CN113403602A - PCBN cutter with nano-diamond film coating on surface and preparation method thereof - Google Patents
PCBN cutter with nano-diamond film coating on surface and preparation method thereof Download PDFInfo
- Publication number
- CN113403602A CN113403602A CN202110687456.XA CN202110687456A CN113403602A CN 113403602 A CN113403602 A CN 113403602A CN 202110687456 A CN202110687456 A CN 202110687456A CN 113403602 A CN113403602 A CN 113403602A
- Authority
- CN
- China
- Prior art keywords
- diamond
- nano
- cutter
- deposition
- pcbn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002113 nanodiamond Substances 0.000 title claims abstract description 51
- 238000009501 film coating Methods 0.000 title claims abstract description 48
- 239000007888 film coating Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 title claims abstract 15
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 63
- 239000010432 diamond Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000000151 deposition Methods 0.000 claims abstract description 36
- 230000008021 deposition Effects 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000005498 polishing Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 14
- 238000005137 deposition process Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 26
- 239000011248 coating agent Substances 0.000 abstract description 23
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 46
- 239000007789 gas Substances 0.000 description 24
- 238000005520 cutting process Methods 0.000 description 19
- 239000013078 crystal Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000004050 hot filament vapor deposition Methods 0.000 description 8
- 238000010900 secondary nucleation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Images
Classifications
-
- 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
- C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
-
- 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/342—Boron nitride
-
- 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
- C23C16/44—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 method of coating
- C23C16/50—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 method of coating using electric discharges
- C23C16/511—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 method of coating using electric discharges using microwave discharges
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides a PCBN cutter with a nano-diamond film coating on the surface and a preparation method thereof, wherein the preparation method comprises the following steps: dry polishing the pretreated PCBN cutter in nano diamond powder to brightness, then placing the PCBN cutter on a base station, placing the PCBN cutter in a microwave plasma chemical vapor deposition system for vacuumizing, and introducing a first reaction source gas after vacuumizing; starting a microwave plasma chemical vapor deposition system, exciting a first reaction source gas by microwave to generate a plasma ball, introducing a second reaction source gas to start deposition, and obtaining the PCBN cutter with the surface provided with the nano-diamond film coating after the deposition is finished; the preparation method optimizes the microwave plasma chemical vapor deposition process, uniformly deposits the nano-scale diamond coating on the surface of the cutter by regulating and controlling the preparation conditions, effectively improves the film quality and stability of the diamond coating, prolongs the service life of the cutter, and has better industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of superhard material film preparation, and particularly relates to a PCBN cutter with a nano-diamond film coating on the surface and a preparation method thereof.
Background
In recent years, Polycrystalline Cubic Boron Nitride (PCBN) cutters are increasingly used as a novel superhard material in modern precision machining, and particularly show incomparable superiority with other cutter materials in the fields of high-speed cutting, hard cutting, dry cutting and the like. PCBN is an artificial synthetic substance with hardness second to that of diamond, but different from the diamond tool, the PCBN tool has poor affinity with Fe, and is particularly suitable for cutting ferrous metal; compared with a hard alloy cutter, the durability of the PCBN cutter is more than 10 times, the cutting force is small when ultrahigh-strength materials and chemical active materials are cut at high speed, and no accumulated chip is generated in the cutting process; compared with a ceramic cutter, the PCBN cutter has higher hardness, wear resistance and thermal conductivity, better chemical stability, thermal stability and red hardness in machining, and can realize turning instead of grinding under specific cutting conditions, so that the machined workpiece obtains higher machining precision and surface quality and simultaneously greatly improves the production efficiency. However, since the cost of the PCBN tool is high, if it cannot be guaranteed that the tool will have a long life in the machining process, the production cost will be increased, and meanwhile, the severe wear of the tool will cause the workpiece to be scrapped and need to be re-machined, which seriously affects the production efficiency and economic benefits. Therefore, it is of great practical significance to find a method for improving the wear resistance and service life of the tool.
