CN115041679A - Diamond surface modification treatment method and application - Google Patents
Diamond surface modification treatment method and application Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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Abstract
The invention provides a diamond surface modification treatment method and application, comprising the following steps: 1) mixing sodium chloride, active reaction metal powder and metal alloy powder to obtain mixed powder for surface modification, which is recorded as BSH powder; 2) mixing BSH powder and diamond powder to obtain diamond modified mixed powder, which is marked as DGH powder; 3) sequentially adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixed material with a sandwich-like layered structure before reaction; 4) firing the mixed material under a vacuum condition, and then cooling along with a furnace; the diamond powder with the surface modified is obtained through cleaning, ultrasonic treatment, drying and sieving. The invention has simple reaction conditions, controllable reaction process, convenient operation, quick reaction and low energy consumption, and can realize diamond surface modification at relatively low temperature. The modified diamond particles and the diamond tool can be prepared under the simple environment-friendly condition, and the diamond tool can be applied to the fields of machining and the like.
Description
Technical Field
The invention relates to the technical field of diamond surface treatment and products, in particular to a diamond surface modification treatment method and application.
Background
The diamond has many excellent characteristics of super hardness, low expansion, light weight, insulation and the like, so that the diamond can be widely applied to the fields of machinery, building materials, metallurgy and the like. At present, the artificial diamond replaces the majority of industrial diamond in the world, the granular diamond is an excellent grinding material, the application of the diamond granules for manufacturing various tools such as saw blades, drill bits and the like is more common, and the manufacturing mode mainly comprises embedding the diamond. The embedded diamond is fixed by using resin, ceramic or metal as a bonding agent, and finally prepared into different structures to meet different requirements.
In the working process of the diamond tool, the diamond is exposed on the surface of the tool after the metal blank is worn, and the comprehensive performance of the diamond tool is improved by means of the high hardness of the diamond. Because the diamond and most of matrix materials have higher interfacial energy, the bonding force between the diamond particles and the matrix materials is poorer, the diamond is easy to separate from a matrix and fall off when the diamond is subjected to cutting force, the service life and the processing efficiency of the diamond tool are greatly reduced, and the diamond tool cannot enter a high-end market.
In order to improve the comprehensive performance of diamond tools, a layer of metal or alloy is often coated on the surfaces of diamond particles by a physical or chemical method to reduce the interface energy between diamond and a matrix material, so that the diamond particles and a matrix can have better bonding force, and the falling of diamond in the working process of the diamond tool is reduced. In addition, the diamond surface modification metal layer also has a protection function, and can prevent the diamond particles from directly contacting with the outside, thereby preventing the diamond particles from graphitizing during high-temperature sintering; after the diamond particles are plated with metal, the hardness of the saw blade can be improved, so that the service performance of the diamond tool is improved.
With the progress of scientific research technology, the technology of diamond metallization is more and more, the types of coatings are continuously enriched, diamond tools are continuously optimized, and various diamond-coated tools are widely applied in industry. At present, chemical plating, vacuum evaporation, magnetron sputtering and the like are commonly used methods for the metallization of the surfaces of diamond particles at home and abroad. The methods have the problems that a metal layer formed on the surface of the diamond is physically combined with the diamond matrix, the combination performance between the diamond and matrix metal is not greatly improved, and the existing diamond surface metallization method has the problems of expensive equipment, complex preparation process, high preparation cost and the like and is difficult to produce in batches.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a diamond surface modification treatment method and application, which can be used for preparing modified diamond particles and a diamond tool under simple and environment-friendly conditions, wherein the diamond tool can be applied to the fields of machining and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a diamond surface modification treatment method comprises the following steps:
step 1, mixing and grinding sodium chloride, active reaction metal powder and metal alloy powder to obtain mixed powder for surface modification, which is recorded as BSH powder;
step 2, according to BSH powder: 10 parts of diamond powder: 1, weighing the raw materials, mixing and stirring to obtain diamond modified mixed powder which is marked as DGH powder;
and 3, sequentially adding the BSH powder, the DGH powder and the BSH powder into the crucible in sequence to form a mixed material A which is of a sandwich-like layered structure before reaction, wherein the BSH powder: DGH powder: the mass ratio of BSH powder is 1: 4: 1;
step 4, firing the mixed material A obtained in the step 3 under a vacuum condition, and cooling along with the furnace after firing; and cleaning and ultrasonically treating the cooled sample, drying and sieving to obtain the surface modified diamond powder.
