WO2012063318A1 - Cvdダイヤモンド析出用基体及び析出面の形成方法 - Google Patents
Cvdダイヤモンド析出用基体及び析出面の形成方法 Download PDFInfo
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- WO2012063318A1 WO2012063318A1 PCT/JP2010/069888 JP2010069888W WO2012063318A1 WO 2012063318 A1 WO2012063318 A1 WO 2012063318A1 JP 2010069888 W JP2010069888 W JP 2010069888W WO 2012063318 A1 WO2012063318 A1 WO 2012063318A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/131—Wire arc spraying
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- the present invention relates to a substrate that is effective as a basis for forming a diamond coating layer by chemical vapor deposition (CVD), and a method for forming a precipitation surface on such a substrate.
- CVD chemical vapor deposition
- Tools and wear-resistant materials that use diamond characteristics that excel in hardness, thermal conductivity, friction coefficient, etc. contribute to the improvement of productivity at manufacturing sites. Since diamond is extremely difficult to machine, it is a preferable usage form that it is disposed in a thin film state only on a required working surface on a base member formed in a predetermined shape.
- High quality diamond films are made by CVD via a plasma state, but silicon is predominantly used as a base material for heteroepitaxial growth, and molybdenum and platinum are also slightly used. Even when these materials are used as a base material, if the purpose is to form a dense and smooth film by increasing the nucleation density, fine diamond is placed on the base material in advance without relying on spontaneous nucleation. A homoepitaxial growth technique is used as a growth starting point.
- the above-mentioned problem-solving substrate for diamond precipitation that is, a tool material such as cemented carbide, or a basic member such as a structural material made of an iron group metal, is not affected by the component components.
- An object of the present invention is to provide a technique for forming a diamond film.
- the inventors of the present invention have adhered a diamond film to a base material to be deposited to form a thin film intermediate layer mainly composed of a ceramic or intermetallic compound, and the intermediate layer is isolated from the base material.
- the diamond film was successfully formed without being affected by the basic material by dispersing finely divided diamond, which is the starting point of growth.
- the gist of the present invention is a substrate for CVD diamond precipitation in which a coating layer containing a seed diamond crystal in a matrix is bonded to the surface of a base material made of a hard material, and (1) a diamond particle (2) one or more first metal species selected from the group consisting of Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and / or an average particle size of 1 ⁇ m or less
- a diffusion layer is formed by diffusion of the first group of metal atoms and metal atoms constituting the hard material, or one of them, at the junction with the layer.
- the base material is an object viewed as a target of diamond layer deposition by CVD
- the base member is such that the object is created in some shape as a structural member
- the substrate (for precipitation) is a base material or a base member Is used as a term that refers to the entire structure in which a coating layer containing seed crystals is formed on the surface.
- such a deposition base is prepared by the following steps: (1) a part of the surface of a base material made of a hard material, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo A first metal compound which is a compound of one or more first metal species selected from the first metal group consisting of W and / or a non-metallic substance selected from boron, carbon or nitrogen. (2) distributing the diamond particles on the surface of the base material, and (3) the matrix containing the first metal species and / or the first metal compound.
- At least one of the steps (1) to (3) is performed under the influence of heat, and (4) at the boundary between the base material made of the hard material and the matrix, Consists of atoms of the first metal species and the hard material Both or one of the atoms of the genus atom form joint diffused by method in which bonding a basic agent and a matrix made of a hard material via the the bonding portion is created effectively.
- the matrix material firmly holds the diamond particles and is firmly bonded to the base material by the diffusion action that proceeds between the matrix material. Since the precipitation of diamond proceeds from the finely divided diamond particles contained in the matrix as the growth starting point, it is smooth without being affected by the base material, that is, on a cemented carbide or stainless steel material, which was impossible in the past. A diamond film can be formed.
- the material of the base material can be arbitrarily selected according to the application.
- cemented carbide with a high cobalt content stainless steel for large structural materials where wear resistance is important, and copper where wear resistance and heat dissipation are required simultaneously can be used.
