatment is finished after the treatment for 20-30 min.
Example 1
A pretreatment method of a hard alloy cutter for preparing a diamond coating comprises the following specific steps: wherein, the schematic structural diagram of the cemented carbide tool before pretreatment is shown in fig. 1.
S1, etching a hard alloy cutter by using a Murakami reagent, then cleaning the hard alloy cutter by using clear water, wherein the structural schematic diagram of the processed hard alloy cutter is shown in figure 2; wherein the Murakami reagent is 10g K3[Fe(CN)]6And 10g KOH dissolved in 100mL water, the ultrasonic treatment etching time is 25 min;
s2, etching the hard alloy cutter processed by the step S1 by using an acid solution to expose the subsurface cobalt, and then cleaning the hard alloy cutter by using clear water, wherein the structural schematic diagram of the processed hard alloy cutter is shown in FIG. 3; wherein the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 3:7, and the etching time is 5 s.
S3, preparing a mixed solution of copper sulfate and chromium sulfate for later use; wherein the mass fraction of copper sulfate in the mixed solution is 2%; the mass fraction of the chromium sulfate is 0.5%.
S4, placing the hard alloy cutter processed by the step S2 into the mixed solution of the step S3, reacting in an environment with the ultrasonic power of 50W, controlling the reaction for 10min, and performing replacement until the subsurface cobalt is completely covered, wherein the schematic structural diagram of the hard alloy cutter after the reaction is shown in FIG. 4.
S5, preparing diamond powder suspension by using ethanol as a solvent, placing the hard alloy cutter processed by the S4 into the suspension, and carrying out crystal planting for 25min under the environment of 50W of ultrasonic power to finish the pretreatment, wherein the structural schematic diagram of the hard alloy cutter after crystal planting is shown in FIG 5. Wherein, the diamond powder suspension is prepared by mixing 0.5 percent of nano diamond with ethanol solvent.
Example 2
A pretreatment method of a hard alloy cutter for preparing a diamond coating comprises the following specific steps: .
S1, etching a hard alloy cutter by using a Murakami reagent, and then cleaning the hard alloy cutter by using clear water; wherein the Murakami reagent is 10g K3[Fe(CN)]6And 10g of NaOH dissolved in 100mL of water, and carrying out ultrasonic treatment on the mixed solution for etching for 20 min;
s2, etching the hard alloy cutter processed by the step S1 by using an acid solution to expose the cobalt on the subsurface, and then cleaning the hard alloy cutter by using clear water; wherein the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 4:6, and the etching time is 7 s.
S3, preparing a mixed solution of copper sulfate and chromium sulfate for later use; wherein the mass fraction of copper sulfate in the mixed solution is 1.4%; the mass fraction of the chromium sulfate is 0.6%.
And S4, putting the hard alloy cutter processed by the step S2 into the mixed solution of the step S3, reacting in an environment with ultrasonic power of 60W, controlling the reaction for 14min, and replacing until the subsurface cobalt is completely covered.
S5, preparing diamond powder suspension by using ethanol as a solvent, placing the hard alloy cutter processed by the S4 into the suspension, and carrying out crystal planting for 20min under the environment that the ultrasonic power is 60W to finish the pretreatment. Wherein, the diamond powder suspension is prepared by mixing 0.8 percent of nano diamond with ethanol solvent.
Example 3
A pretreatment method of a hard alloy cutter for preparing a diamond coating comprises the following specific steps:
s1, etching a hard alloy cutter by using a Murakami reagent, and then cleaning the hard alloy cutter by using clear water; wherein the Murakami reagent is 10g K3[Fe(CN)]6And 10g KOH dissolved in 100mL water, the ultrasonic treatment etching time is 30 min;
s2, etching the hard alloy cutter processed by the step S1 by using an acid solution to expose the cobalt on the subsurface, and then cleaning the hard alloy cutter by using clear water; wherein the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 2:8, and the etching time is 4 s.
S3, preparing a mixed solution of copper sulfate and chromium sulfate for later use; wherein the mass fraction of copper sulfate in the mixed solution is 2.2%; the mass fraction of the chromium sulfate is 0.3%.
And S4, putting the hard alloy cutter processed by the step S2 into the mixed solution of the step S3, reacting in an environment with ultrasonic power of 40W, controlling the reaction for 9min, and replacing until the subsurface cobalt is completely covered.
S5, preparing diamond powder suspension by using ethanol as a solvent, placing the hard alloy cutter processed by the S4 into the suspension, and carrying out crystal planting for 30min under the environment that the ultrasonic power is 40W to finish the pretreatment. Wherein, the diamond powder suspension is prepared by mixing 1 percent of nano diamond and ethanol solvent.
Comparative example 1
Compared with a normal two-step pretreatment technology: the method comprises the following specific steps:
s1, etching a hard alloy cutter by using a Murakami reagent, and then cleaning the hard alloy cutter by using clear water; wherein the Murakami reagent is 10g K3[Fe(CN)]6And 10g KOH dissolved in 100mL water, the ultrasonic treatment etching time is 25 min;
s2, etching the hard alloy cutter processed by the step S1 by using an acid solution to expose the cobalt on the subsurface, and then washing the hard alloy cutter by using clear water to finish the pretreatment; wherein the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 3:7, and the etching time is 30 s.
S3, preparing a diamond powder suspension by using ethanol as a solvent, placing the hard alloy cutter treated by the S2 into the suspension, and carrying out crystal planting for 25min under the environment of 50W of ultrasonic power to finish pretreatment. Wherein, the diamond powder suspension is prepared by mixing 0.5 percent of nano diamond with ethanol solvent.