Covering a layer of diamond film on the surface of the PCBN cutter is an effective means for prolonging the service life of the PCBN cutter. The existing Chemical Vapor Deposition diamond film coating technology mainly uses a Hot Filament Chemical Vapor Deposition (HFCVD) method, but the HFCVD method has a complex preparation process, and the prepared diamond film has Filament pollution and great difficulty in improving the quality of the film. In addition, since the temperature of the filament in the HFCVD method is generally more than 2000 ℃, the filament material is volatilized into the reaction chamber, thereby introducing impurities into the thin film, reducing the purity of the diamond film, and resulting in low reproducibility and yield. In addition, the substrate material is mainly concentrated on diamond cutters, hard alloy cutters and ceramic cutters, and most of the diamond films on the surfaces of the coated cutters are in micron-scale. However, the micron diamond film has coarse and uneven grains, a rough coating surface, and difficulty in surface polishing, and causes great wear and high cutting force when the tool contacts with a workpiece, thereby seriously affecting the service life of the coated tool.
CN105861995A discloses ZrTiN-MoS2The tool with laminated Ti/Zr coating is made of high speed steel, hard alloy, cubic boron nitride or diamond as base material and MoS on the surface2the/Ti/Zr lubricating coating comprises a Ti transition layer, a Ti/Zr transition layer, a ZrTiN hard coating and MoS from a substrate to the surface of the coating in sequence2a/Ti/Zr lubricating coating alternating laminated composite structure; the cutter has more coatings, is prepared by adopting an arc plating and medium-frequency magnetron sputtering composite coating method, and has more complex process flow and higher cost.
CN106637143A discloses a preparation method of an MPCVD diamond film, which adopts inert gas Ar as catalytic gas in the deposition process to play the roles of refining the crystal grains of the diamond film, improving the hardness of the diamond film and improving the quality of the diamond film; however, the inert gas Ar can cause the reduction of the hydrogen concentration, so that enough active hydrogen atoms are not etched, the non-diamond phase components are increased, and the quality of the diamond film is influenced.
In summary, how to provide a continuous and compact thin film coating with a certain thickness that is deposited uniformly on the surface of the PCBN tool, which ensures that the bonding force and the supporting force between the thin film coating and the substrate are not changed, and improves the cutting performance, is a problem that needs to be solved at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a PCBN cutter with a nano-diamond film coating on the surface and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a preparation method of a PCBN cutter with a nano-diamond film coating on the surface, which comprises the following steps:
(1) dry polishing the pretreated PCBN cutter in nano diamond powder to brightness, then placing the PCBN cutter on a base station, placing the PCBN cutter in a microwave plasma chemical vapor deposition system for vacuumizing, and introducing a first reaction source gas after vacuumizing;
(2) and starting a microwave plasma chemical vapor deposition system, exciting a first reaction source gas by microwave to generate a plasma ball, introducing a second reaction source gas to start deposition, and obtaining the PCBN cutter with the surface provided with the nano-diamond film coating after the deposition is finished.
According to the preparation method, by adopting and optimizing a Microwave Plasma Chemical Vapor Deposition (MPCVD) process, a transition layer is not required to be prepared or surface modification is not required to be carried out on a PCBN cutter substrate, and the nano-scale diamond film coating which is continuous, compact, high in adhesive strength, large in binding force, uniform in coating thickness and smooth and flat in surface can be obtained through Deposition, so that abrasion and cutting force generated when the PCBN cutter is in contact with a workpiece can be effectively reduced, and the service life of the coated cutter is prolonged; compared with the conventional Hot Filament Chemical Vapor Deposition (HFCVD) process, the method simplifies the process flow, avoids the problem of film growth stability caused by uneven wire drawing, avoids the problem of product surface pollution caused by Hot Filament breakage in the preparation process, and greatly improves the product yield.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the pretreatment in the step (1) comprises ultrasonic cleaning and drying.
Preferably, the cleaning solution adopted by the ultrasonic cleaning is acetone.
Preferably, the ultrasonic cleaning time is 8-12 min, such as 8min, 9min, 10min, 11min or 12min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the drying is carried out in a constant temperature drying oven.
Preferably, the drying time is not less than 4min, such as 4min, 5min, 6min, 7min, 8min, or 9min, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the drying temperature is 45 to 55 ℃, for example, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃ or 55 ℃, but not limited to the values listed, and other values not listed within the range of values are also applicable.