- the diamond growth layer is effectively isolated by an intermediate layer made of a material that does not promote the graphitization of diamond, so that a sound diamond layer can be formed.
- the base material By making the base material into a member with a predetermined shape in advance, it is possible to save the labor and time of finishing after forming the diamond film, and it is possible to produce wear-resistant materials of various sizes and shapes. became.
- the basic material can be a normal cemented carbide containing WC and Co as main components.
- a diamond film is also formed on an iron group metal, for example, a stainless steel plate such as SUS. Formation is possible.
- a material (carbide or nitride) having an intermediate thermal expansion coefficient between diamond and the base material as the diamond-containing intermediate layer, the diamond film forming process and the use conditions accompanying the temperature rise Troubles due to peeling of the diamond forming layer can be greatly reduced.
- pulverized powder of diamond abrasive grains synthesized using a static ultra-high pressure can be used as the diamond particles distributed in the matrix. That is, these particles are mainly crushed cracks, and are pulverized single crystal fragments starting from the location where the crystal structure is disturbed, so that the crystallinity is good and the surface is single. It is only covered with one or several layers of heteroatoms or functional groups. Furthermore, impurities incorporated in the crystal in the purification step after pulverization are removed by chemical treatment, so that the amount of foreign elements mixed in is also reduced. This type of diamond therefore serves as a good starting point for growth.
- Detonation type diamond can also be used as a growth starting point.
- the primary particle size of this type is 10nm or less, but in the dry state it is strongly condensed and apparently becomes secondary particles of 100nm or more, so it is dispersed as much as possible to the primary particle size before use. It is necessary to keep. Note that the detonation diamond using dynamic ultra-high pressure has a very short synthesis time, and thus has a large amount of defects and a broken surface, and the crystallinity is not good.
- the diamond particles are dispersed in the matrix and serve as a starting point for forming a diamond film, submicron, that is, fine powder having an average particle diameter of 1 ⁇ m or less is preferable. Meter grade fine powder is preferred.
- the diamond content in the diamond-containing intermediate layer is preferably in the range of 1 to 40% as a mass percentage with respect to the entire matrix.
- the content of diamond is 1%, it may be difficult to form a smooth film with a uniform thickness due to insufficient growth starting point.
- the content exceeds 40%, the starting point diamond by the intermediate layer matrix The formed film may peel off due to a decrease in the fixing strength.
- the sized varieties have a narrow particle size distribution width.
- the surface is often covered with oxygen-containing functional groups.
- these functional groups are desorbed and the diamond surface is in a hydrogen-terminated state, so it is not necessary to consider the surface state of the starting diamond for diamond formation.
- the surface In the stage, the surface must be pre-terminated with hydrogen in order to improve adhesion to the matrix material (dispersion medium) in the intermediate layer of the growth origin, and to prevent oxidation or graphitization of diamond during the intermediate layer coating formation operation. Is desirable.
- a combination of a metal element and a non-metallic element forming a carbide, nitride, or boride of a transition metal (periodic table IV, V, or VI group metal) is used as a starting material.
- a combination of a metal element and a non-metallic element forming a carbide, nitride, or boride of a transition metal (periodic table IV, V, or VI group metal) is used as a starting material.
- These can be joined to the base material by welding due to heat generated during compound formation.
- an intermetallic compound can be further added to the above starting material.
- a carbide formed by a combination of a metal selected from (Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W) and a non-metal selected from (B, C), These powders are mixed with diamond fine powder as a matrix material for the purpose of forming borides and nitrides by carrying out the intermediate layer forming reaction in a nitrogen atmosphere, and further forming a mixture thereof.
- Boron nitride fine powder is also used as a source of boron and nitrogen.
- materials starting from metallic titanium include metals such as TiB, TiC, TiN, TiCN, Ti-BN, and Ti-B-C.
- metals such as TiB, TiC, TiN, TiCN, Ti-BN, and Ti-B-C.