Sodium chloride in the step 1: active reaction metal powder: the mass ratio of the metal alloy powder is 8-12: 0.8-2.0: 0.2; the active reaction metal powder is analytically pure, and the particle size is 1-10 mu m; the grain diameter of the metal alloy powder is 5 mu m; sodium chloride is analytically pure; the diamond powder is diamond single crystal powder which passes through 40 meshes to 50 meshes.
The active reaction metal powder is metal titanium or metal chromium; the metal alloy powder is Cu 85 Sn 15 And (3) pulverizing.
The grinding method in the step 1 comprises the following steps: stirring and grinding by using an agate mortar, and alternately grinding clockwise and anticlockwise for 3min for 1 h; the stirring treatment method in the step 2 comprises the following steps: stirring at the rotating speed of 200r/min for 10 min; the firing process in the step 4 comprises the following steps: the heating rate is 5 ℃/min, the firing temperature is 945 to 985 ℃, the temperature is kept for 60 to 90min after the target temperature is reached, and the vacuum degree is less than 0.05 Pa.
The cleaning method in the step 4 comprises the following steps: putting the cooled sample into deionized water, heating to 75-85 ℃, keeping for 1h, pouring the deionized water dissolved with sodium chloride, and repeating the cleaning method for 5 times;
the ultrasonic method comprises the following steps: putting the sample cleaned by the deionized water into absolute ethyl alcohol for ultrasonic treatment, wherein the ultrasonic treatment time is 20-30 min;
the drying condition is 100-120 ℃, and the drying time is 6 h.
The surface-modified diamond powder obtained by the method is applied to the preparation of diamond tool products.
Mixing the surface modified diamond powder with matrix metal, and performing dry pressing molding and hot pressing firing to obtain a diamond tool product.
The above-mentionedThe matrix metal includes: alloy powder for diamond tools, electrolytic copper powder, tin powder and ferrophosphorus powder; wherein the mass ratio of alloy powder, electrolytic copper powder, tin powder, ferrophosphorus powder and surface modified diamond for the diamond tool is 60:25:8:5: 0.6; the dry pressing molding adopts a four-column press for one-time dry pressing molding, and the molding pressure is 5-8 tons/cm 2 And sintering at 850-860 ℃ for 30-40 min in a bell jar furnace after molding to obtain the ceramic material.
The alloy powder, the electrolytic copper powder, the tin powder and the ferrophosphorus powder for the diamond tool are analytically pure, and the particle size is 1-10 mu m.
The alloy powder for the diamond tool is 65Mn powder.
The invention has the beneficial effects that:
1. the used diamond modified raw materials are low in price, are all commercial chemical reagents, do not need further purification and are environment-friendly.
2. The method has the advantages of simple reaction conditions, controllable reaction process, convenient operation, quick reaction and low energy consumption, and can realize diamond surface modification at relatively low temperature.
3. The diamond surface modification reaction device is simple, and only a simple tube furnace is adopted, so that the defects of high vacuum, high energy consumption, complex operation and the like of preparation methods such as vacuum evaporation, magnetron sputtering and the like are overcome.
4. The diamond surface modification and the diamond matrix are subjected to molten salt disproportionation reaction, active reaction metal powder diffusion, in-situ chemical reaction of the active reaction metal powder and the diamond and in-situ deposition of alloy, so that a diamond surface modification layer and the diamond matrix form chemical bonding, and an alloy layer formed on the surface of the prepared surface modified diamond particles has better bonding performance with the metal matrix.
5. By controlling the firing temperature, the heating rate, the heat preservation time and the formula, the thickness of the diamond surface modification layer and the generated new phase are controllable, the equipment for diamond surface modification is simple, only a crucible and an atmosphere high-temperature furnace are used, and batch production can be realized.
6. The diamond tool prepared by the invention has the advantages of more excellent hardness, cutting performance and the like.
