CN109368635A - A kind of method of diamond surface plating boron doping metal carbides - Google Patents
A kind of method of diamond surface plating boron doping metal carbides Download PDFInfo
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- CN109368635A CN109368635A CN201811298110.5A CN201811298110A CN109368635A CN 109368635 A CN109368635 A CN 109368635A CN 201811298110 A CN201811298110 A CN 201811298110A CN 109368635 A CN109368635 A CN 109368635A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/507—Borides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Polishing Bodies And Polishing Tools (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of methods of diamond surface plating boron doping metal carbides.This method uniformly mixes diamond with metal powder, boron powder, inorganic salt powder, and in an inert atmosphere, 800~1500 DEG C under conditions of constant temperature 0.5~6 hour, make diamond surface plate boron doping metal carbides film.Boron doping metal carbides coating obtained by the present invention can effectively inhibit oxidation of the diamond in high temperature air, can also improve the Interface adhesive strength of diamond and metallic matrix in diamond compact.The diamond that this kind is coated with boron doping metal carbides can be applied not only in the cuttings and polishing tool such as drill bit, saw blade, grinding wheel, can also be applied in the heat dissipation element of electronic equipment.
Description
Technical field
The present invention relates to a kind of methods of diamond surface plating boron doping metal carbides.
Background technique
Hardness and excellent heating conduction of the diamond because of its superelevation are counted as the outstanding reinforced phase of one kind and are added to again
In condensation material, it is widely used in the grinding tools such as drill bit, grinding wheel and electronic radiation original part.In general Buddha's warrior attendant lapicide
High temperature is directed in the manufacture and use process of tool.However, the aerial oxidizing temperature of diamond is about 700 DEG C, when in sky
It is more than the oxidizing temperature in gas, the mechanical property of diamond can reduce greatly, and which has limited diamond in an oxidizing environment wide
General application.Therefore, many diamond tools need to also be prepared in anaerobic sublimity up to now.
In general diamond tool is all diamond metal based composites, preparation is at high temperature sintered
Journey.Common metallic matrix includes copper and VIII race's metallic element, such as iron, cobalt and nickel.But in high temperature preparation process, VIII race gold
Diamond graphitization can be catalyzed by belonging to element, caused the hardness of diamond and compression strength sharply to decline, greatly reduced diamond
The performance of tool and service life.Although copper is often used as bonding agent, the wetting of copper and diamond in diamond composite
Property is poor, causes boundary strength between the two low, diamond is easy to be pulled out in use, shortens the use of diamond tool
Service life.
Currently, the common method to solve the above problems be diamond surface painting be covered with diamond have good wettability and
The material of chemical bonding ability, such as metal, boron, silicon.And physical vapour deposition (PVD) (PVD) and chemical vapor deposition (CVD) are then
Most common two kinds of method of coating.But both methods is also each defective, PVD method production coating and diamond link compared with
It is weak, because prepared coating does not form chemical bond connection with diamond, and need to use in CVD method toxic, inflammable or rotten
The gas of corrosion has biggish security risk as reaction source.
United States Patent (USP) No.6524357 proposes a kind of method in diamond surface plating metal coating: first in indifferent gas
Atmosphere heats diamond and metal oxide powder at 500 DEG C, and then sample is heated in hydrogen to 700-800 DEG C and protected
Temperature 30 minutes, except oxide layer finally forms the coat of metal in diamond surface.Patent EP0352811 has been further described through this
Application of the kind coat of metal diamond in cutting tool and composite sheet.In addition, United States Patent (USP) No.4968326 also describes one
The method that kind improves the diamond tool service life, i.e., by generating carbide interface between diamond and basis material.
But metal carbides are limited to the promotion effect of diamond oxidation resistance, golden under about 800 DEG C of aerobic environment
Belong to while carbide coating is oxidized and falling off, cannot effectively improve the oxidation resistance of diamond.Boron element adds
Entering helps to further increase its oxidation resistance.United States Patent (USP) No.7807220 describes a kind of in diamond surface generation carbon
The method for changing boron and boronation cobalt coating, greatly improves the cohesive force of diamond and basis material.This method needs very high
Reaction temperature and reaction time keep the temperature 3h at 1100 DEG C, diamond (100) face can only be made to cover upper boron carbide coating, only
Coating being completely covered in diamond surface is just able to achieve in 1150 DEG C of heat preservation at least 6h.It is reported according to Japan Patent JP 9142932
Road adds the boron oxide or boric acid of certain content in diamond compact, it is strong in drilling process that composite sheet can be improved
Degree.But simple boron carbide coating limits its use due to the volatilization of oxidation at high temperatures boron.
Summary of the invention
The purpose of the present invention is provide a kind of new method, i.e., a kind of gold for the above problem existing for existing processing method
The method that boron doping metal carbides are plated on hard rock surface, can protect diamond not by oxygen for a long time under 1000 DEG C of high temperature
Change, prevents the diamond graphitization as caused by VIII race's element, while can effectively improve diamond and other metal materials
Adhesive strength, more fully utilize expensive diamond.