- Non-metal combinations Ti-Al-C, Ti-Cr-C, Ti-Si-C, Ti-Ta-C, Ti-Mo-C, Ti-WC, Ti-Al-WC, Ti -Cr-Ni-C, Ti-Al-Ni-C, Ti-Al-B, Ti-Cr-B, Ti-Mo-B, Ti-Al-N, Ti-Si-N, Ti-Al-Si -N, Ti-Al-BN, Ti-Cr-BN, Ti-Si-BN, Ti-Al-Si-BN, Ti-Si-B-CN, etc.
- Metal-nonmetal combinations are possible. Furthermore, combinations in which Ti is replaced with other transition metal elements Cr, Ta, V
- Si, Al, and Ni in the components included above are the formation of intermetallic compounds with transition metals and, as a relatively low melting point component, the strongness between the base material and the diamond layer through the intermediate layer by diffusion and melting. It is considered to contribute to secure bonding. It is recognized that Ni, which is known to promote the graphitization of diamond, is not a hindrance when the content is as low as several percent or less. Therefore, when it is desired to contain an intermetallic compound with a transition metal in the matrix, Si, Al or a small amount of Ni is added.
- a preformed carbide or nitride fine powder such as WC, TiC, TaC, Cr 3 C 2 , TiN, and TaN can be added.
- fine powder or ultrafine powder is often used as it is for these starting raw material powders, but by subjecting the starting raw material powder to surface activation treatment by MA (mechanical alloying or mechanical activation) technology using a planetary mill or the like in advance. If the combustion temperature during the formation of the coating is lowered, it is effective for preventing the graphitization of diamond and reducing the strain generated in the formed film.
- MA mechanical alloying or mechanical activation
- the matrix material constituting the intermediate layer must be fixed on the base material by a chemical bond to form the diamond-containing intermediate layer.
- middle layer is accelerated
- a matrix raw material component for fixing diamond is attached to the surface of the base material, and then a method of causing mutual diffusion between the matrix raw material component and the base material component by a heating operation, or a base material component melt is applied to the matrix.
- the joining method by the method of infiltrating into a component can be mentioned.
- a welding technique is effective in which the coating layer material is transferred and deposited on the surface of the base material in a molten or semi-molten droplet state.
- high-temperature generation technology with a short duration includes spark discharge (ESD) to spark discharge alloying (ESA), arc discharge and other discharge technologies that prevent deterioration of diamond due to low energy,
- ESD spark discharge
- ESA spark discharge alloying
- arc discharge arc discharge
- other discharge technologies that prevent deterioration of diamond due to low energy
- a thermal spraying technique capable of forming a film is a suitable example. In both methods using electric discharge and thermal spraying, the temperature reached locally is higher than 2000 ° C, but since the high temperature duration is short, the film formation reaction is completed within the induction time for diamond to graphitize. It has been confirmed.
- the formation of the diamond-containing material film by the ESD technique is known.
- a consumable electrode (anode) 1 in which a welding material is formed into a rod shape is held in a holder 2 and fixed to a work table 3 or the like (base material) 4 Is connected to a power source (omitted) as a cathode.
- a minute discharge is generated between the two electrodes, the coating layer material (consumable electrode component) is transferred as a droplet, and is fixed to the surface of the material to be treated in a molten state, thereby forming the coating layer 5.
- a minute pulse vibration of several hundreds of Hz is given between the tip of the anode rod and the cathode surface, and a short intermittent (pulse) discharge having a duration of the order of microseconds keeps the discharge energy low and welds. Increase in temperature of objects can be suppressed.
- the discharge energy (E joule) per pulse is preferably in the range of 0.01 ⁇ E (J) ⁇ 10 as the ESD (ESA) operation condition for the coating material containing diamond. If E is less than 0.01 J, the input energy is insufficient, so that the coating raw material is not softened or melted. If it exceeds 10 J, the calorific value becomes excessive, and the graphitization of diamond becomes remarkable.
- the combination of the total number of pulses (N) in the total deposition step: 500 ⁇ N ⁇ 5400000 and the frequency of the pulse current (fHz): 0.0185 ⁇ f / N ⁇ 0.1 is a preferable range.