Drawings
FIG. 1 is a diagram showing the macroscopic effects of diamond powder prepared in example 1 of the present invention before and after surface modification;
wherein, a, before treatment; b, after treatment;
FIG. 2 is an SEM image of a diamond surface after modification treatment prepared in example 1 of the present invention;
FIG. 3 is an EDS map of a diamond surface after a modification treatment prepared in example 1 of the present invention;
FIG. 4 is a macroscopic view of a diamond tool prepared in example 1 of the present invention;
FIG. 5 is an SEM image of the interface of a diamond tool produced in example 1 of the present invention;
wherein, a and b are diamond tools prepared by diamond with surface modification treatment; c. d, adopting a diamond tool prepared by diamond without surface modification treatment;
FIG. 6 is a diagram showing the macroscopic effect of diamond powder surface modification prepared in example 2 of the present invention;
FIG. 7 is an SEM image of a diamond surface after modification treatment prepared in example 2 of the present invention;
FIG. 8 is an EDS map of a diamond surface after a modification treatment prepared in example 2 of the present invention;
fig. 9 is a macroscopic view of a diamond tool prepared in example 2 of the present invention;
fig. 10 is an SEM image of an interface of a diamond tool prepared in example 2 of the present invention;
FIG. 11 is an SEM image of a diamond surface after modification treatment prepared in example 3 of the present invention;
fig. 12 is an SEM image of an interface of a diamond tool prepared in example 3 of the present invention;
fig. 13 is an SEM image of the diamond surface after the surface modification treatment prepared in example 4 of the present invention;
FIG. 14 is an SEM image of a diamond surface after modification treatment prepared in example 5 of the present invention;
fig. 15 is an SEM image of the diamond surface-modified according to example 6 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood and practical for those skilled in the art, the present invention is further described with reference to the following drawings and specific examples, which are not intended to limit the present invention.
The test methods in the following examples, which are not specifically described, were carried out according to conventional methods and conditions in the art, and the materials used were commercially available unless otherwise specified.
Wherein the active reaction metal powder (metal titanium or metal chromium) is analytically pure, and the particle size is 1-10 mu m; metal alloy powder (Cu) 85 Sn 15 Powder) particle size was 5 μm; sodium chloride is analytically pure; the diamond powder is diamond single crystal powder which passes through 40 meshes to 50 meshes.
The alloy powder (65Mn powder), the electrolytic copper powder, the tin powder and the ferrophosphorus powder for the diamond tool are analytically pure, and the particle size is 1-10 mu m.
Example 1
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metal titanium: cu 85 Sn 15 Powder 10: 1: weighing the raw materials according to the mass ratio of 0.2, mixing, stirring and grinding by using an agate mortar, wherein the grinding method comprises clockwise and anticlockwise alternate grinding, the alternate time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, which is recorded as BSH powder;
step 2, according to BSH powder: 10 parts of diamond powder: 1, weighing the raw materials, mixing, stirring at a rotating speed of 200r/min for 10min to obtain diamond modified mixed powder, and recording the diamond modified mixed powder as DGH powder;
and 3, sequentially adding the BSH powder, the DGH powder and the BSH powder into the crucible in sequence to form a mixed material A which is of a sandwich-like layered structure before reaction, wherein the BSH powder: DGH powder: the mass ratio of BSH powder is 1: 4: 1;
step 4, firing the mixed material A obtained in the step 3 under a vacuum condition, wherein the firing process comprises the steps of heating rate of 5 ℃/min, firing temperature of 950 ℃, heat preservation time of 80min and vacuum degree of less than 0.05Pa, and furnace cooling after firing;
putting the fired sample into deionized water, heating to 80 ℃, keeping the temperature for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample to repeatedly wash for 5 times; and putting the sample cleaned by the deionized water into absolute ethyl alcohol, drying after carrying out ultrasonic treatment for 20min under the drying condition of 110 ℃ for 6h, and sieving the dried sample by using a mesh sieve to obtain the surface modified diamond powder.
The method only adopts a simple tube furnace (firing process), and overcomes the defects of high vacuum, high energy consumption, complex operation and the like of preparation methods such as vacuum evaporation, magnetron sputtering and the like. The diamond surface modification and the diamond matrix are subjected to molten salt disproportionation reaction, active reaction metal powder diffusion, in-situ chemical reaction of the active reaction metal powder and the diamond and in-situ deposition of alloy, so that a diamond surface modification layer and the diamond matrix form chemical bonding, and an alloy layer formed on the surface of the prepared surface modified diamond particles has better bonding performance with the metal matrix.
The application comprises the following steps: mixing the surface gradient modified diamond powder prepared in the step 4 with a matrix metal to obtain a mixture B, wherein the matrix metal comprises: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of the 65Mn powder to the electrolytic copper powder to the tin powder to the ferrophosphorus powder to the surface modified diamond is 60:25:8:5: 0.6; placing the mixture B in a die, and performing one-step dry pressing molding by adopting a four-column press, wherein the molding pressure is 7 tons/cm 2 And sintering at 860 deg.c in a bell jar furnace for 30min to obtain the surface modified diamond saw blade.
According to the above-mentioned process, the diamond saw blade without surface treatment was obtained without adding the surface-modified diamond powder prepared in this example.