The applicable diamond type of the method for the present invention includes that natural diamond, high temperature and pressure diamond, polycrystalline diamond are multiple
Diamond made from piece and chemical vapor deposition is closed, the pattern of diamond includes particle, micro mist, thin slice and other specific shapes
Shape.
The boron doping metal carbides coating that method through the invention is plated in diamond surface, ingredient can be boron ginseng
One of miscellaneous titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, chromium carbide, molybdenum carbide and tungsten carbide or
Multiple combinations, thickness of coating range are 0.1~20 micron.
The method of the present invention is to plate boron doping gold in diamond surface by molten-salt growth method under inert atmosphere heating condition
Belong to carbide membrane.
The present invention comprising the following specific steps
1) diamond surface is cleaned by ultrasonic；
2) it boron powder, salt powder and diamond will be contained will be ground in mortar and mixed them thoroughly, and obtain mixed raw material；
3) by step 2) obtain mixed raw material be placed into furnace body, be passed through inert gas discharge furnace body in air, and
Inert gas circulation is kept in preparation process；
4) furnace body temperature is risen to 800-1500 DEG C and constant temperature 0.5-6 hours；
5) furnace temperature of furnace body, which is cooled to room temperature, separates plating metal boride diamond and cleans with waste material, obtains surface plating
There is the diamond of plating boron doping metal carbides film.
Containing boron powder used in the step 2) is boron powder, boron oxide powder, boric acid powder, borax
(Na2B4O710H2O) or other contain boron powder.
Inert gas used in the step 3) is one of helium, neon, argon gas, xenon, Krypton and nitrogen
Or multiple gases mixing.
Beneficial effects of the present invention:
Boron doping metal carbides coating obtained by the present invention can effectively inhibit diamond in high temperature air
Oxidation, can also improve the Interface adhesive strength of diamond and metallic matrix in diamond compact.This kind is coated with boron doping
The diamond of metal carbides can be applied not only in the cuttings and polishing tool such as drill bit, saw blade, grinding wheel, can also be applied to
In the heat dissipation element of electronic equipment.
Specific embodiment
Example 1:
By the natural diamond particles of 70/80 mesh of 16g and 6.4g titanium (Ti) powder, 3.5g boron (B) powder, 9.8g sodium chloride
(NaCl) powder and 14.1g potassium chloride (KCl) powder uniformly mix 2 hours at room temperature.It is contained with refractory ceramics boat sufficiently mixed
Raw material after conjunction is placed in tube furnace, is passed through argon gas into tube furnace to remove furnace air.It will with 6 DEG C/min of speed
In-furnace temperature rises to 1200 DEG C, and constant temperature 6 hours at 1200 DEG C；Or in-furnace temperature is risen to 6 DEG C/min of speed
1500 DEG C, and constant temperature 0.5 hour at 1500 DEG C；Or in-furnace temperature is risen to 800 DEG C with 6 DEG C/min of speed, and
Constant temperature 6 hours at 800 DEG C；To plate the carbonization titanium coating that boron mixes in diamond surface.During the preparation process, argon gas is in furnace
Interior holding circulation is until furnace temperature is cooled to room temperature.After furnace temperature is cooled to room temperature, sample is dipped in distilled water and is boiled, removed
Inorganic salts obtain the mixing of the diamond containing coating after filtration washing.Diamond is separated with waste material with sub-sieve, surface is obtained and contains
The diamond of Dark grey coating.XRD is the result shows that the diamond surface Coating composition obtained with the method is based on titanium carbide
With a small amount of titanium boride.XPS is the result shows that boron content is about 10at% in coating
Example 2:
Using method identical with example 1, in addition to by the high temperature and pressure diamond of 40/45 mesh of 16g and 3.2g zirconium (Zr)
Powder, 3.5g boron (B) powder, 9.8g sodium chloride (NaCl) powder and 14.0g sodium carbonate (Na2CO3) powder mixing, it is protected at 1000 DEG C
Temperature 6 hours.Taupe is presented in diamond surface after cleaning and separating.XRD is the result shows that the diamond surface obtained with the method
Coating composition is based on zirconium carbide with a small amount of zirconium boride.XPS is the result shows that boron content is about 10at% in coating
Example 3:
Using method identical with example 2, in addition to by the polycrystalline diamond of 40/45 mesh of 16g and 3.2g titanium (Ti) powder,
6.1g zirconium (Zr) powder, 3.5g boron (B) powder, 9.8g sodium chloride (NaCl) powder and 14.0g sodium carbonate (Na2CO3) powder mixing.XRD
The result shows that the diamond surface Coating composition obtained with the method is based on titanium carbide and zirconium carbide with a small amount of boronation
Titanium and zirconium boride.
Example 4:
Using method identical with example 1, in addition to titanium valve surface used has one layer of oxide skin.XRD the result shows that with
The diamond surface Coating composition that the method obtains is based on titanium carbide with a small amount of titanium boride.
