CN109047775B - Titanium carbide-plated diamond and production process thereof - Google Patents

Titanium carbide-plated diamond and production process thereof Download PDF

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CN109047775B
CN109047775B CN201810964400.2A CN201810964400A CN109047775B CN 109047775 B CN109047775 B CN 109047775B CN 201810964400 A CN201810964400 A CN 201810964400A CN 109047775 B CN109047775 B CN 109047775B
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diamond
titanium carbide
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plated diamond
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CN109047775A (en
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刘乾坤
张风岭
杨怀建
李鹏涛
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Zhongnan Diamond Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17Metallic particles coated with metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1003Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007Atmosphere
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/223Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating specially adapted for coating particles
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001Cutting tools, earth boring or grinding tool other than table ware
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Abstract

The invention relates to and belongs to the technical field of industrial diamond, in particular to a production process of titanium carbide-plated diamond, which is obtained by sintering titanium carbide-plated on the surface in a carbon-containing mixed gas atmosphere; the volume ratio of each component of the carbon-containing mixed gas is as follows: CO 225 to 15 parts by weight of H25 to 15 parts of CH425-45 parts. The specific conditions of sintering are as follows: and preserving the heat for 90-180 minutes at 550-750 ℃. The titanium carbide-plated diamond is obtained by sintering the titanium-plated diamond on the surface in the atmosphere of carbon-containing mixed gas; the titanium carbide-plated diamond can further improve the binding force between diamond particles and a matrix and improve the durability of a tool, and meanwhile, the coating is inert, so that the adverse effect that a pure metal titanium coating pollutes a processed material when processing materials such as rare earth metals is solved, and the titanium carbide-plated diamond can be applied to high-strength operation according to high requirements of cutting or processing objects on components of the tool.

