CN115041679B - 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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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, and marking the mixed powder as BSH powder; 2) Mixing BSH powder and diamond powder to obtain diamond modified mixed powder, and marking the diamond modified mixed powder 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 vacuum, and then cooling along with a furnace; cleaning, ultrasonic processing, drying and sieving to obtain the surface modified diamond powder. 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. 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 a plurality of excellent characteristics of super-hard, 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 has replaced most industrial diamond in the world, the granular diamond is an excellent grinding material, the application of using diamond particles to manufacture various saw blades, drill bits and other tools is more common, and the manufacturing mode mainly comprises diamond inlaying. The diamond is fixed by using resin, ceramic or metal as a binding agent, and finally different structures are prepared to meet different requirements.
In the working process of the diamond tool, after the metal blank is worn, diamond is exposed on the surface of the tool, and the comprehensive performance of the diamond tool is improved by virtue of the high hardness of the diamond. Because of the high interface energy between diamond and most matrix materials, the binding force between diamond particles and matrix materials is poor, and the diamond is easy to separate from the matrix and fall off when being subjected to cutting force, so that 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 the diamond tool, a layer of metal or alloy is coated on the surface of diamond particles by adopting a physical or chemical method to reduce the interface energy between diamond and a matrix material, so that the diamond tool has better binding force with a matrix and the falling-off of the diamond in the working process of the diamond tool is reduced. In addition, the diamond surface modified metal layer has a protective effect, and can prevent diamond particles from directly contacting with the outside, so that the diamond particles are prevented from graphitizing during high-temperature sintering; the hardness of the saw blade can be improved after the diamond particles are plated with metal, 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 plating variety is continuously rich, the diamond tool is also continuously optimized, and various diamond plating tools are widely applied to industry. At present, common methods for metallizing the surfaces of diamond particles at home and abroad include chemical plating, vacuum evaporation, magnetron sputtering and the like. The method has the advantages that the metal layer formed on the diamond surface is physically combined with the diamond matrix, the combination property between the diamond and matrix metal is not greatly improved, in addition, the existing diamond surface metallization method has the problems of expensive equipment, complex preparation flow, high preparation cost and the like, and the mass production is difficult.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a diamond surface modification treatment method and application, and diamond particles and diamond tools with modification can be prepared under simple and environment-friendly conditions, and the diamond tools can be applied to the fields of machining and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
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, and marking the mixed powder as BSH powder;
step 2, according to BSH powder: diamond powder = 10:1, weighing the raw materials, mixing and stirring to obtain diamond modified mixed powder, and marking the diamond modified mixed powder as DGH powder;
step 3, adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixture A with a sandwich-like layered structure before reaction, wherein the BSH powder is prepared by the following steps: DGH powder: the mass ratio of the BSH powder is 1:4:1, a step of;
step 4, firing the mixed material A in the step 3 under a vacuum condition, and cooling along with a furnace after the firing is finished; and (3) cleaning and ultrasonically treating the cooled sample, drying and sieving to obtain the surface-modified diamond powder.
Sodium chloride in the step 1: reactive metal powder: the mass ratio of the metal alloy powder is 8-12: 0.8 to 2.0:0.2; the active reaction metal powder is analytically pure and has the particle size of 1-10 mu m; the particle size of the metal alloy powder is 5 mu m; sodium chloride is analytically pure; the diamond powder is diamond monocrystal powder with 40-50 meshes.
The active reaction metal powder is metallic titanium or metallic chromium; the metal alloy powder is Cu 85 Sn 15 And (5) powder.
The grinding method in the step 1 is as follows: stirring and grinding by an agate mortar, wherein clockwise and anticlockwise grinding is performed alternately, the alternating time is 3min, and the grinding time is 1h; the stirring treatment method in the step 2 is as follows: stirring at 200r/min for 10min; the firing process in the step 4 is as follows: heating rate is 5 ℃/min, firing temperature is 945-985 ℃, heat preservation is carried out for 60-90 min after reaching target temperature, and vacuum degree is less than 0.05Pa.
The cleaning method in the step 4 is as follows: putting the cooled sample into deionized water, heating to 75-85 ℃ and 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 deionized water into absolute ethyl alcohol for ultrasonic treatment for 20-30 min;
the drying condition is 100-120 ℃ and the drying time is 6h.