TABLE 1 comparison of Properties
As can be seen from Table 1, the Rockwell hardness of the diamond saw blade with the modified surface prepared by the present example was increased by 3.19% to 97HRB, compared with the diamond saw blade without the modified surface. The sawing experiment adopts the self-timing cutting equipment, the cutting rates of the diamond saw blade without surface treatment and the diamond saw blade with surface modification treatment prepared in the embodiment 1 are compared, the length of the material to be cut, namely the Wulian safflower granite, is 60cm, the thickness is 20mm, the shorter the time for cutting off the diamond saw blade with surface modification treatment prepared in the embodiment 1 is, the sharper the saw blade is, the higher the cutting rate is, and the average cutting rate of six times of cutting is improved by 19.17%.
Fig. 1 shows the macroscopic effect diagrams before and after the surface modification of the diamond powder prepared by the method of example 1, and as can be seen from fig. 1, the color of the diamond powder (the surface-modified diamond powder obtained in step 4) after the surface modification treatment by the process of this example is changed into black (see fig. 1b), and it can be preliminarily judged from the macroscopic color development that the coating rate of the surface-modified diamond powder prepared by the process of this example is high.
Fig. 2 shows an SEM image of the diamond surface-modified (surface-modified diamond powder obtained in step 4) prepared by the method of example 1, and it can be seen that a dense coating layer is formed on the diamond surface after the surface-modification treatment, and the coating layer has a scale-like structure of about 200 nm.
Fig. 3 shows an EDS (EDS) diagram of the diamond surface-modified diamond powder prepared by the method of example 1 (the surface-modified diamond powder obtained in step 4), and it can be seen from the EDS diagram that the diamond surface after the surface-modification mainly includes three elements of carbon, titanium, and copper, and the three elements are, by weight: 30.05 wt% of carbon, 67.99 wt% of titanium and 1.96 wt% of copper.
Fig. 4 shows a macroscopic view of the diamond tool (resulting surface-modified diamond saw blade) prepared by the method of example 1.
Fig. 5 is an SEM image of the interface of the diamond tool manufactured by the method of example 1, and it can be seen that the surface-treated diamond particles manufactured by the method of example 1 have no voids at the interface with the matrix metal (see fig. 5(a-b), and the resulting surface-modified diamond saw blade has good interfacial bonding), while the diamond tool manufactured by the diamond without the surface-modified diamond has large voids at the interface (see fig. 5(c-d), and the resulting diamond saw blade without the surface-modified diamond blade).
Example 2
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metallic chromium: cu 85 Sn 15 Powder 12: 2.0: weighing the raw materials according to the mass ratio of 0.2, mixing, stirring and grinding by using an agate mortar, wherein the grinding method comprises clockwise and anticlockwise alternate grinding, the alternate time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, which is recorded as BSH powder;
step 2, according to BSH powder: 15 parts of diamond powder: 1, weighing the raw materials, mixing, stirring at a rotating speed of 200r/min for 10min to obtain diamond modified mixed powder, and recording the diamond modified mixed powder as DGH powder;
and 3, sequentially adding the BSH powder, the DGH powder and the BSH powder into the crucible in sequence to form a mixed material A which is of a sandwich-like layered structure before reaction, wherein the BSH powder: DGH powder: the mass ratio of BSH powder is 1: 4: 1;
step 4, firing the mixed material A obtained in the step 3 under a vacuum condition, wherein the firing process comprises the steps of heating rate of 5 ℃/min, firing temperature of 945 ℃, heat preservation time of 90min and vacuum degree of less than 0.05Pa, and furnace cooling after firing;
putting the fired sample into deionized water, heating to 85 ℃, keeping the temperature for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample to repeatedly wash for 5 times; and putting the sample cleaned by the deionized water into absolute ethyl alcohol, drying after carrying out ultrasonic treatment for 20min under the drying condition of 120 ℃ for 6h, and sieving the dried sample by using a mesh sieve to obtain the surface modified diamond powder.
The application comprises the following steps: mixing the surface gradient modified diamond powder prepared in the step 4 with a matrix metal to obtain a mixture B, wherein the matrix metal comprises: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of the 65Mn powder to the electrolytic copper powder to the tin powder to the ferrophosphorus powder to the surface modified diamond is 60:25:8:5: 0.6; placing the mixture B in a die, and performing one-step dry pressing molding by adopting a four-column press, wherein the molding pressure is 5 tons/cm 2 Formed and then placed in a bell jar furnaceSintering at 850 deg.C for 30min to obtain the diamond saw blade with surface modified.
