CN109368635B - Method for plating boron-doped metal carbide on surface of diamond - Google Patents

Method for plating boron-doped metal carbide on surface of diamond Download PDF

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CN109368635B
CN109368635B CN201811298110.5A CN201811298110A CN109368635B CN 109368635 B CN109368635 B CN 109368635B CN 201811298110 A CN201811298110 A CN 201811298110A CN 109368635 B CN109368635 B CN 109368635B
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powder
diamond
boron
metal carbide
doped metal
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CN109368635A (en
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孟庆南
张弛
吴金昊
孙友宏
何林恺
高科
刘宝昌
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Jilin University
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Jilin University
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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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a method for plating boron-doped metal carbide on the surface of diamond. The method comprises the steps of uniformly mixing diamond with metal powder, boron powder and inorganic salt powder, and plating a boron-doped metal carbide film on the surface of the diamond in an inert atmosphere at the constant temperature of 800-1500 ℃ for 0.5-6 hours. The boron-doped metal carbide coating prepared by the invention can effectively inhibit the oxidation of diamond in high-temperature air and can also improve the interface bonding capability of diamond and a metal matrix in the diamond compact. The diamond coated with the boron-doped metal carbide can be applied to cutting and polishing tools such as drill bits, saw blades, grinding wheels and the like, and can also be applied to heat dissipation elements of electronic equipment.