Description

Titanium carbide-plated diamond and production process thereof
Technical Field
The invention belongs to the technical field of superhard materials, and particularly relates to titanium carbide-plated diamond and a production process thereof.
Background
Industrial diamond particles are widely used as superabrasive particles in the manufacture of various abrasive articles.
Most diamond abrasive tools are made by bonding diamond particles to a substrate using a metal bond. Because of the low adhesion of diamond to metal, most industrial diamond particles tend to fall off the substrate when the tool is used due to abrasive forces. The metal titanium coating is plated on the surface of the industrial diamond, titanium is combined with the diamond through titanium carbide bonds, and surface titanium is combined with the base metal in an alloy form, so that the falling loss of diamond particles can be greatly reduced, the holding force of a tool base body on the diamond particles is improved, the service life of a grinding tool is prolonged, and the processing efficiency is improved. The plating layer can isolate the diamond and the tool base metal, so that the iron alloy base with the erosion function to the diamond can be widely applied to replace cobalt and other noble metals. Titanium plated diamond has become popular in the machine tool industry.
It has been found that when a superabrasive tool made of titanium-plated diamond is used to process rare earth metals, the titanium metal used as the plating layer is likely to form a solid solution with the material to be processed, and the material to be processed is contaminated, thereby affecting the purity and performance of the material to be processed. Therefore, it is highly desirable to provide a non-metallic titanium-plated diamond with a function of plating titanium diamond to overcome the defects of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the titanium carbide plated diamond, so that the excellent performances of high holding force and the like of the titanium plated diamond are further improved, and the adverse effect that a pure metal titanium coating pollutes a processed material when processing materials such as rare earth metals and the like is solved.
The invention also provides a production process of the titanium carbide-plated diamond.
In order to achieve the purpose, the invention adopts the following technical scheme:
a production process of titanium carbide-plated diamond is formed by combining a titanium plating process on the surface of diamond and a process for converting titanium into titanium carbide; the process for converting titanium into titanium carbide is obtained by sintering diamond with titanium plated on the surface in the atmosphere of carbon-containing mixed gas; the volume ratio of each component of the carbon-containing mixed gas is as follows: CO 225 to 15 parts by weight of H25 to 15 parts of CH425-45 parts.
Further, the specific conditions of sintering are as follows: and preserving the heat for 90-180 minutes at 550-750 ℃. Further preferably, it may be: arranging stainless steel barrels with titanized diamond on the surface in a vacuum sintering chamber, and pumping the vacuum sintering chamber to 10 degrees-4Pa high vacuum, heating to control the temperature in the vacuum sintering chamber to 550-750 ℃, preserving heat for 90-180 minutes, and introducing carbon-containing mixture into the furnace during heat preservationAnd (5) mixing the gases, filling argon into the vacuum sintering chamber after the heat preservation is finished, and cooling to obtain the titanium carbide-plated diamond.
In the production process of the titanium carbide-plated diamond, the titanium plating process on the surface of the diamond is formed by mixing and evaporating the diamond, the plating powder and the binding agent; wherein the surface titanium-plated diamond is prepared by the following steps:
1) preparing plating layer powder: respectively weighing TiO with the particle size not larger than 300 meshes according to the proportion2、MgCl2Mixing with Al powder, and making into coating powder;
2) preparing an adhesive: respectively weighing absolute ethyl alcohol, butanol and glycerol according to the proportion, and uniformly mixing to prepare an adhesive for later use;
3) preparing mixed raw materials: respectively weighing diamond and adhesive according to a ratio, adding the diamond and the adhesive into a container, uniformly stirring, pouring the coating powder according to the ratio, continuously uniformly stirring to prepare mixed raw materials, separately pouring the mixed raw materials into a plurality of stainless steel barrels, and compacting the mixed raw materials for later use;
4) evaporation: arranging the stainless steel barrels filled with the mixed raw materials in a vacuum evaporation chamber, and pumping the vacuum evaporation chamber to 10 degrees-4Heating to enable the temperature in the vacuum evaporation chamber to be controlled at 750-850 ℃ under the high vacuum of Pa, designing heat preservation for 50-100 minutes according to the thickness of a titanium film, and filling argon into the vacuum evaporation chamber to cool after the heat preservation is finished;
5) separation: and when the pressure and the temperature in the vacuum evaporation chamber reach the ambient atmospheric pressure and temperature, taking out the stainless steel barrel, pouring out the evaporation material, screening out residual powder, and cleaning to obtain the coating.
Specifically, in the step 1), the coating powder comprises raw material components of TiO in parts by mass232 to 37 parts of MgCl243-53 parts and 10-15 parts of Al powder.
Specifically, in the step 2), the adhesive comprises the following raw material components in parts by mass: 80-120 parts of absolute ethyl alcohol, 8-12 parts of butanol and 3-4 parts of glycerol.
Specifically, in the step 3), the mass parts of the diamond, the plating powder and the adhesive are respectively as follows: 90-150 parts, 15-35 parts and 0.7-2.5 parts. In the present application, the diamond particle size ranges from 325/400 and in coarse individual sizes.
The invention also provides the titanium carbide-plated diamond produced by the production process.
Compared with the prior art, the invention has the beneficial effects that:
the titanium carbide-plated diamond is obtained by sintering the titanium-plated diamond on the surface in the atmosphere of carbon-containing mixed gas; further improves the excellent performances of chemical bonding between the coating of the titanium-plated diamond and the C-Ti on the surface of the diamond, and the like, and simultaneously solves the adverse effect that the pure metal titanium coating pollutes the processed material when processing materials such as rare earth metals and the like. The titanium carbide-plated diamond can improve the durability of the tool by improving the binding force between diamond particles and a substrate, and the plating layer is inert and is not easy to pollute a processed object, so that the titanium carbide-plated diamond can be applied to operation with high requirement on the purity of the processed object. In addition, the titanium carbide-plated diamond of the invention has simple production process and convenient operation, and is suitable for large-scale production.
Drawings
FIG. 1 is a micrograph of titanium carbide-plated diamond according to the present invention;
fig. 2 is an X-ray scan of a titanium carbide-plated diamond of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
In the following examples, the diamond product manufactured by Zhongnan Diamond Co., Ltd. having a particle size of 35/40 and a brand number of ZND2280 is exemplified for details.
A production process of titanium carbide-plated diamond specifically comprises the following steps:
1) preparing plating layer powder: respectively weighing TiO with the particle size of less than or equal to 300 meshes according to the mass ratio232 parts of MgCl247 parts of Al powder and 12 parts of Al powder are put into a powder mixer to be mixed for 60 minutes and uniformly mixed to prepare plating powder for standby;
2) preparing an adhesive: respectively weighing 90 parts of analytically pure absolute ethyl alcohol, 9 parts of analytically pure butanol and 3 parts of analytically pure glycerol according to the proportion, and uniformly mixing to prepare an adhesive for later use;
3) preparing mixed raw materials: respectively weighing 140 parts of diamond and 0.8 part of adhesive according to the proportion, adding the diamond and the adhesive into a container, uniformly stirring, pouring 15 parts of plating powder according to the proportion, continuously uniformly stirring to prepare a mixed raw material, and separately pouring the mixed raw material into a plurality of stainless steel barrels and compacting the mixed raw material for later use;
4) evaporation: arranging the stainless steel barrels filled with the mixed raw materials in a vacuum evaporation chamber, and pumping the vacuum evaporation chamber to 10 degrees-4Pa, heating to control the temperature in the vacuum evaporation chamber to 810 ℃, preserving heat for 75 minutes, and filling argon into the vacuum evaporation chamber to cool after the heat preservation is finished;
5) separation: when the pressure and the temperature in the vacuum evaporation chamber reach the ambient atmospheric pressure and temperature, taking out the stainless steel barrel, pouring out the evaporation material, screening out residual powder, and cleaning to obtain the diamond with the titanium plated surface;
6) vacuum heating: arranging stainless steel barrels with titanized diamond on the surface in the vacuum sintering chamber, and pumping the vacuum sintering chamber to 10 degrees-4Pa, heating to control the temperature in the vacuum sintering chamber to 580 ℃ and keeping the temperature for 100 minutes;
7) carbon-containing gas filling: when the temperature in the furnace rises to 580 ℃, CO is respectively opened2 、H2、CH4Gas cylinder valves for three gases and a gas pipeline electromagnetic valve leading to the heating furnace; the flow rates of the three gases are respectively adjusted to 6 liters/minute, 6 liters/minute and 30 liters/minute; when the pressure in the furnace reaches 1 x 105And when Pa, opening a furnace top air release valve and igniting. CO is turned off at the end of the heat preservation2 、H2、CH4The charging valve and the gas cylinder valve are charged with argon until the flame of the furnace top gas-release valve is extinguished;
8) forced cooling: closing the air release valve at the furnace top, starting the cooling fan until the temperature in the furnace reaches below 60 ℃, opening the furnace door and taking out the product, namely the titanium carbide-plated diamond.
The microphotographs and X-ray scanning images of the titanium carbide-plated diamond produced as described above are shown in FIGS. 1 and 2. As can be seen from fig. 1 and 2: the main component of the coating of the titanium carbide-plated diamond is titanium carbide.
The titanium carbide-plated diamond obtained by the production is subjected to correlation performance test and is compared with the surface titanium-plated diamond prepared in the step 5), and the test results are shown in table 1. As can be seen from table 1: the titanium carbide-plated diamond can further improve the holding force of diamond particles, thereby improving durability.
Table 1: comparative test of diamond, titanium-plated diamond and titanium carbide-plated diamond performance
Figure 957252DEST_PATH_IMAGE001
Example 2
This example is described in detail by way of example with respect to a diamond product manufactured by Zhongnan diamond Limited having a particle size of 325/400 and a designation ZND 2010.
A production process of titanium carbide-plated diamond specifically comprises the following steps:
1) preparing plating layer powder: respectively weighing TiO with the particle size of less than or equal to 300 meshes according to the mass ratio237 parts of MgCl253 parts of Al powder and 15 parts of Al powder are put into a powder mixer to be mixed for 60 minutes and uniformly mixed to prepare plating powder for standby;
2) preparing an adhesive: respectively weighing 120 parts of analytically pure absolute ethyl alcohol, 12 parts of analytically pure butanol and 4 parts of analytically pure glycerol according to the proportion, and uniformly mixing to prepare an adhesive for later use;
3) preparing mixed raw materials: respectively weighing 90 parts of diamond and 2.5 parts of adhesive according to the proportion, adding the diamond and the adhesive into a container, uniformly stirring, pouring 35 parts of plating powder according to the proportion, continuously uniformly stirring to prepare a mixed raw material, and separately pouring the mixed raw material into a plurality of stainless steel barrels and compacting the mixed raw material for later use;
4) evaporation: arranging the stainless steel barrels filled with the mixed raw materials in a vacuum evaporation chamber, and pumping the vacuum evaporation chamber to 10 degrees-4Pa, heating to control the temperature in the vacuum evaporation chamber to 810 ℃, preserving the heat for 80 minutes, and filling argon into the vacuum evaporation chamber to cool after the heat preservation is finished;
5) separation: when the pressure and the temperature in the vacuum evaporation chamber reach the ambient atmospheric pressure and temperature, taking out the stainless steel barrel, pouring out the evaporation material, screening out residual powder, and cleaning to obtain the diamond with the titanium plated surface;
6) vacuum heating: arranging stainless steel barrels with titanized diamond on the surface in the vacuum sintering chamber, and pumping the vacuum sintering chamber to 10 degrees-4Pa, heating to control the temperature in the vacuum sintering chamber to 580 ℃ and keeping the temperature for 150 minutes;
7) carbon-containing gas filling: when the temperature in the furnace rises to 580 ℃, CO is respectively opened2 、H2、CH4Gas cylinder valves for three gases and a gas pipeline electromagnetic valve leading to the heating furnace; the flow rates of the three gases are respectively adjusted to 6 liters/minute, 6 liters/minute and 30 liters/minute; when the pressure in the furnace reaches 1 x 105And when Pa, opening a furnace top air release valve and igniting. CO is turned off at the end of the heat preservation2 、H2、CH4The charging valve and the gas cylinder valve are charged with argon until the flame of the furnace top gas-release valve is extinguished;
8) forced cooling: closing the air release valve at the furnace top, starting the cooling fan until the temperature in the furnace reaches below 60 ℃, opening the furnace door and taking out the product, namely the titanium carbide-plated diamond.
Example 3
The production process of titanium carbide-plated diamond is the same as that in example 1 in raw material proportion and operation steps, and has the difference that the heat preservation temperature in evaporation is 850 ℃ and the heat preservation time is 50 minutes; the other difference is that the temperature of the heat preservation is 750 ℃ and the heat preservation time is 90 minutes when the air is ventilated and sintered.
The titanium carbide-plated diamond obtained by the production is subjected to a correlation performance test, and the test result shows that: the titanium carbide plated diamond can further improve the holding force of diamond particles, thereby improving the durability.