According to the above-mentioned process, the diamond saw blade without surface treatment was obtained without adding the surface-modified diamond powder prepared in this example.
TABLE 2 comparison of Properties
As can be seen from Table 2, the Rockwell hardness of the surface-modified diamond saw blade prepared in this example was improved by 2% to 95.88HRB, as compared with the diamond saw blade without surface treatment. The sawing experiment adopts the self-timing cutting equipment, the cutting rates of the diamond saw blade without surface treatment and the diamond saw blade with surface modification treatment prepared in the embodiment 2 are compared, the length of the material to be cut, namely the Wulian safflower granite, is 60cm, the thickness of the material is 20mm, the shorter the time for cutting off the diamond saw blade with surface modification treatment prepared in the embodiment 2 is, the sharper the saw blade is, the higher the cutting rate is, and the average cutting rate for six times of cutting is improved by 13.85%.
Fig. 6 shows a macroscopic effect diagram of the diamond powder prepared by the method of example 2 after surface modification, and as can be seen from fig. 6, the color of the diamond powder subjected to surface modification treatment by the process of this example changes to black, and it can be preliminarily determined from the macroscopic color development that the surface-modified diamond powder prepared by the process of this example has a high coating rate.
Fig. 7 shows an SEM image of the diamond surface-modified according to the method of example 2, and it can be seen that a dense coating layer is formed on the diamond surface after the surface modification.
Fig. 8 shows an EDS (EDS) diagram of the diamond surface modified by the method of example 2, and it can be seen that the diamond surface after the surface modification mainly includes three elements, namely, carbon, chromium, and copper, and the three elements are, by weight: 20.21 wt% of carbon, 79.54 wt% of chromium and 0.25 wt% of copper.
Fig. 9 shows a macroscopic view of the diamond tool produced by the method of example 2.
Fig. 10 is an SEM image of the interface of the diamond tool manufactured by the method of example 2, and it can be seen that the surface-treated diamond particles manufactured by the method of example 2 have no voids at the interface with the matrix metal, and the interface bonding property is good.
Example 3
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metal titanium: cu 85 Sn 15 Powder 10: 2.0: weighing the raw materials according to the mass ratio of 0.2, mixing, stirring and grinding by using an agate mortar, wherein the grinding method comprises clockwise and anticlockwise alternate grinding, the alternate time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, which is recorded as BSH powder;
step 2, according to BSH powder: 10 parts of diamond powder: 1, weighing the raw materials, mixing, stirring at a rotating speed of 200r/min for 10min to obtain diamond modified mixed powder, and recording the diamond modified mixed powder as DGH powder;
and 3, sequentially adding the BSH powder, the DGH powder and the BSH powder into the crucible in sequence to form a mixed material A which is of a sandwich-like layered structure before reaction, wherein the BSH powder: DGH powder: the mass ratio of BSH powder is 1: 4: 1;
step 4, firing the mixed material A obtained in the step 3 under a vacuum condition, wherein the firing process comprises the steps of heating rate of 5 ℃/min, firing temperature of 985 ℃, heat preservation time of 70min and vacuum degree of less than 0.05Pa, and furnace cooling after firing;
putting the fired sample into deionized water, heating to 75 ℃, keeping the temperature for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample to repeatedly wash for 5 times; and putting the sample cleaned by the deionized water into absolute ethyl alcohol, drying after carrying out ultrasonic treatment for 20min under the drying condition of 100 ℃ for 6h, and sieving the dried sample by using a mesh sieve to obtain the surface modified diamond powder.
The application comprises the following steps: mixing the surface gradient modified diamond powder prepared in the step 4 with matrix metal to obtain a mixture B, wherein the matrix metal comprises: 65Mn powder, electrolytic copper powder, tin powder, ferro-phosphorus powderThe mass ratio of 65Mn powder to electrolytic copper powder to tin powder to ferro-phosphorus powder to surface modified diamond is 60:25:8:5: 0.6; placing the mixture B in a die, and performing one-step dry pressing molding by adopting a four-column press, wherein the molding pressure is 5 tons/cm 2 And sintering at 850 deg.c for 30min in a bell jar furnace to obtain the surface modified diamond saw blade.
According to the above-mentioned process, the diamond saw blade without surface treatment was obtained without adding the surface-modified diamond powder prepared in this example.