Description

Method for plating boron-doped metal carbide on surface of diamond
Technical Field
The invention relates to a method for plating boron-doped metal carbide on the surface of diamond.
Background
Diamond is considered to be an excellent reinforcing phase added to composite materials due to its ultrahigh hardness and excellent heat conductivity, and is widely applied to grinding tools such as drills and grinding wheels and electronic heat dissipation elements. High temperatures are typically involved in the manufacture and use of diamond tools. However, the oxidation temperature of diamond in air is about 700 ℃, and when the oxidation temperature is exceeded in air, the mechanical properties of diamond are greatly reduced, which limits the wide application of diamond in an oxidizing environment. Thus, many diamond tools have to date been manufactured in an anaerobic environment.
Diamond tools are generally diamond metal matrix composites that are prepared by a sintering process at high temperatures. Common metal matrices include copper and group VIII metals, such as iron, cobalt and nickel. However, in the high-temperature preparation process, the VIII group metal elements can catalyze the graphitization of the diamond, so that the hardness and the compressive strength of the diamond are reduced rapidly, and the performance and the service life of the diamond tool are greatly reduced. Although copper is often used as a bonding agent in diamond composite materials, the wettability of copper and diamond is poor, so that the strength of the interface between the copper and the diamond is low, the diamond is easy to pull out in the using process, and the service life of the diamond tool is shortened.
At present, the common method for solving the above problems is to coat the surface of diamond with a material having good wettability and chemical bonding ability with diamond, such as metal, boron, silicon, etc. Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD) are the two most commonly used plating methods. However, the two methods have respective defects that the coating made by the PVD method is weakly bonded with the diamond, and the prepared coating is not chemically bonded with the diamond, while the CVD method requires toxic, flammable or corrosive gas as a reaction source, thereby having a great potential safety hazard.
U.S. patent No.6524357 proposes a method of plating a diamond surface with a metal coating: firstly, heating diamond and metal oxide powder at 500 ℃ in an inert atmosphere, then heating a sample to 700-800 ℃ in hydrogen and preserving the temperature for 30 minutes, removing an oxide layer and finally forming a metal coating on the surface of the diamond. Patent EP0352811 further describes the use of such metal coated diamonds in cutting tools and compacts. In addition, U.S. patent No.4968326 describes a method of increasing the life of a diamond tool by creating a carbide interface between the diamond and the substrate material.
However, the effect of improving the oxidation resistance of diamond by the metal carbide is limited, and the metal carbide coating is oxidized and falls off in an aerobic environment at about 800 ℃, so that the oxidation resistance of diamond cannot be effectively improved. The addition of boron element is helpful to further improve the oxidation resistance. Us patent No.7807220 describes a method of forming a coating of boron carbide and cobalt boride on the surface of diamond to greatly improve the adhesion of the diamond to the substrate material. The method needs very high reaction temperature and reaction time, the heat preservation is carried out for 3 hours at 1100 ℃, only the surface of the diamond (100) is covered with the boron carbide coating, and the complete coverage of the coating on the surface of the diamond can be realized only by preserving the heat for at least 6 hours at 1150 ℃. According to the report of Japanese patent JP 9142932, the strength of the composite sheet during drilling can be improved by adding a certain content of boron oxide or boric acid into the diamond composite sheet. However, the use of pure boron carbide coatings is limited by the volatilization of boron oxide at high temperatures.
Disclosure of Invention
The invention aims to solve the problems of the existing treatment method and provide a novel method, namely a method for plating boron-doped metal carbide on the surface of diamond, which can protect the diamond from being oxidized for a long time at the high temperature of 1000 ℃, prevent diamond graphitization caused by group VIII elements, effectively improve the bonding strength of the diamond and other metal materials and more fully utilize expensive diamond materials.
The diamond types suitable for the method comprise natural diamond, high-temperature and high-pressure diamond, polycrystalline diamond compact and diamond prepared by chemical vapor deposition, and the appearance of the diamond comprises particles, micro powder, slices and other specific shapes.
The boron-doped metal carbide coating plated on the surface of the diamond by the method disclosed by the invention can be one or a combination of more of boron-doped titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, chromium carbide, molybdenum carbide and tungsten carbide, and the thickness of the coating ranges from 0.1 to 20 micrometers.
The method of the invention is to plate a boron-doped metal carbide film on the surface of the diamond by a molten salt method under the heating condition of inert atmosphere.
The invention comprises the following specific steps:
1) carrying out ultrasonic cleaning on the surface of the diamond;
2) grinding the boron-containing powder, the salt powder and the diamond in a mortar to fully mix the boron-containing powder, the salt powder and the diamond to obtain a mixed raw material;
3) placing the mixed raw material obtained in the step 2) into a furnace body, introducing inert gas to discharge air in the furnace body, and keeping the inert gas in circulation in the preparation process;
4) the temperature in the furnace body is raised to 800-1500 ℃ and is kept constant for 0.5-6 hours;
5) and (3) after the furnace temperature of the furnace body is reduced to room temperature, separating and cleaning the metal boride-plated diamond from the waste to obtain the diamond with the surface plated with the boron-doped metal carbide film.
The boron-containing powder used in the step 2) is boron powder, boron oxide powder, boric acid powder, borax (Na2B4O7 & 10H2O) or other boron-containing powder.
The inert gas used in the step 3) is one or a mixture of helium, neon, argon, xenon and krypton.
The invention has the beneficial effects that:
the boron-doped metal carbide coating prepared by the invention can effectively inhibit the oxidation of diamond in high-temperature air and can also improve the interface bonding capability of diamond and a metal matrix in the diamond compact. The diamond coated with the boron-doped metal carbide can be applied to cutting and polishing tools such as drill bits, saw blades, grinding wheels and the like, and can also be applied to heat dissipation elements of electronic equipment.
Detailed Description
Example 1:
16g of 70/80 mesh natural diamond particles were uniformly mixed with 6.4g of titanium (Ti) powder, 3.5g of boron (B) powder, 9.8g of sodium chloride (NaCl) powder, and 14.1g of potassium chloride (KCl) powder at room temperature for 2 hours. And (3) using a high-temperature ceramic boat to contain the fully mixed raw materials, placing the raw materials into a tubular furnace, and introducing argon into the tubular furnace to remove air in the furnace. The temperature in the furnace is increased to 1200 ℃ at the speed of 6 ℃/min, and the temperature is kept constant at 1200 ℃ for 6 hours; or raising the temperature in the furnace to 1500 ℃ at the speed of 6 ℃/min, and keeping the temperature at 1500 ℃ for 0.5 hour; or raising the temperature in the furnace to 800 ℃ at the speed of 6 ℃/min, and keeping the temperature at 800 ℃ for 6 hours; thereby plating a boron-doped titanium carbide plating layer on the surface of the diamond. During the preparation process, argon gas is kept circulating in the furnace until the furnace temperature is cooled to room temperature. And cooling the furnace to room temperature, soaking the sample in distilled water, boiling, removing inorganic salt, filtering and washing to obtain the mixed material containing the coated diamond. Separating the diamond from the waste material by using a sample separating sieve to obtain the diamond with the dark gray plating layer on the surface. XRD results show that the diamond surface coating obtained by the method contains mainly titanium carbide and a small amount of titanium boride. XPS results show that the boron content of the coating is about 10 at%.
Example 2:
the same method as in example 1 was employed except that 16g of 40/45-mesh high-temperature high-pressure diamond was mixed with 3.2g of zirconium (Zr) powder, 3.5g of boron (B) powder, 9.8g of sodium chloride (NaCl) powder, and 14.0g of sodium carbonate (Na)2CO3) The powders were mixed and incubated at 1000 ℃ for 6 hours. The diamond surface appeared brown-gray after cleaning and separation. XRD results show that the diamond surface coating obtained by the method contains mainly zirconium carbide and a small amount of zirconium boride. The XPS result shows that the boron content in the coating is about 10 at%
Example 3:
the same method as in example 2 was used, except that 16g of 40/45-mesh polycrystalline diamond was mixed with 3.2g of titanium (Ti) powder, 6.1g of zirconium (Zr) powder, 3.5g of boron (B) powder, 9.8g of sodium chloride (NaCl) powder, and 14.0g of sodium carbonate (Na)2CO3) And (4) mixing the powder. XRD results show that the diamond surface coating obtained by the method contains mainly titanium carbide and zirconium carbide with a small amount of titanium boride and zirconium boride.
Example 4:
the same procedure as in example 1 was followed, except that titanium powder having an oxide scale on the surface thereof was used. XRD results show that the diamond surface coating obtained by the method contains mainly titanium carbide and a small amount of titanium boride.
Example 5:
the same method as in example 1 was used except that 16g of high temperature and high pressure diamond of 20/25 mesh was mixed with 10.7g of titanium oxide (TiO)2) Powder, 3.5g boron (B) powder, 9.8g sodium chloride (NaCl) powder and 14.0g sodium carbonate (Na)2CO3) And (4) mixing the powder. XRD results show that the diamond surface coating obtained by the method contains mainly titanium carbide and a small amount of titanium boride.
Example 6:
the same method as in example 1 was used except that 16g of 20/25-mesh high-temperature high-pressure diamond was mixed with 6.8g of vanadium (V) powder, 4.0g of boron (B) powder, 9.8g of sodium chloride (NaCl) powder, and 14.0g of sodium carbonate (Na)2CO3) And (4) mixing the powder. XRD results show that the diamond surface coating obtained by the method contains mainly vanadium carbide and a small amount of vanadium boride.
Example 7:
the same procedure as in example 1 was followed except that 6 diamond chips (. PHI.10 mm. times.1 mm) produced by chemical vapor deposition were intercalated with 7.0g of chromium (Cr) powder, 4.2g of boron (B) powder, 14.1g of sodium chloride (KCl) powder and 14.0g of sodium carbonate (Na)2CO3) In a mixture of powders. After cleaning and separation, a uniform and complete coating is formed on the surface of the CVD diamond sheet. XRD results show that the diamond surface coating obtained by the method contains mainly chromium carbide and a small amount of chromium boride.