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, hot pressing and firing to obtain the diamond tool product.
The carcass metal comprises: alloy powder, electrolytic copper powder, tin powder and ferrophosphorus powder for diamond tools; wherein the mass ratio of the alloy powder for the diamond tool 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; the dry-pressing molding adopts a four-column press for one-step dry-pressing molding, and the molding pressure is 5-8 tons/cm 2 And (5) after molding, placing the molded product in a bell jar furnace for sintering at a high temperature of 850-860 ℃ for 30-40 min, and obtaining the ceramic material.
The alloy powder, the electrolytic copper powder, the tin powder and the phosphorus iron powder for the diamond tool are all 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, only adopts a simple tube furnace, and overcomes the defects of high vacuum, high energy consumption, complex operation and the like of the preparation methods such as vacuum evaporation, magnetron sputtering and the like.
4. The diamond surface modification and the diamond matrix are subjected to molten salt disproportionation reaction, active reaction metal powder diffusion, active reaction metal powder and diamond in-situ chemical reaction and alloy in-situ deposition process, so that a chemical bond is formed between the diamond surface modification layer and the diamond matrix, and the prepared alloy layer formed on the surface of the surface modified diamond particle has better bonding performance with the metal matrix.
5. The thickness of the diamond surface modification layer and the generated new phase are controllable by controlling the firing temperature, the heating rate, the heat preservation time and the formula, and the equipment for diamond surface modification is simple and can be produced in batch only by using a crucible and an atmosphere high-temperature furnace.
6. The diamond tool prepared by the method has the advantages of more excellent hardness, cutting performance and the like.
Drawings
FIG. 1 is a graph showing 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 after the diamond surface modification treatment according to example 1 of the present invention;
FIG. 3 is an EDS chart after the diamond surface modification treatment prepared in example 1 of the present invention;
FIG. 4 is a macroscopic view of a diamond tool prepared according to example 1 of the present invention;
FIG. 5 is an SEM image of a diamond tool made in example 1 of the invention;
wherein, a and b are diamond tools prepared by adopting diamond with surface modification treatment; c. d, a diamond tool prepared by using diamond without surface modification treatment;
FIG. 6 is a graph showing macroscopic effects of the diamond powder prepared in example 2 of the present invention after surface modification;
FIG. 7 is an SEM image after the diamond surface modification treatment according to example 2 of the present invention;
FIG. 8 is an EDS chart of the diamond surface modification treatment prepared in example 2 of the present invention;
FIG. 9 is a macroscopic view of a diamond tool made in accordance with example 2 of the present invention;
FIG. 10 is an SEM image of a diamond tool made according to example 2 of the invention;
FIG. 11 is an SEM image after the diamond surface modification treatment according to example 3 of the present invention;
FIG. 12 is an SEM image of a diamond tool made according to example 3 of the invention;
FIG. 13 is an SEM image after the diamond surface modification treatment according to example 4 of the present invention;
FIG. 14 is an SEM image after the diamond surface modification treatment according to example 5 of the present invention;
fig. 15 is an SEM image of the diamond surface modification treatment prepared in example 6 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the accompanying drawings and specific examples, but the examples are not intended to limit the present invention.
The test procedures, which are not specifically described in the examples below, were carried out according to methods and conditions conventional in the art, and the materials used, unless otherwise specified, were commercially available.
Wherein, the active reaction metal powder (metallic titanium or metallic chromium) is analytically pure, and the particle size is 1-10 mu m; metal alloy powder (Cu) 85 Sn 15 Powder) having a particle size of 5 μm; sodium chloride is analytically pure; the diamond powder is diamond monocrystal powder with 40-50 meshes.