TABLE 3 comparison of Properties
As can be seen from Table 3, the Rockwell hardness of the surface-modified diamond saw blade prepared in this example was increased by 2.12% to 96HRB, as compared with the diamond saw blade without surface treatment. The sawing test used an autonomous timing cutting device, comparing the cutting rates of the diamond saw blade without surface treatment and the diamond saw blade with surface modification treatment prepared in example 1, the length of the cut material, namely, the length of the material, namely, the material, and the material. The shorter the time taken for the surface-modified diamond saw blade prepared in example 3 to cut off once, the sharper the saw blade and the higher the cutting rate, the higher the average cutting rate of six cuts by 15.38%.
Fig. 11 shows an SEM image of the diamond surface-modified according to the method of example 3, and it can be seen that a dense coating layer is formed on the diamond surface after the surface modification.
Fig. 12 is an SEM image of the interface of the diamond tool manufactured by the method of example 3, and it can be seen that the surface-treated diamond particles manufactured by the method of example 3 have no voids at the interface with the matrix metal and have good interface bondability.
Example 4
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metallic chromium: cu 85 Sn 15 Powder 8: 0.8: weighing the raw materials according to the mass ratio of 0.2, mixing, stirring and grinding by using an agate mortar, wherein the grinding method comprises clockwise and anticlockwise alternate grinding, the alternate time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, which is recorded as BSH powder;
step 2, according to BSH powder: diamond powder 11: 1, weighing the raw materials, mixing, stirring at a rotating speed of 200r/min for 10min to obtain diamond modified mixed powder, and recording the diamond modified mixed powder as DGH powder;
and 3, sequentially adding the BSH powder, the DGH powder and the BSH powder into the crucible in sequence to form a mixed material A which is of a sandwich-like layered structure before reaction, wherein the BSH powder: DGH powder: the mass ratio of BSH powder is 1: 4: 1;
step 4, firing the mixed material A obtained in the step 3 under a vacuum condition, wherein the firing process comprises the steps of heating rate of 5 ℃/min, firing temperature of 945 ℃, heat preservation time of 80min, vacuum degree of less than 0.05Pa, and furnace cooling after firing;
putting the fired sample into deionized water, heating to 70 ℃, keeping the temperature for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample to repeatedly wash for 5 times; and putting the sample cleaned by the deionized water into absolute ethyl alcohol, drying after carrying out ultrasonic treatment for 20min under the drying condition of 110 ℃ for 6h, and sieving the dried sample by using a mesh sieve to obtain the surface modified diamond powder.
The application comprises the following steps: mixing the surface gradient modified diamond powder prepared in the step 4 with matrix metal to obtain a mixture B, wherein the matrix metal comprises: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of the 65Mn powder to the electrolytic copper powder to the tin powder to the ferrophosphorus powder to the surface modified diamond is 60:25:8:5: 0.6; placing the mixture B in a die, and performing one-step dry pressing molding by adopting a four-column press, wherein the molding pressure is 7 tons/cm 2 And sintering the formed diamond saw blade at 855 ℃ for 30min to obtain the diamond saw blade with the surface modified.
According to the above-mentioned process, the diamond saw blade without surface treatment was obtained without adding the surface-modified diamond powder prepared in this example.
TABLE 4 comparison of Properties
As can be seen from Table 4, the Rockwell hardness of the surface-modified diamond saw blade prepared by the example is improved by 2.65% and reaches 96.5HRB compared with the diamond saw blade without surface treatment. The sawing test used an autonomous timing cutting device, comparing the cutting rates of the diamond saw blade without surface treatment and the diamond saw blade with surface modification treatment prepared in this example 4, the length of the cut material, penthorum chinense pursh, safflower carthamus, was 60cm and the thickness was 20 mm. The shorter the time taken to cut off the surface-modified diamond saw blade prepared in example 4, the sharper the saw blade and the higher the cutting rate, which is 13.85% higher than the average cutting rate of six cuts.
Fig. 13 shows an SEM image of the diamond surface-modified according to the method of example 4, and it can be seen that a dense coating layer is formed on the diamond surface after the surface modification.
Example 5
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metallic chromium: cu 85 Sn 15 Powder 12: 2.0: weighing the raw materials according to the mass ratio of 0.2, mixing, stirring and grinding by using an agate mortar, wherein the grinding method comprises clockwise and anticlockwise alternate grinding, the alternate time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, which is recorded as BSH powder;
step 2, according to BSH powder: 15 parts of diamond powder: 1, weighing the raw materials, mixing, stirring at a rotating speed of 200r/min for 10min to obtain diamond modified mixed powder, and recording the diamond modified mixed powder as DGH powder;
and 3, sequentially adding the BSH powder, the DGH powder and the BSH powder into the crucible in sequence to form a mixed material A which is of a sandwich-like layered structure before reaction, wherein the BSH powder: DGH powder: the mass ratio of BSH powder is 1: 4: 1;
step 4, firing the mixed material A obtained in the step 3 under a vacuum condition, wherein the firing process comprises the steps of heating rate of 5 ℃/min, firing temperature of 955 ℃, heat preservation time of 80min and vacuum degree of less than 0.05Pa, and furnace cooling is carried out after firing is finished;
putting the fired sample into deionized water, heating to 85 ℃, keeping the temperature for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample to repeatedly wash for 5 times; and putting the sample cleaned by the deionized water into absolute ethyl alcohol, drying after carrying out ultrasonic treatment for 20min under the drying condition of 100 ℃ for 6h, and sieving the dried sample by using a mesh sieve to obtain the surface modified diamond powder.