- transition metal powder can be used as a starting material, and diamond can be used as a carbon source combined therewith.
- amount of diamond powder mixed with metal powder of titanium or tungsten to be equal to or higher than the stoichiometric ratio related to carbide formation, an intermediate layer in which diamond powder is firmly fixed in diamond-derived carbide can be obtained, and carbide While maintaining the physical properties of the alloy substrate, a composite material having a diamond film starting from diamond fine powder in the carbide coating layer formed on the surface can be obtained.
- CVD and PVD methods can also be used.
- a material containing a metal that promotes the graphitization of diamond is used as a base material or a base member
- a ceramic layer or a ceramic raw material metal layer is formed in advance by a CVD or PVD method as an underlayer.
- the diamond particles are fixed in the ceramic layer, and at the same time, the basic material is caused by mutual diffusion between the basic material component and the ceramic component. Can be bonded to the ceramic layer.
- a coating layer was formed in a configuration according to FIG.
- a diamond film having a thickness of about 5 ⁇ m was formed by hot filament CVD using diamond in the core as a core, and used as a rotary sealing material for a sand pump.
- a diamond film having a thickness of about 5 ⁇ m was formed by a hot filament method using the diamond particles in the coating as a core, and used as a rotary sealant for a sand pump.
- Metallic titanium fine powder Toho Titanium, average particle size 20 ⁇ m
- carbon black Tokai Carbon, SRF, average particle size 66 nm, specific surface area 27 m 2 / g
- 50 nm diamond MD50-OB in mass ratio 77: 16: 6 was weighed, mixed thoroughly, and finished into a rod-shaped electrode bar having a diameter of 5 mm, a length of 50 mm, and a relative density of 80% by pressure molding.
- a titanium carbide layer having a thickness of about 15 ⁇ m and containing about 2% diamond was formed on the conical surface of a cemented carbide tip (13% Co-WC) base material for a race center by using an ESD technique.
- the formation layer was smoothed using a diamond grindstone, and a diamond film having a thickness of about 15 ⁇ m was formed thereon using a hot filament method.
- Metal chromium powder (PKh-1, GOST 5905-2004, average particle size 25 ⁇ m) and 50 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ nm diamond (MD50-OB, manufactured by Tomei Diamond) are weighed at a mass ratio of 95: 5 and mixed thoroughly. , A round bar electrode with a diameter of 5 mm, a length of 50 mm, and a relative density of 75% was manufactured.
- the coating layer was lightly polished and flattened with a # 400 diamond grindstone, and then a diamond film having a thickness of about 10 ⁇ m was formed using a hot filament CVD method.
- a rod-shaped electrode rod having a diameter of 5 mm, a length of 50 mm, and a relative density of 80% was finished by pressure molding.
- the workpiece as the base member is a SK-3 steel race center with a diameter of 12mm, a tip angle of 60 °, and a length of 18mm. This is mounted on the spark discharge device KPM50 and rotated at 30r.pm while discharging current 1.0 As A, a coating layer having a thickness of about 3 ⁇ m was formed.
- the covering layer contained about 2% (about 6 vol%) fine diamond.
- a diamond layer having a thickness of about 10 ⁇ m was formed using a microwave CVD apparatus and used as a center of a cylindrical grinder for polishing a cemented carbide roll.
- a chromium vapor deposition film having a thickness of about 0.1 ⁇ m was formed on a base material of cemented carbide (13% Co-WC). On this, diamond particles having an average particle diameter of 1 ⁇ m were dispersed by a spin coating method, and a chromium vapor deposition film having a thickness of about 1.2 ⁇ m was further formed.
- the obtained base material was held at 800 ° C. for 20 minutes in a hydrogen atmosphere, and a diffusion layer was formed between the cemented carbide and the chromium deposited film.
- the surface was lightly polished with a slurry in which diamond powder having an average particle diameter of about 1 ⁇ m was dispersed to expose the diamond, and diamond was deposited thereon by a hot filament CVD method.