Comparative example 2
A pretreatment method of a hard alloy cutter for preparing a diamond coating comprises the following specific steps:
s1, etching a hard alloy cutter by using a Murakami reagent, and then cleaning the hard alloy cutter by using clear water; wherein the Murakami reagent is 10g K3[Fe(CN)]6And 10g KOH dissolved in 100mL water, the ultrasonic treatment etching time is 25 min;
s2, etching the hard alloy cutter processed by the step S1 by using an acid solution to expose the cobalt on the subsurface, and then cleaning the hard alloy cutter by using clear water; wherein the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 3:7, and the etching time is 5 s.
S3, preparing a mixed solution of copper sulfate and chromium sulfate for later use; wherein the mass fraction of copper sulfate in the mixed solution is 2%; the mass fraction of the chromium sulfate is 0.5%.
And S4, putting the hard alloy cutter processed by the step S2 into the mixed solution of the step S3, reacting in an environment with the ultrasonic power of 50W, controlling the reaction for 10min, replacing until the subsurface cobalt is completely covered, and finishing the pretreatment.
The cemented carbide tools pretreated in example 1, comparative example 1 and comparative example 2 were placed in a CVD apparatus for deposition of the diamond coating.
The test method comprises the following steps: and (3) a sand blasting method, wherein the sand grain diameter is 120 meshes, the material is corundum, the pressure is 0.5MPa, the distance between a spray gun and the coating is 5-10mm, the angle is 75-90 degrees, the cracking and stripping time of the coating is recorded, and the longer the time is, the larger the binding force between the coating and the hard alloy substrate is.
And (3) testing results: the peel time of the coating of example 1 was 118s, that of comparative example 1 was 60s, and that of comparative example 2 was 49 s.
The bonding force of the coating subjected to acid-base-Cu/Cr replacement-crystal implantation treatment is far better than that of the coating obtained by the traditional acid-base-crystal implantation treatment, the crystal implantation step in the method is also very important, and if the Cu/Cr coating covering the WC crystal grains is not removed by the diamond particles oscillated in the crystal implantation step and the Cu/Cr layer which is not firmly attached to the cobalt on the subsurface layer is removed, the bonding strength of the coating and the hard alloy is reduced.
In conclusion, the subsurface cobalt is replaced by the Cu and the Cr, the Cu and the Cr cover the surface of the subsurface cobalt, the Cu/Cr layer covering the surface of the WC is removed by the crystal implantation, and the Cu/Cr layer cannot cover the WC particles, so that the rough appearance of the surface of the cutter can be kept, the surface has higher roughness, and the occlusion tightness of the diamond particles and the surface of the cutter can be ensured; meanwhile, through the crystal planting process, the Cu/Cr layer which is not firmly attached to the substrate can be peeled off, and the Cu/Cr layer with good adhesive force is left, so that the quality and the bonding strength of the Cu/Cr layer are greatly improved; the pretreatment method has reliable process and low cost.
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.
Claims (9)
1. A pretreatment method of a hard alloy cutter for preparing a diamond coating is characterized by comprising the following specific steps:
s1, etching a hard alloy cutter by using a Murakami reagent, and then cleaning the hard alloy cutter by using clear water;
s2, etching the hard alloy cutter processed by the step S1 by using an acid solution to expose the cobalt on the subsurface, and then cleaning the hard alloy cutter by using clear water;
s3, preparing a mixed solution of copper sulfate and chromium sulfate for later use;
s4, placing the hard alloy cutter processed in the step S2 into the mixed solution of the step S3, then reacting in an ultrasonic environment, controlling the reaction time, and replacing until the subsurface cobalt is completely covered;
s5, preparing diamond powder suspension by using ethanol as a solvent, and placing the hard alloy cutter processed by the S4 into the suspension for crystal implantation in an ultrasonic environment to finish pretreatment.
2. The method as claimed in claim 1, wherein the Murakami reagent is etched for 20-30min in S1.
3. The pretreatment method of the hard alloy cutter for preparing the diamond coating according to claim 1, wherein in S2, the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide, and the volume ratio of the sulfuric acid to the hydrogen peroxide in the mixed solution is 2-4: 6-8.
4. The pretreatment method for preparing the hard alloy cutter with the diamond coating according to claim 3, wherein the volume ratio of sulfuric acid to hydrogen peroxide in the mixed solution is 3: 7.
5. The method of claim 1, wherein the acid solution is used to etch the tool for 4-7S in S2.
6. The pretreatment method for cemented carbide tools for producing diamond coatings according to claim 1, wherein in S3, the mass fraction of copper sulfate in the mixed solution is 1.4-2.2%, and the copper sulfate is copper sulfate pentahydrate; the mass fraction of the chromium sulfate is 0.3-0.6%, and the chromium sulfate is chromium sulfate pentahydrate.
7. The pretreatment method for preparing a diamond coated cemented carbide tool according to claim 1, wherein the power of the ultrasonic wave is 40-60W and the reaction time is 9-14min in S4.
8. The pretreatment method for preparing a diamond coated cemented carbide tool according to claim 1, wherein the ultrasonic wave has a power of 40-60W and a treatment time of 20-30min at S5.
9. Use of the method of pre-treatment of a cemented carbide tool according to any one of claims 1-8 in a low cobalt cemented carbide tool or a high cobalt cemented carbide tool.
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| WO2024050571A1 (en) | 2022-09-05 | 2024-03-14 | Carboncompetence Gmbh | Method for preparing a substrate coated with an intermediate layer and a diamond layer |
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