Example 5:
Using method identical with example 1, in addition to by the high temperature and pressure diamond of 20/25 mesh of 16g and 10.7g titanium oxide
(TiO2) powder, 3.5g boron (B) powder, 9.8g sodium chloride (NaCl) powder and 14.0g sodium carbonate (Na2CO3) powder mixing.XRD result
Show that the diamond surface Coating composition obtained with the method is based on titanium carbide with a small amount of titanium boride.
Example 6:
Using method identical with example 1, in addition to by the high temperature and pressure diamond of 20/25 mesh of 16g and 6.8g vanadium (V) powder,
4.0g boron (B) powder, 9.8g sodium chloride (NaCl) powder and 14.0g sodium carbonate (Na2CO3) powder mixing.XRD is the result shows that use this
The diamond surface Coating composition that method obtains is based on vanadium carbide with a small amount of vanadium boride.
Example 7:
Using method identical with example 1, in addition to by diamond chip made from 6 chemical vapor depositions (Φ 10mm*1mm)
It is inserted into 7.0g chromium (Cr) powder, 4.2g boron (B) powder, 14.1g sodium chloride (KCl) powder and 14.0g sodium carbonate (Na2CO3) powder it is mixed
It closes in object.Cvd diamond piece surface forms uniform complete coating after cleaning and separating.XRD is the result shows that use the method
The diamond surface Coating composition of acquisition is based on chromium carbide with a small amount of chromium boride.
Claims (3)
1. a kind of method of diamond surface plating boron doping metal carbides, comprising the following steps:
1) diamond surface is cleaned by ultrasonic；
2) it boron powder, salt powder and diamond will be contained will be ground in mortar and mixed them thoroughly, and obtain mixed raw material；
3) mixed raw material that step 2) obtains is placed into furnace body, is passed through air in inert gas discharge furnace body, and preparing
Inert gas circulation is kept in the process；
4) furnace body temperature is risen to 800-1500 DEG C and constant temperature 0.5-6 hours；
5) furnace temperature of furnace body, which is cooled to room temperature, separates plating metal boride diamond and cleans with waste material, obtains to surface and is coated with plating
The diamond of boron doping metal carbides film.
2. a kind of method of diamond surface plating boron doping metal carbides according to claim 1, it is characterised in that: institute
State used in step 2) containing boron powder be boron powder, boron oxide powder, boric acid powder or borax powder.
3. a kind of method of diamond surface plating boron doping metal carbides according to claim 1, it is characterised in that: institute
Inert gas used in step 3) is stated, is one or more of helium, neon, argon gas, xenon, Krypton and nitrogen gas
Body mixing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811298110.5A CN109368635B (en) | 2018-11-02 | 2018-11-02 | Method for plating boron-doped metal carbide on surface of diamond |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811298110.5A CN109368635B (en) | 2018-11-02 | 2018-11-02 | Method for plating boron-doped metal carbide on surface of diamond |
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| CN109368635B CN109368635B (en) | 2021-10-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484009A (en) * | 2020-03-14 | 2020-08-04 | 严仙荣 | Surface chromizing method for nano diamond |
| CN112456485A (en) * | 2020-09-24 | 2021-03-09 | 上海江信超硬材料有限公司 | Preparation method of boron-doped diamond micro powder |
| CN113697811A (en) * | 2021-08-26 | 2021-11-26 | 河北师范大学 | Three-dimensional layered boron-doped titanium carbide and preparation method and application thereof |
| CN114956086A (en) * | 2022-05-26 | 2022-08-30 | 无锡迈新纳米科技有限公司 | Boron-doped two-dimensional transition metal carbide material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110312176A1 (en) * | 2010-06-22 | 2011-12-22 | International Business Machines Corporation | Forming an electrode having reduced corrosion and water decomposition on surface using an organic protective layer |
| CN104591783A (en) * | 2015-01-29 | 2015-05-06 | 吉林大学 | Method for plating boron carbide on diamond surface |
-
2018
- 2018-11-02 CN CN201811298110.5A patent/CN109368635B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110312176A1 (en) * | 2010-06-22 | 2011-12-22 | International Business Machines Corporation | Forming an electrode having reduced corrosion and water decomposition on surface using an organic protective layer |
| CN104591783A (en) * | 2015-01-29 | 2015-05-06 | 吉林大学 | Method for plating boron carbide on diamond surface |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484009A (en) * | 2020-03-14 | 2020-08-04 | 严仙荣 | Surface chromizing method for nano diamond |
| CN112456485A (en) * | 2020-09-24 | 2021-03-09 | 上海江信超硬材料有限公司 | Preparation method of boron-doped diamond micro powder |
| CN113697811A (en) * | 2021-08-26 | 2021-11-26 | 河北师范大学 | Three-dimensional layered boron-doped titanium carbide and preparation method and application thereof |
| CN114956086A (en) * | 2022-05-26 | 2022-08-30 | 无锡迈新纳米科技有限公司 | Boron-doped two-dimensional transition metal carbide material |
| CN114956086B (en) * | 2022-05-26 | 2023-09-19 | 无锡迈新纳米科技有限公司 | Boron-doped two-dimensional transition metal carbide material |
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