According to the invention, the surface purification and crystal planting process is comprehensively optimized by the cutter pretreatment method, and the adsorbates and pollutants on the surface of the cutter are effectively removed by selecting a proper reagent, so that the surface microscopic quality is improved; and then nano diamond powder is used for dry polishing until the surface is bright, so that the activity and high-energy points of the surface of the cutter are increased. Compared with ultrasonic treatment of a diamond powder-containing suspension, the crystal planting process can obtain more defects such as scratches, dislocations, crystal boundaries and the like, the defects provide nucleation work for diamond nucleation, and diamond powder fragments remained in the defects on the surface of the cutter provide nucleation points for MPCVD deposited diamond, so that the nucleation density is improved. Meanwhile, the nucleation growth mode enables the diamond film and the cutter to act with an anchor chain effect, so that the adhesive force of the film and the substrate is improved.
As a preferable embodiment of the present invention, the nano-diamond powder of the step (1) has a particle size of 10to 500nm, for example, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm or 500nm, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the dry polishing time in step (1) is 10to 25min, for example, 10min, 12min, 15min, 18min, 20min, 22min, or 25min, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the present invention, the height of the base in the step (1) is 40to 55mm, for example, 40mm, 42mm, 45mm, 48mm, 50mm, 52mm, or 55mm, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, the height of the base has a certain influence on the quality of the final film formation. If the height of the base station is too high, the ionization degree of a sample contacting the center position of the plasma is increased; if the height of the base station is too low, the distance between the plasma ball and the sample is increased, and the plasma glow cannot completely cover the sample; both of which lead to a decrease in the surface uniformity and film stability of the coating.
In the invention, the step (1) of vacuumizing to limit vacuum avoids poor crystal texture quality of the nano diamond coating and high impurity content in the film caused by impurity gas contained in an MPCVD system.
In a preferred embodiment of the present invention, the first precursor gas in step (1) is H2。
Preferably, the second precursor gas of step (1) is CH4。
Preferably, the CH4And H2The gas flow rate ratio is (0.5 to 8):50, for example, 1:100, 1:50, 1:25, 3:50, 2:25, 1:10, 3:25, 7:50, or 4:25, but is not limited to the recited values, and other values not recited within the range of the values are also applicable.
In the present invention, the CH4And H2The gas flow rate is given in units of "sccm".
In the present invention, during the deposition processThe proportion of the source gases for the reaction is of critical importance. If the carbon source (CH)4) When the content is excessive, H is inevitably reduced2The concentration and a large amount of hydrocarbon groups absorbed on the surface of the cutter are not etched by enough active hydrogen atoms, so that the non-diamond phase components are increased, and the purity of diamond in the film is reduced; in addition, the high concentration of the carbon source can cause the nucleation and growth rate of diamond grains to be too fast, and the film thickness is not easy to control. If H is2When the content is too large, the surface of the cutter does not have enough hydrocarbon groups for forming diamond grains, so that the deposition rate of the film coating is reduced; in addition, fewer hydrocarbon groups reduce the probability of secondary nucleation, and thus smaller size diamond grains cannot be obtained.
In a preferred embodiment of the present invention, in the process of generating the plasma sphere in the step (2), the power of the microwave is 500 to 700W, for example, 500W, 550W, 600W, 650W, 700W, etc., but the microwave is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the pressure of the working chamber during the plasma ball generation in step (2) is 8to 12Torr, such as 8Torr, 9Torr, 10Torr, 11Torr, or 12Torr, but not limited to the values listed, and other values not listed in this range are also applicable.
In a preferred embodiment of the present invention, in the deposition process in step (2), the power of the microwave is adjusted to 1000 to 2000W, for example, 1000W, 1100W, 1200W, 1300W, 1400W, 1500W, 1600W, 1700W, 1800W, 1900W, 2000W, etc., but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the pressure of the working chamber during the deposition in step (2) is 20to 60Torr, such as 20Torr, 30Torr, 40Torr, 50Torr or 60Torr, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
According to the preparation method, the volume and the density of the generated plasma spheres are further controlled by cooperatively regulating the microwave power and the working cavity air pressure, so that the uniformity of the surface temperature field of the cutter substrate, and the deposition rate and the growth quality of a film are improved. If the microwave power is too high during deposition, the intensity of the plasma is correspondingly increased, so that the surface of the cutter is bombarded more intensely by ions, and the temperature of the base body of the cutter is increased; if the microwave power is too low during deposition, the volume of the plasma ball is reduced, and the plasma density is reduced; both fail to obtain a high quality nano-diamond film with a uniform surface. If the air pressure of the working cavity during deposition is too high, the average free path of molecules is reduced, the average free path of hydrogen atoms and carbon-containing groups is shortened, secondary nucleation is not easy to generate when the hydrogen atoms and the carbon-containing groups collide with a cutter matrix, and diamond particles are easy to grow; if the air pressure of the working cavity during deposition is too small, the number of free radicals in the reaction chamber is reduced, and carbon elements capable of generating diamond are reduced to a certain extent, so that the growth rate of the diamond is reduced, and the cutting performance of the diamond coated tool is finally influenced along with the appearance of more graphite and amorphous carbon in the film and the reduction of adhesive force between the coating and the tool substrate.