Claims (3)

1. A method for plating boron-doped metal carbide on the surface of diamond comprises the following steps:
1) carrying out ultrasonic cleaning on the surface of the diamond;
2) grinding metal powder or oxide thereof, boron-containing powder, salt powder and diamond in a mortar to fully mix the metal powder, the boron-containing powder, the salt powder and the diamond to obtain a mixed raw material;
3) placing the mixed raw material obtained in the step 2) into a furnace body, introducing inert gas to discharge air in the furnace body, and keeping the inert gas in circulation in the preparation process;
4) the temperature in the furnace body is raised to 800-1500 ℃ and is kept constant for 0.5-6 hours;
5) after the furnace temperature of the furnace body is reduced to room temperature, separating and cleaning the metal boride-plated diamond from the waste to obtain diamond with a boron-plated doped metal carbide film plated on the surface;
the salt powder in the step 2 is a mixture of sodium chloride powder and potassium chloride powder or a mixture of sodium chloride powder and sodium carbonate powder;
and the metal powder in the step 2 is titanium powder, zirconium powder, vanadium powder or chromium powder.
2. The method for plating the surface of the diamond with the boron-doped metal carbide as claimed in claim 1, wherein the method comprises the following steps: the boron-containing powder used in the step 2) is boron powder, boron oxide powder, boric acid powder or borax powder.
3. The method for plating the surface of the diamond with the boron-doped metal carbide as claimed in claim 1, wherein the method comprises the following steps: the inert gas used in the step 3) is one or a mixture of helium, neon, argon, xenon and krypton.
CN201811298110.5A 2018-11-02 2018-11-02 Method for plating boron-doped metal carbide on surface of diamond Active CN109368635B (en)

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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
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

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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

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