- a chromium nitride film having a thickness of about 0.5 ⁇ m was formed as a base by vapor deposition.
- a chromium metal film having a thickness of about 0.1 ⁇ m was formed by vapor deposition on a cemented carbide (6% Co—WC) plate as a base material, and then a chromium nitride film was similarly formed on the metal chromium film by vapor deposition.
- a VC film having a thickness of about 0.5 ⁇ m is formed on a cemented carbide (20% Co—WC alloy) plate by sputtering, and diamond particles having an average particle diameter of 0.2 ⁇ m are deposited thereon by a dipping method.
- a 2 ⁇ m VC film was formed by sputtering.
- the temperature was maintained at 900 ° C. at 10 ⁇ 4 Torr, and diffusion of the cobalt component in the cemented carbide into the VC film was mainly performed.
- the surface was lightly polished using a slurry in which diamond powder having an average particle diameter of about 1 ⁇ m was dispersed to expose the diamond, and diamond was formed by a hot filament CVD method.
- the sprayed surface is ground using a # 800 diamond grindstone to expose the diamond buried in the sprayed material, and the TiC coating on the diamond particle surface is removed to expose the crystal surface. Formation was performed.
- diamond can be grown without being affected by the material of the base material, it is firmly bonded onto a cemented carbide or various steel materials containing an iron group metal having a growth inhibiting action. Since a healthy diamond layer can be deposited, a wear resistant coating can be formed on a wide range of components.
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Abstract
Description
放電や熔射を利用する手法は共に、局所における到達温度は2000℃を超える高温となるものの、高温持続時間が短いことから、ダイヤモンドがグラファイト化するための誘導時間内に膜形成反応が完結することが確認されている。なおESD技術によるダイヤモンド含有材料膜の形成は公知である。
次いで被覆中のダイヤモンド粒子を核として、熱フィラメント法により厚さ約5μmのダイヤモンド膜の形成を行い、サンドポンプの回転シール材に供した。
2 ホルダー
3 作業テーブル
4 被処理材(基礎材)
5 被覆層
Claims (15)
- 硬質材料からなる基礎材に、種子ダイヤモンド結晶をマトリックス中に保持含有する被覆層が表面に接合されたCVDダイヤモンド析出用基体であって、
(1) 前記種子ダイヤモンド結晶としてのダイヤモンド粒子の平均粒径が1μm以下であり、
(2) マトリックスがSi、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、Wからなる第一金属群から選ばれる1種以上の第一金属種及び/又は、該第一金属種とホウ素、炭素又はチッ素から選ばれる非金属物質との化合物である第一金属化合物を含有し、上記ダイヤモンド粒子は該マトリックス中に分散され、
(3) 上記硬質材料と被覆層との接合部に、上記第一金属種の金属原子及び硬質材料を構成する金属原子、或いはその一方の拡散によるに拡散層が形成されていることを特徴とする析出用基体。 - 前記マトリックスが前記第一金属化合物を主成分とし、さらに前記第一金属種と、Al、Si、Niからなる第二金属群から選ばれる第二金属種との間の金属間化合物をより少量含有する、請求項1に記載の析出用基体。