Preferably, in the deposition process in the step (2), the temperature of the base is 600 to 900 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the deposition time in step (2) is 6-12 h, such as 6h, 7h, 8h, 9h, 10h, 11h or 12h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the preparation method effectively inhibits the growth of crystal grains through secondary nucleation, thereby improving the film quality and stability of the diamond coating.
In a preferred embodiment of the present invention, the thickness of the nanodiamond thin film coating in step (2) is 5 to 15 μm, for example, 5 μm, 6 μm, 7 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, or 15 μm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) ultrasonically cleaning a PCBN cutter for 8-12 min by using acetone, drying for not less than 4min at 45-55 ℃, then dry-polishing in diamond powder with the particle size of 10-500 nm for 10-25 min, then placing on a base station with the height of 40-55 mm, placing in a microwave plasma chemical vapor deposition system, vacuumizing to the limit vacuum, and introducing a first reaction source gas after vacuumizing;
(2) starting a microwave plasma chemical vapor deposition system, setting the microwave power to be 500-700W, setting the air pressure of a working cavity to be 8-12 Torr, exciting a first reaction source gas to generate a plasma ball, then introducing a second reaction source gas to start deposition, wherein the gas flow ratio of the second reaction source gas to the first reaction source gas is (0.5-8): 50, adjusting the microwave power to be 1000-2000W in the deposition process, setting the air pressure of the working cavity to be 20-60 Torr, setting the temperature of a base station to be 600-900 ℃, depositing for 6-12 h, and obtaining the PCBN cutter with the nano diamond film coating of 5-15 mu m on the surface after deposition is finished.
In another aspect, the invention provides a PCBN cutter, and the surface of the PCBN cutter is provided with the nano-diamond film coating prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the invention adopts and optimizes the MPCVD process, and can directly deposit and obtain the continuous compact, high adhesive strength, large binding force, even coating thickness and smooth and flat surface nano-scale diamond film coating without preparing a transition layer or surface modification on the PCBN cutter substrate in advance, thereby solving the problems of complex preparation process, micron-scale crystal grains on the surface of the coating, poor binding force between the film and the cutter, difficult post-polishing and the like in the prior art for preparing the diamond coating by the HFCVD process; the height of a base station, microwave power, working chamber air pressure and gas proportion in the MPCVD process are further controlled, so that the grain size and the film uniformity are further controlled, the abrasion and cutting force generated when the cutter is in contact with a workpiece are reduced, and the service life of the cutter is further prolonged;
(2) the preparation method has simple process flow, MPCVD has no internal electrode, can avoid electrode discharge, and the axisymmetric plasma ball is not contacted with the wall of the vacuum vessel, thereby reducing pollution.
Drawings
Fig. 1 is a process flow chart of the process of preparing a cutting tool with a nano-diamond film coating on the surface according to example 1 of the present invention.
FIG. 2 is a surface topography of the nano-diamond film coating on the surface of the cutting tool provided in example 1 of the present invention.
FIG. 3 is a grain morphology diagram of the tool surface nano-diamond thin film coating provided in example 1 of the present invention.
FIG. 4 is a sectional view of the tool surface nano-diamond film coating provided in example 1 of the present invention.
Fig. 5 is an XRD pattern of the nano-diamond film coating on the surface of the tool provided in example 1 of the present invention.
FIG. 6 is a Raman spectrum of the nano-diamond film coating on the surface of the cutting tool provided in example 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of a cutting tool with a nano-diamond film coating on the surface, and the process flow chart of the preparation method is shown in figure 1.