The application comprises the following steps: mixing the surface gradient modified diamond powder prepared in the step 4 with matrix metal to obtain a mixture B, wherein the matrix metal comprises: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of the 65Mn powder to the electrolytic copper powder to the tin powder to the ferrophosphorus powder to the surface modified diamond is 60:25:8:5: 0.6; placing the mixture B in a die, and performing one-step dry pressing molding by adopting a four-column press, wherein the molding pressure is 5 tons/cm 2 And sintering at 850 deg.c for 30min in a bell jar furnace to obtain the surface modified diamond saw blade.
According to the above-mentioned process, the diamond saw blade without surface treatment was obtained without adding the surface-modified diamond powder prepared in this example.
TABLE 5 comparison of Properties
As can be seen from Table 5, the Rockwell hardness of the surface-modified diamond saw blade prepared by this example was improved by 2.12% to 96HRB, compared with the diamond saw blade without surface treatment. The sawing test used an autonomous timing cutting device, comparing the cutting rates of the diamond saw blade without surface treatment and the diamond saw blade with surface modification treatment prepared in example 5, the length of the cut material, namely, the length of the material, namely, the material, and the material, and the material. The shorter the time taken for the surface modified diamond saw blade prepared in example 5 to cut once, the sharper the saw blade and the higher the cutting rate, the more the average cutting rate increased by 11.54% for six cuts.
Fig. 14 shows an SEM image of the diamond surface-modified according to the method of example 5, and it can be seen that a dense coating layer is formed on the diamond surface after the surface modification.
Example 6
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metal titanium: cu 85 Sn 15 Powder 11: 1.1: weighing the raw materials according to the mass ratio of 0.2, mixing, stirring and grinding by using an agate mortar, wherein the grinding method comprises clockwise and anticlockwise alternate grinding, the alternate time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, which is recorded as BSH powder;
step 2, according to BSH powder: diamond powder 13: 1, weighing the raw materials, mixing, stirring at a rotating speed of 200r/min for 10min to obtain diamond modified mixed powder, and recording the diamond modified mixed powder as DGH powder;
and 3, sequentially adding the BSH powder, the DGH powder and the BSH powder into the crucible in sequence to form a mixed material A which is of a sandwich-like layered structure before reaction, wherein the BSH powder: DGH powder: the mass ratio of BSH powder is 1: 4: 1;
step 4, firing the mixed material A obtained in the step 3 under a vacuum condition, wherein the firing process comprises the steps of heating rate of 5 ℃/min, firing temperature of 985 ℃, heat preservation time of 60min and vacuum degree of less than 0.05Pa, and furnace cooling after firing;
putting the fired sample into deionized water, heating to 75 ℃, keeping the temperature for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample to repeatedly wash for 5 times; and putting the sample cleaned by the deionized water into absolute ethyl alcohol, drying after carrying out ultrasonic treatment for 20min under the drying condition of 100 ℃ for 6h, and sieving the dried sample by using a mesh sieve to obtain the surface modified diamond powder.
The application comprises the following steps: mixing the surface gradient modified diamond powder prepared in the step 4 with matrix metal to obtain a mixture B, wherein the matrix metal comprises: 65Mn powder, electrolytic copper powder, tin powder, ferrophosphorus powder, 65Mn powder electrolytic copperThe mass ratio of tin powder to ferrophosphorus powder to surface-modified diamond is 60:25:8:5: 0.6; placing the mixture B in a die, and performing one-step dry pressing molding by adopting a four-column press, wherein the molding pressure is 8 tons/cm 2 And sintering at 860 deg.c in a bell jar furnace for 30min to obtain the surface modified diamond saw blade.
According to the above-mentioned process, the diamond saw blade without surface treatment was obtained without adding the surface-modified diamond powder prepared in this example.