The alloy powder (65 Mn powder), electrolytic copper powder, tin powder and phosphorus iron powder for the diamond tool are all 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: metallic titanium: cu (Cu) 85 Sn 15 Powder = 10:1:0.2, weighing the raw materials, mixing, stirring and grinding by an agate mortar, wherein the grinding method is that clockwise and anticlockwise grinding is performed alternately, the alternating time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, and the mixed powder is marked as BSH powder;
step 2, according to BSH powder: diamond powder = 10:1, weighing the raw materials according to the mass ratio, mixing and stirring for 10min at the rotating speed of 200r/min to obtain diamond modified mixed powder, and marking the diamond modified mixed powder as DGH powder;
step 3, adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixture A with a sandwich-like layered structure before reaction, wherein the BSH powder is prepared by the following steps: DGH powder: the mass ratio of the BSH powder is 1:4:1, a step of;
step 4, firing the mixed material A in the step 3 under vacuum condition, wherein the firing process is that the heating rate is 5 ℃/min, the firing temperature is 950 ℃, the heat preservation time is 80min, the vacuum degree is less than 0.05Pa, and cooling along with the furnace after the firing is finished;
placing the fired sample into deionized water, heating to 80 ℃ for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample for repeated cleaning for 5 times; and (3) putting the sample cleaned by deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 20min, drying at 110 ℃ for 6h, and sieving the dried sample through 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 the 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, active reaction metal powder and diamond in-situ chemical reaction and alloy in-situ deposition process, so that a chemical bond is formed between the diamond surface modification layer and the diamond matrix, and the prepared alloy layer formed on the surface of the surface modified diamond particle has better bonding performance with the metal matrix.
Application: surface gradient modified diamond prepared in step 4Mixing the powder 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 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 into a mould, and performing dry press molding by adopting a four-column press at one time, wherein the molding pressure is 7 tons/cm 2 And (3) after molding, placing the diamond saw blade in a bell jar furnace for high-temperature sintering at 860 ℃ for 30min, and obtaining the diamond saw blade with the surface modified treatment.
According to the above process method, the diamond saw blade without surface treatment is obtained without adding the surface-modified diamond powder prepared in this example.
Table 1 performance comparison
As is clear from Table 1, the Rockwell hardness of the surface-modified diamond saw blade prepared in this example was improved by 3.19% to 97HRB as compared with the diamond saw blade without surface treatment. The sawing experiment adopts autonomous timing cutting equipment, and the cutting rates of an untreated diamond saw blade and the surface modification treatment diamond saw blade prepared in the embodiment 1 are compared, the length of a material to be cut, namely five-lotus red granite, is 60cm, the thickness of the material to be cut is 20mm, the shorter the time for cutting the surface modification treatment diamond saw blade prepared in the embodiment 1 once, the sharper the saw blade is, the higher the cutting rate is, and the average cutting rate for six times of cutting is increased by 19.17%.
Fig. 1 shows macroscopic effects before and after surface modification of diamond powder prepared by the method of example 1, and as can be seen from fig. 1, the diamond powder prepared by the method of example has a high coating rate, which can be primarily judged from macroscopic color development, after the diamond surface modification treatment (the surface modified diamond powder obtained in step 4) is changed into black (see fig. 1 b).
Fig. 2 shows an SEM image of the diamond surface-modified diamond powder obtained in step 4 after the diamond surface-modification treatment prepared in example 1, and it is clear from the figure that the diamond surface after the surface-modification treatment forms a dense coating layer composed of a scale-like structure of about 200 nm.
Fig. 3 shows EDS diagrams of diamond surface modification treatment (surface modified diamond powder obtained in step 4) prepared by the method of example 1, and the surface modified diamond surface mainly includes three elements of carbon, titanium and copper, wherein the weight percentages of the three elements are respectively: 30.05wt% of carbon, 67.99wt% of titanium and 1.96wt% of copper.
Fig. 4 shows a macroscopic view of a diamond tool (resulting surface-modified diamond saw blade) prepared by the method of example 1.
Fig. 5 shows an SEM image of the interface of the diamond tool prepared by the method of example 1, and it is understood that the surface-treated diamond particles prepared by the method of example 1 have no voids at the metal interface with the matrix (see fig. 5 (a-b), the resulting surface-modified diamond saw blade) has good interfacial bonding, and the diamond tool prepared by the diamond without surface modification has larger voids (see fig. 5 (c-d), the resulting diamond saw blade without surface modification).