The preparation method comprises the following steps:
(1) ultrasonically cleaning PCBN cutter with acetone for 10min, drying at 50 deg.C for 4min, and adjusting the particle diameter toDry polishing 100nm diamond powder for 15min to brightness, placing on a 40 mm-high base table, placing in an MPCVD system, vacuumizing to limit vacuum, introducing H2；
(2) Starting the MPCVD system, setting the microwave power to be 600W, setting the air pressure of the working chamber to be 10Torr, and exciting H2Generating plasma ball, and introducing CH4Starting deposition of said CH4And H2The gas flow ratio of the gas flow ratio is 1:50, the microwave power is adjusted to be 1500W in the deposition process, the air pressure of the working cavity is 40Torr, the temperature of the base station is 700 ℃, the deposition is carried out for 10h, and the PCBN cutter with the nano-diamond film coating on the surface is obtained after the deposition is finished.
The nano-diamond film coating on the surface of the PCBN cutter is characterized, the surface topography is shown as figure 2, the grain topography is shown as figure 3, the cross-sectional topography is shown as figure 4, the XRD spectrum is shown as figure 5, and the Raman spectrum is shown as figure 6.
As can be seen from FIG. 2, the nano-diamond coating has been uniformly deposited on the surface of the PCBN tool, the coated diamond film is continuous, compact in structure and high in surface smoothness, obvious grain boundaries exist among grains, and an obvious secondary nucleation phenomenon can be observed at the grain boundaries, which indicates that the prepared nano-diamond film has high quality.
As can be seen from fig. 3, the diamond grains in the thin film coating have good crystallinity, are clustered and have a typical nanoscale diamond structure, i.e., a so-called cauliflower-like morphology, and the diamond grains have substantially the same size and an average size of 50nm or less.
As can be seen from fig. 4, the nano-diamond film does not grow in a columnar shape as in the conventional film, but is a growth mode in which grains are stacked. The secondary nucleation phenomenon is continuously generated on the surface of the film in the process of the growth of the nano-diamond film, the growth of crystal grains is inhibited, the crystal grains are refined, and the diamond crystal grains are continuously accumulated on the surface of the film along with the extension of the deposition time. In addition, it can be observed from the cross-sectional morphology that the surface of the nano-diamond film was smooth and flat, which is consistent with the results obtained in fig. 2.
As is clear from fig. 5, there are two distinct diffraction peaks at 43.92 ° 2 θ and 75.32 ° 2 θ, which correspond to the (111) and (220) crystal planes of the diamond crystal, respectively, indicating that the nano-diamond film has high crystallinity and high grain orientation density.
As can be seen from FIG. 6, the depth is 1332cm-1A wider raman scattering peak (D peak) appears, indicating that the film contains diamond phase. The reason why the peak is wide is that the D peak and the diamond characteristic peak in the vicinity thereof are superimposed on each other. At 1579cm-1The G peak at (a) corresponds to graphitic and amorphous carbon structures. At 1150cm-1The characteristic peaks of the nano-diamond appearing nearby show that the diamond component in the film is increased, the crystal grains are refined, and the purity of the film is higher. In addition, the drift amount of the G peak in the Raman spectrum is small, which shows that the residual stress in the film coating is small, and the quality of the nano-diamond film is high.
Example 2:
the embodiment provides a preparation method of a PCBN cutter with a nano-diamond film coating on the surface, which comprises the following steps:
(1) ultrasonically cleaning PCBN cutter with acetone for 8min, drying at 45 deg.C for 5min, dry-polishing in diamond powder with particle size of 10nm for 20min to brightness, placing on a base station with height of 55mm, placing in MPCVD system, vacuumizing to limit vacuum, vacuumizing, and introducing H2；
(2) Starting the MPCVD system, setting the microwave power at 500W and the working chamber pressure at 8Torr, exciting H2Generating plasma ball, and introducing CH4Starting deposition of said CH4And H2The gas flow ratio of the deposition process of the PCBN tool is 4:25, the gas pressure of the working cavity is 20Torr, the temperature of the base platform is 600 ℃, the deposition is carried out for 12 hours, and the PCBN tool with the nano-diamond film coating on the surface is obtained after the deposition is finished.
Example 3:
the embodiment provides a preparation method of a PCBN cutter with a nano-diamond film coating on the surface, which comprises the following steps:
(1) firstly, the PCBN cutter is firstlyUltrasonically cleaning with acetone for 12min, drying at 45 deg.C for 4min, dry-polishing in 500nm diamond powder for 18min to brightness, placing on a 45mm height base table, vacuumizing in MPCVD system to limit vacuum, vacuumizing, and introducing H2；
(2) Starting the MPCVD system, setting the microwave power at 700W and the working chamber pressure at 12Torr, exciting H2Generating plasma ball, and introducing CH4Starting deposition of said CH4And H2The gas flow ratio of the gas flow ratio is 1:100, the microwave power is adjusted to be 2000W in the deposition process, the air pressure of the working cavity is 60Torr, the temperature of the base station is 900 ℃, the deposition is carried out for 6h, and the PCBN cutter with the nano-diamond film coating on the surface is obtained after the deposition is finished.