TABLE 6 comparison of properties
As can be seen from Table 6, the Rockwell hardness of the surface-modified diamond saw blade prepared in this example was improved by 3.0% to 96.82HRB, compared to the diamond saw blade without surface treatment. The sawing test used an autonomous timing cutting device, comparing the cutting rates of the diamond saw blade without surface treatment and the diamond saw blade with surface modification treatment prepared in this example 6, the length of the cut material, penthorum chinense pursh, safflower carthamus, was 60cm and the thickness was 20 mm. The shorter the time taken to cut off the surface modified diamond saw blade prepared in example 6, the sharper the saw blade and the higher the cutting rate, which is an improvement of 16.67% in the average cutting rate of six cuts.
Fig. 15 shows an SEM image of the diamond surface-modified surface prepared by the method of example 6, and it can be seen that a dense coating layer of a scale-like structure is formed on the diamond surface after the surface modification.
Claims (10)
1. A diamond surface modification treatment method is characterized by comprising the following steps:
step 1, mixing and grinding sodium chloride, active reaction metal powder and metal alloy powder to obtain mixed powder for surface modification, which is recorded as BSH powder;
step 2, according to BSH powder: 10 parts of diamond powder: 1, weighing the raw materials, mixing and stirring to obtain diamond modified mixed powder which is marked as DGH powder;
and 3, sequentially adding the BSH powder, the DGH powder and the BSH powder into the crucible in sequence to form a mixed material A which is of a sandwich-like layered structure before reaction, wherein the BSH powder: DGH powder: the mass ratio of BSH powder is 1: 4: 1;
step 4, firing the mixed material A obtained in the step 3 under a vacuum condition, and cooling along with the furnace after firing; and cleaning and ultrasonically treating the cooled sample, drying and sieving to obtain the surface modified diamond powder.
2. The method of claim 1, wherein the ratio of sodium chloride: active reaction metal powder: the mass ratio of the metal alloy powder is 8-12: 0.8-2.0: 0.2; the active reaction metal powder is analytically pure, and the particle size is 1-10 mu m; the grain diameter of the metal alloy powder is 5 mu m; sodium chloride is analytically pure; the diamond powder is diamond single crystal powder which passes through 40 meshes to 50 meshes.
3. The method of claim 2, wherein the reactive metal powder is metallic titanium or metallic chromium; the metal alloy powder is Cu 85 Sn 15 And (3) pulverizing.
4. The method of claim 1, wherein the grinding method in step 1 is: stirring and grinding by using an agate mortar, and alternately grinding clockwise and anticlockwise for 3min for 1 h; the stirring treatment method in the step 2 comprises the following steps: stirring at the rotating speed of 200r/min for 10 min; the firing process in the step 4 comprises the following steps: the heating rate is 5 ℃/min, the firing temperature is 945 to 985 ℃, the temperature is kept for 60 to 90min after the target temperature is reached, and the vacuum degree is less than 0.05 Pa.
5. The method of claim 1, wherein the cleaning method in step 4 is: putting the cooled sample into deionized water, heating to 75-85 ℃, keeping for 1h, pouring the deionized water dissolved with sodium chloride, and repeating the cleaning method for 5 times;
the ultrasonic method comprises the following steps: putting the sample cleaned by the deionized water into absolute ethyl alcohol for ultrasonic treatment, wherein the ultrasonic treatment time is 20-30 min;
the drying condition is 100-120 ℃, and the drying time is 6 h.
6. Use of the surface modified diamond powder obtained by the method of claim 1 in the manufacture of diamond tool products.
7. The use according to claim 6, wherein the surface modified diamond powder is mixed with a matrix metal and subjected to dry pressing, hot pressing and firing to obtain a diamond tool product.
8. Use according to claim 7, wherein said matrix metal comprises: alloy powder for diamond tools, electrolytic copper powder, tin powder and ferrophosphorus powder; wherein the mass ratio of alloy powder, electrolytic copper powder, tin powder, ferrophosphorus powder and surface modified diamond for the diamond tool is 60:25:8:5: 0.6; the dry pressing molding adopts a four-column press for one-time dry pressing molding, and the molding pressure is 5-8 tons/cm 2 And sintering at 850-860 ℃ for 30-40 min in a bell jar furnace after molding to obtain the ceramic material.
9. The use according to claim 8, wherein the alloy powder for diamond tools, the electrolytic copper powder, the tin powder and the ferrophosphorus powder are analytically pure powders, and the particle sizes are all 1 to 10 μm.
10. The use of claim 9, wherein the alloy powder for diamond tools is 65Mn powder.
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