Example 2
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metal chromium: cu (Cu) 85 Sn 15 Powder = 12:2.0:0.2, weighing the raw materials, mixing, stirring and grinding by an agate mortar, wherein the grinding method is that clockwise and anticlockwise grinding is performed alternately, the alternating time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, and the mixed powder is marked as BSH powder;
step 2, according to BSH powder: diamond powder = 15:1, weighing the raw materials according to the mass ratio, mixing and stirring for 10min at the rotating speed of 200r/min to obtain diamond modified mixed powder, and marking the diamond modified mixed powder as DGH powder;
step 3, adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixture A with a sandwich-like layered structure before reaction, wherein the BSH powder is prepared by the following steps: DGH powder: the mass ratio of the BSH powder is 1:4:1, a step of;
step 4, firing the mixed material A in the step 3 under vacuum condition, wherein the firing process is that the heating rate is 5 ℃/min, the firing temperature is 945 ℃, the heat preservation time is 90min, the vacuum degree is less than 0.05Pa, and cooling along with the furnace after the firing is finished;
placing the fired sample into deionized water, heating to 85 ℃ for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample for repeated cleaning for 5 times; and (3) putting the sample cleaned by deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 20min, drying at 120 ℃ for 6h, and sieving the dried sample through a mesh sieve to obtain the surface modified diamond powder.
Application: 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 the following components: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of 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 into a mould, and performing dry press molding by adopting a four-column press at one time, wherein the molding pressure is 5 tons/cm 2 And (3) after molding, placing the diamond saw blade in a bell jar furnace for high-temperature sintering at 850 ℃ for 30min, and obtaining the diamond saw blade with the surface modified treatment.
According to the above process method, the diamond saw blade without surface treatment is obtained without adding the surface-modified diamond powder prepared in this example.
Table 2 performance comparison
As can be seen from table 2, the surface-modified diamond saw blade prepared by this example has a 2% increase in rockwell hardness to 95.88HRB as compared to the non-surface-modified diamond saw blade. The sawing experiment adopts autonomous timing cutting equipment, and the cutting rates of an untreated diamond saw blade and the surface modification treatment diamond saw blade prepared in the embodiment 2 are compared, the length of a material to be cut, namely five-lotus red granite, is 60cm, the thickness of the material to be cut is 20mm, the shorter the time for cutting the surface modification treatment diamond saw blade prepared in the embodiment 2 once, the sharper the saw blade is, the higher the cutting rate is, and the average cutting rate for cutting six times 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 diamond powder prepared by the process of this example has a high coating rate, and the surface modification diamond powder prepared by the process of this example can be primarily judged from macroscopic color.
Fig. 7 shows SEM images of the diamond surface modification prepared by the method of example 2, and it is understood that a dense coating layer is formed on the diamond surface after the surface modification.
Fig. 8 shows EDS diagrams after the surface modification treatment of the diamond prepared by the method of example 2, and the surface modification treatment of the diamond mainly includes three elements including carbon, chromium and copper, wherein the weight percentages of the three elements are as follows: 20.21wt% of carbon, 79.54wt% of chromium and 0.25wt% of copper.
Fig. 9 shows a macroscopic view of a diamond tool prepared by the method of example 2.
Fig. 10 shows an SEM image of the interface of the diamond tool prepared by the method of example 2, and it can be seen from the figure that the surface-treated diamond particles prepared by the method of example 2 have no void at the metal interface of the matrix, and have good interface bonding.
Example 3
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metallic titanium: cu (Cu) 85 Sn 15 Powder = 10:2.0:0.2, weighing the raw materials, mixing, stirring and grinding by an agate mortar, wherein the grinding method is that clockwise and anticlockwise grinding is performed alternately, the alternating time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, and the mixed powder is marked as BSH powder;
step 2, according to BSH powder: diamond powder = 10:1, weighing the raw materials according to the mass ratio, mixing and stirring for 10min at the rotating speed of 200r/min to obtain diamond modified mixed powder, and marking the diamond modified mixed powder as DGH powder;
step 3, adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixture A with a sandwich-like layered structure before reaction, wherein the BSH powder is prepared by the following steps: DGH powder: the mass ratio of the BSH powder is 1:4:1, a step of;
step 4, firing the mixed material A in the step 3 under vacuum condition, wherein the firing process is that the heating rate is 5 ℃/min, the firing temperature is 985 ℃, the heat preservation time is 70min, the vacuum degree is less than 0.05Pa, and cooling along with the furnace after the firing is finished;
placing the fired sample into deionized water, heating to 75 ℃ for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample for repeated cleaning for 5 times; and (3) putting the sample cleaned by deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 20min, drying at 100 ℃ for 6h, and sieving the dried sample through a mesh sieve to obtain the surface modified diamond powder.