Claims (7)

1. A production process of titanium carbide-plated diamond is characterized in that the titanium carbide-plated diamond is obtained by sintering the titanium carbide-plated diamond on the surface in the atmosphere of carbon-containing mixed gas; the volume ratio of each component of the carbon-containing mixed gasComprises the following steps: CO 225 to 15 parts by weight of H25 to 15 parts of CH425-45 parts of a solvent;
the main component of the coating of the titanium carbide-plated diamond is titanium carbide.
2. The process for producing titanium carbide-plated diamond according to claim 1, wherein the specific conditions for sintering are: and preserving the heat for 90-180 minutes at 550-750 ℃.
3. The titanium carbide-plated diamond production process according to claim 1, wherein the surface titanium-plated diamond is produced by the steps of:
1) preparing plating layer powder: respectively weighing TiO with the particle size not larger than 300 meshes according to the proportion2、MgCl2Mixing with Al powder, and making into coating powder;
2) preparing an adhesive: respectively weighing absolute ethyl alcohol, butanol and glycerol according to the proportion, and uniformly mixing to prepare an adhesive for later use;
3) preparing mixed raw materials: respectively weighing the diamond and the adhesive according to the proportion, adding the diamond and the adhesive into a container, uniformly stirring, adding the plating powder according to the proportion, and continuously uniformly stirring to prepare a mixed raw material for later use;
4) evaporation: and (3) putting the mixed raw materials into a vacuum evaporation chamber, heating to 750-850 ℃ under a vacuum condition, preserving heat for 50-100 minutes, and filling argon into the vacuum evaporation chamber after the heat preservation is finished to cool down to obtain the composite material.
4. The production process of titanium carbide-plated diamond according to claim 3, wherein in the step 1), the mass part ratio of each raw material component of the plating powder is TiO232 to 37 parts of MgCl243-53 parts and 10-15 parts of Al powder.
5. The production process of titanium carbide-plated diamond according to claim 3, wherein in the step 2), the raw material components of the adhesive are in parts by mass as follows: 80-120 parts of absolute ethyl alcohol, 8-12 parts of butanol and 3-4 parts of glycerol.
6. The production process of the titanium carbide-plated diamond according to claim 3, wherein in the step 3), the mass parts of the diamond, the plating powder and the adhesive are respectively as follows: 90-150 parts, 15-35 parts and 0.7-2.5 parts.
7. The titanium carbide-plated diamond produced by the production process according to any one of claims 1 to 6.
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CN110257756B (en) * 2019-07-23 2021-08-31 海南海控特玻科技有限公司 Preparation method of surface titanium carbide metal product
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CN115233197B (en) * 2022-08-09 2023-09-15 中南钻石有限公司 Titanium nitride plating diamond and production process thereof

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CN101033535A (en) * 2007-04-10 2007-09-12 中国矿业大学 Medical titanium alloy hip joint bulb surface carburization process
CN102242341A (en) * 2011-07-01 2011-11-16 中南钻石股份有限公司 High-temperature-resistant titanium film super-hard composite material and production process thereof
CN107267837A (en) * 2017-06-27 2017-10-20 武汉新锐合金工具有限公司 Gradient hard alloy that a kind of Binder Phase changes in gradient and preparation method thereof

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JPS58110654A (en) * 1981-12-22 1983-07-01 Mitsubishi Metal Corp Cermet tip for cutting with reactive surface layer and its manufacture
CN101033535A (en) * 2007-04-10 2007-09-12 中国矿业大学 Medical titanium alloy hip joint bulb surface carburization process
CN102242341A (en) * 2011-07-01 2011-11-16 中南钻石股份有限公司 High-temperature-resistant titanium film super-hard composite material and production process thereof
CN107267837A (en) * 2017-06-27 2017-10-20 武汉新锐合金工具有限公司 Gradient hard alloy that a kind of Binder Phase changes in gradient and preparation method thereof

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