- 前記マトリックスがさらに、予め形成された遷移金属の炭化物、窒化物、ホウ化物を含有する、請求項1又は2に記載の析出用基体。
- 前記ダイヤモンド粒子の平均粒径が0.1μm以下である、請求項1に記載の析出用基体。
- 前記マトリックスが、全体に対する質量比にてダイヤモンド粒子を1乃至40%含有する、請求項1に記載の析出用基体。
- 前記基礎材が主成分としてWC及びCoを含有する、請求項1に記載の析出用基体。
- 前記ダイヤモンド粒子が整粒された粒子であり、かつ累積粒度分布表示においてD50値に対するD10値の比が0.6以上、またD90値の比が1.6以下である、請求項4~6の何れか一項に記載の析出用基体。
- 請求項1に記載のダイヤモンド析出用基体における析出面の形成方法であって、
(1) 硬質材料からなる基礎材の表面の一部を、Si、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、Wからなる第一金属群から選ばれる1種以上の第一金属種及び/又は、該第一金属種とホウ素、炭素又はチッ素から選ばれる非金属物質との化合物である第一金属化合物を含有するマトリックスで覆う工程、
(2) ダイヤモンド粒子を上記基礎材表面に分布せしめる工程、及び
(3) 上記ダイヤモンド粒子を、前記第一金属種及び/又は前記第一金属化合物を含有する前記マトリックスで保持する工程を有し、この際
(4) 上記工程(1)乃至(3)の少なくとも一つを熱の影響下で行うことにより上記硬質材料からなる基礎材とマトリックスとの境界に、前記第一金属種の原子及び上記硬質材料を構成する金属原子の双方或いは一方の原子が拡散した接合部を形成し、該接合部を介して硬質材料からなる基礎材とマトリックスとを接合せしめることを特徴とする方法。 - (5) Si、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、Wからなる第一金属群から選ばれる1種以上の前記第一金属種の粉末と、該第一金属種とホウ素、炭素又はチッ素から選ばれる非金属物質の粉末とを密に混合して混合粉とする工程、及び
(6) 該混合粉を加圧成形して電極棒とする工程
をさらに含み、
前記工程(6)において加圧成形された電極棒と前記基礎材との間で放電を行うことにより電極棒に含有された前記第一金属種を溶滴として前記基礎材の表面に到達せしめると共に、前記第一金属種のホウ化物、炭化物又はチッ化物である前記第一金属化合物を生成して基礎材の表面の一部にマトリックスを形成する
ことを特徴とする請求項8に記載のダイヤモンド析出用基体における析出面の形成方法。 - (5) Si、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、Wからなる第一金属群から選ばれる1種以上の前記第一金属種の粉末を加圧成形して電極棒とする工程をさらに含み、
前記電極棒を用いて前記第一金属種の粒子を基礎材の表面に移行させ、さらに基礎材の表面に移行した前記第一金属種を大気中の窒素との反応により窒化物に変換することで、基礎材表面に前記第一金属種及び第一金属化合物を含有する前記マトリックスを形成する
ことを特徴とする請求項8に記載のダイヤモンド析出用基体における析出面の形成方法。 - 前記放電が前記電極棒と基礎材との間における火花放電又はアーク放電であり、該放電により前記粉末を溶滴として移行させる、請求項9又は10に記載の方法。
- 前記移行を、前記第一金属種をターゲット材としてスパッタリングによって行う、請求項9又は10に記載の方法。
- 前記第一金属種に、Al、Si、Niからからなる第二金属群から選ばれる第二金属種の粉末を密に混合し、前記放電の際に発生熱の影響下で両者の反応により金属間化合物とし、マトリックス中に含有させる、請求項9の方法。
- 前記放電における単パルスエネルギーE、パルス電流の周波数f、及び全析出工程におけるパルス総数Nを次の範囲に設定して操作を制御する請求項11に記載の方法。
単パルスエネルギー E 0.01 ≦ E(J) ≦ 10
全析出工程におけるパルス総数 N 500 ≦ N ≦ 5400000
パルス電流の周波数 f 0.0185 ≦ f/N ≦ 0.1 - 請求項8~14の何れか一項に記載のダイヤモンド析出用基体における析出面の形成方法において用いられる電極棒であって、
Si、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、Wからなる第一金属群から選ばれる1種以上の前記第一金属種の粉末及び/又は該第一金属種とホウ素、炭素又はチッ素から選ばれる非金属物質の粉末とを密に混合して混合粉とし、該混合粉を加圧成形して成る
ことを特徴とするダイヤモンド析出用基体における析出面の形成方法において用いられる電極棒。
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CN117512384A (zh) * | 2023-10-31 | 2024-02-06 | 北京市计量检测科学研究院 | 一种金刚石/铜复合材料及其电弧成形方法 |
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