Application: 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 the following components: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of 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 into a mould, and performing dry press molding by adopting a four-column press at one time, wherein the molding pressure is 5 tons/cm 2 And (3) after molding, placing the diamond saw blade in a bell jar furnace for high-temperature sintering at 850 ℃ for 30min, and obtaining the diamond saw blade with the surface modified treatment.
According to the above process method, the diamond saw blade without surface treatment is obtained without adding the surface-modified diamond powder prepared in this example.
Table 3 performance comparison
As can be seen from Table 3, the surface-modified diamond saw blade prepared in this example has a Rockwell hardness increased by 2.12% and reached 96HRB as compared with the non-surface-modified diamond saw blade. The sawing experiment adopts an autonomous timing cutting device, and the cutting rates of the non-surface-treated diamond saw blade and the surface-modified diamond saw blade prepared by adopting the embodiment 1 are compared, wherein the length of the material to be cut, namely the five-lotus red granite, is 60cm, and the thickness of the material to be cut is 20mm. The shorter the time it takes for the surface modification treatment diamond saw blade prepared in this example 3 to cut once, the sharper the saw blade, and the higher the cutting rate, the average cutting rate of six cuts increased by 15.38%.
Fig. 11 shows SEM images of the diamond surface modification prepared by the method of example 3, and it is understood that the diamond surface modification forms a dense coating layer.
Fig. 12 shows an SEM image of the interface of the diamond tool prepared by the method of example 3, and it is clear from the figure that the surface-treated diamond particles prepared by the method of example 3 have no void at the metal interface of the matrix, and the interface bonding property is good.
Example 4
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metal chromium: cu (Cu) 85 Sn 15 Powder = 8:0.8:0.2, weighing the raw materials, mixing, stirring and grinding by an agate mortar, wherein the grinding method is that clockwise and anticlockwise grinding is performed alternately, the alternating time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, and the mixed powder is marked as BSH powder;
step 2, according to BSH powder: diamond powder = 11:1, weighing the raw materials according to the mass ratio, mixing and stirring for 10min at the rotating speed of 200r/min to obtain diamond modified mixed powder, and marking the diamond modified mixed powder as DGH powder;
step 3, adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixture A with a sandwich-like layered structure before reaction, wherein the BSH powder is prepared by the following steps: DGH powder: the mass ratio of the BSH powder is 1:4:1, a step of;
step 4, firing the mixed material A in the step 3 under vacuum condition, wherein the firing process is that the heating rate is 5 ℃/min, the firing temperature is 945 ℃, the heat preservation time is 80min, the vacuum degree is less than 0.05Pa, and cooling along with the furnace after the firing is finished;
placing the fired sample into deionized water, heating to 70 ℃ for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample for repeated cleaning for 5 times; and (3) putting the sample cleaned by deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 20min, drying at 110 ℃ for 6h, and sieving the dried sample through a mesh sieve to obtain the surface modified diamond powder.
Application: 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 the following components: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of 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 into a mould, and performing dry press molding by adopting a four-column press at one time, wherein the molding pressure is 7 tons/cm 2 And (5) after molding, placing the diamond saw blade in a bell jar furnace for sintering at a high temperature of 855 ℃ for 30min to obtain the diamond saw blade with the surface modified treatment.
According to the above process method, the diamond saw blade without surface treatment is obtained without adding the surface-modified diamond powder prepared in this example.
Table 4 performance comparison
As can be seen from Table 4, the Rockwell hardness of the surface-modified diamond saw blade prepared by this example was improved by 2.65% as compared with that of the non-surface-modified diamond saw blade, and reached to 96.5HRB. The sawing experiment adopts an autonomous timing cutting device, and the cutting rates of the non-surface-treated diamond saw blade and the surface-modified treated diamond saw blade prepared by adopting the embodiment 4 are compared, wherein the length of the material to be cut, namely the five-lotus red granite, is 60cm, and the thickness of the material to be cut is 20mm. The shorter the time it takes for the surface modification treatment diamond saw blade prepared in this example 4 to cut once, the sharper the saw blade, and the higher the cutting rate, the average cutting rate of six cuts increased by 13.85%.
Fig. 13 shows SEM images of the diamond surface modification prepared by the method of example 4, and it is understood that the diamond surface modification forms a dense coating layer.
Example 5
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metal chromium: cu (Cu) 85 Sn 15 Powder = 12:2.0:0.2, weighing the raw materials, mixing, stirring and grinding by an agate mortar, wherein the grinding method is that clockwise and anticlockwise grinding is performed alternately, the alternating time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, and the mixed powder is marked as BSH powder;
step 2, according to BSH powder: diamond powder = 15:1, weighing the raw materials according to the mass ratio, mixing and stirring for 10min at the rotating speed of 200r/min to obtain diamond modified mixed powder, and marking the diamond modified mixed powder as DGH powder;
step 3, adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixture A with a sandwich-like layered structure before reaction, wherein the BSH powder is prepared by the following steps: DGH powder: the mass ratio of the BSH powder is 1:4:1, a step of;
step 4, firing the mixed material A in the step 3 under vacuum condition, wherein the firing process is that the heating rate is 5 ℃/min, the firing temperature is 955 ℃, the heat preservation time is 80min, the vacuum degree is less than 0.05Pa, and cooling along with the furnace after the firing is finished;
placing the fired sample into deionized water, heating to 85 ℃ for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample for repeated cleaning for 5 times; and (3) putting the sample cleaned by deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 20min, drying at 100 ℃ for 6h, and sieving the dried sample through a mesh sieve to obtain the surface modified diamond powder.
Application: 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 the following components: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of 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 into a mould, and performing dry press molding by adopting a four-column press at one time, wherein the molding pressure is 5 tons/cm 2 After molding, placing the diamond saw blade in a bell jar furnace for high-temperature sintering at 850 ℃ for 30min to obtain the diamond saw blade with surface modified treatment。
According to the above process method, the diamond saw blade without surface treatment is obtained without adding the surface-modified diamond powder prepared in this example.
Table 5 performance comparison
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% as compared with that of the non-surface-modified diamond saw blade, reaching 96HRB. The sawing experiment adopts an autonomous timing cutting device, and the cutting rates of the non-surface-treated diamond saw blade and the surface-modified diamond saw blade prepared by adopting the embodiment 5 are compared, wherein the length of the material to be cut, namely the five-lotus red granite, is 60cm, and the thickness of the material to be cut is 20mm. The shorter the time it takes for the surface modification treatment diamond saw blade prepared in this example 5 to cut once, the sharper the saw blade, and the higher the cutting rate, the average cutting rate of six cuts increased by 11.54%.
Fig. 14 shows SEM images of the diamond surface modification prepared by the method of example 5, and it is understood that the diamond surface modification forms a dense coating layer.
Example 6
A diamond surface modification treatment method comprises the following steps:
step 1, according to sodium chloride: metallic titanium: cu (Cu) 85 Sn 15 Powder = 11:1.1:0.2, weighing the raw materials, mixing, stirring and grinding by an agate mortar, wherein the grinding method is that clockwise and anticlockwise grinding is performed alternately, the alternating time is 3min, and the grinding time is 1h, so as to obtain mixed powder for surface modification, and the mixed powder is marked as BSH powder;
step 2, according to BSH powder: diamond powder=13: 1, weighing the raw materials according to the mass ratio, mixing and stirring for 10min at the rotating speed of 200r/min to obtain diamond modified mixed powder, and marking the diamond modified mixed powder as DGH powder;
step 3, adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixture A with a sandwich-like layered structure before reaction, wherein the BSH powder is prepared by the following steps: DGH powder: the mass ratio of the BSH powder is 1:4:1, a step of;
step 4, firing the mixed material A in the step 3 under vacuum condition, wherein the firing process is that the heating rate is 5 ℃/min, the firing temperature is 985 ℃, the heat preservation time is 60min, the vacuum degree is less than 0.05Pa, and cooling along with the furnace after the firing is finished;
placing the fired sample into deionized water, heating to 75 ℃ for 1h, pouring the deionized water dissolved with sodium chloride, and continuously adding the deionized water into the sample for repeated cleaning for 5 times; and (3) putting the sample cleaned by deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 20min, drying at 100 ℃ for 6h, and sieving the dried sample through a mesh sieve to obtain the surface modified diamond powder.
Application: 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 the following components: 65Mn powder, electrolytic copper powder, tin powder and ferrophosphorus powder, wherein the mass ratio of 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 into a mould, and performing dry press molding by adopting a four-column press at one time, wherein the molding pressure is 8 tons/cm 2 And (3) after molding, placing the diamond saw blade in a bell jar furnace for high-temperature sintering at 860 ℃ for 30min, and obtaining the diamond saw blade with the surface modified treatment.
According to the above process method, the diamond saw blade without surface treatment is obtained without adding the surface-modified diamond powder prepared in this example.
Table 6 performance comparison
As can be seen from Table 6, the Rockwell hardness of the surface-modified diamond saw blade prepared by this example was improved by 3.0% as compared with that of the non-surface-modified diamond saw blade, reaching 96.82HRB. The sawing experiment adopts an autonomous timing cutting device, and the cutting rates of an untreated diamond saw blade and a surface modification treated diamond saw blade prepared by adopting the embodiment 6 are compared, wherein the length of the material to be cut, namely the five-lotus red granite, is 60cm, and the thickness of the material to be cut is 20mm. The shorter the time it takes for the surface modification treatment diamond saw blade prepared in this example 6 to cut once, the sharper the saw blade, and the higher the cutting rate, the average cutting rate of six cuts increased by 16.67%.
Fig. 15 shows SEM images of the surface modified diamond surface prepared by the method of example 6, and it can be seen that the surface modified diamond surface forms a dense scale structure coating.
Claims (9)
1. The diamond surface modification treatment method is characterized by comprising the following steps of:
step 1, mixing and grinding sodium chloride, active reaction metal powder and metal alloy powder to obtain mixed powder for surface modification, and marking the mixed powder as BSH powder;
the sodium chloride: reactive metal powder: the mass ratio of the metal alloy powder is 8-12: 0.8-2.0: 0.2; the particle size of the active reaction metal powder is 1-10 mu m; the particle size of the metal alloy powder is 5 mu m; diamond powder is diamond monocrystal powder with 40-50 meshes; the active reaction metal powder is metallic titanium or metallic chromium; the metal alloy powder is Cu 85 Sn 15 Powder;
step 2, according to BSH powder: diamond powder = 10:1, weighing the raw materials, mixing and stirring to obtain diamond modified mixed powder, and marking the diamond modified mixed powder as DGH powder;
step 3, adding BSH powder, DGH powder and BSH powder into a crucible in sequence to form a mixture A with a sandwich-like layered structure before reaction, wherein the BSH powder is prepared by the following steps: DGH powder: the mass ratio of the BSH powder is 1:4:1, a step of;
step 4, firing the mixed material A in the step 3 under a vacuum condition, and cooling along with a furnace after the firing is finished; and (3) 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 reactive metal powder is analytically pure and the sodium chloride is analytically pure.
3. The method according to claim 1, wherein the grinding method in step 1 is: stirring and grinding by an agate mortar, wherein clockwise and anticlockwise grinding is performed alternately, the alternating time is 3min, and the grinding time is 1h; the stirring treatment method in the step 2 is as follows: stirring at 200r/min for 10min; the firing process in the step 4 is as follows: heating rate is 5 ℃/min, firing temperature is 945-985 ℃, heat preservation is carried out for 60-90 min after target temperature is reached, and vacuum degree is smaller than 0.05Pa.
4. The method according to claim 1, wherein the cleaning method in step 4 is: placing the cooled sample into deionized water, heating to 75-85 ℃ and keeping the temperature at 1-h, 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 deionized water into absolute ethyl alcohol for ultrasonic treatment, wherein the ultrasonic time is 20-30 min;
the drying condition is 100-120 ℃ and the drying time is 6h.
5. Use of surface modified diamond powder obtained by the method of claim 1 in the preparation of diamond tool products.
6. The method according to claim 5, wherein the diamond tool product is obtained by mixing surface-modified diamond powder with a matrix metal, dry-pressing, hot-pressing and firing.
7. The use of claim 6, wherein the carcass metal comprises: alloy powder, electrolytic copper powder, tin powder and ferrophosphorus powder for diamond tools; wherein the mass ratio of the alloy powder for the diamond tool 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; 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 After molding, placing the mixture in a bell jar furnace for high-temperature sintering at 850-860 ℃ for 30-40 min, thus obtainingObtaining the product.
8. The use according to claim 7, wherein the alloy powder, electrolytic copper powder, tin powder and phosphorus iron powder for diamond tools are all analytically pure and have particle sizes of 1-10 μm.
9. The use according to claim 8, wherein the alloy powder for diamond tools is 65Mn powder.
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