Example 4:
this example provides a method of making a PCBN tool with a nanodiamond thin film coating on the surface, which is comparable to the method of example 1, except that: the height of the base table in the step (1) is 35 mm.
Example 5:
this example provides a method of making a PCBN tool with a nanodiamond thin film coating on the surface, which is comparable to the method of example 2, except that: the height of the base table in the step (1) is 60 mm.
Example 6:
this example provides a method of making a PCBN tool with a nanodiamond thin film coating on the surface, which is comparable to the method of example 2, except that: and (3) adjusting the microwave power to 800W in the deposition process in the step (2).
Example 7:
this example provides a method of making a PCBN tool with a deep sub-micron diamond film coating on the surface, the method being referred to the method of example 3, except that: and (3) adjusting the microwave power to 2200W in the deposition process in the step (2).
Example 8:
this example provides a method of making a PCBN tool with a nanodiamond thin film coating on the surface, which is comparable to the method of example 2, except that: and (3) the pressure of the working chamber in the deposition process in the step (2) is 10 Torr.
Example 9:
this example provides a method of making a PCBN tool with a deep sub-micron diamond film coating on the surface, the method being referred to the method of example 3, except that: and (3) the pressure of the working chamber in the deposition process in the step (2) is 70 Torr.
Comparative example 1:
this comparative example provides a method of making a PCBN tool with a sub-micron diamond film coating on the surface, the method of manufacture being referenced to that of example 1, except that: in the step (1), the PCBN cutter does not carry out nano-diamond powder dry polishing treatment, but adopts a diamond-containing powder alcohol suspension for ultrasonic treatment.
The surface quality, diamond grain size, film thickness and uniformity of the tool with diamond film coating obtained in examples 1to 9 and comparative example 1 were observed, and the results are shown in table 1.
TABLE 1
In the embodiment 1-3, the microwave plasma chemical vapor deposition technology is adopted, the PCBN cutter pretreatment and crystal planting process are optimized, and the reaction conditions in the deposition process are further controlled, so that the surface of the cutter is provided with the nano-diamond film coating which is continuous and compact, uniform in coating thickness, flat and smooth in surface and not easy to cause stress concentration, the abrasion and cutting force generated when the cutter is in contact with a workpiece are effectively reduced, and the service life of the coated cutter is prolonged; in the embodiments 4 to 5, the height of the base table is respectively reduced and increased in the preparation process, so that the distance between the cutter substrate and the plasma ball is remarkably changed, the smoothness of the obtained coating and the stability of the film are reduced, and particularly when the height of the base table is too low, the plasma glow can not completely cover the sample, and the quality of the film is seriously reduced; example 6 the microwave power during deposition was reduced during the preparation process, resulting in a reduction in plasma density, a reduction in thickness and uniformity of the resulting film, and cracks appearing on the surface of the coating; example 7 in the preparation process, the microwave power during deposition is increased, which leads to the increase of the substrate temperature and the reduction of the energy of active groups, thereby reducing the probability of secondary nucleation, increasing the grain size of the obtained diamond film to submicron level, and obviously increasing the surface roughness of the coating; example 8 in the preparation process, the working chamber air pressure is reduced, the growth rate of diamond is reduced, and the cutting performance of the diamond coated cutter is influenced; example 9 the working chamber pressure was increased during the preparation process, the mean free path of hydrogen atoms and carbon containing groups was shortened, secondary nucleation was not easily generated upon collision with the tool substrate, resulting in easy growth of diamond particles.
In the comparative example 1, the conventional crystal planting process is adopted, so that the micro defects and nucleation centers on the surface of the cutter substrate are fewer, the initial and secondary nucleation rates are reduced, and the quality of the obtained diamond film coating is poorer.
It can be seen from the above examples and comparative examples that the preparation method of the present invention, by adopting and optimizing the MPCVD process, can deposit and obtain a continuous, compact, high adhesion strength, large bonding force, uniform coating thickness, smooth and flat surface nanoscale diamond film coating without preparing a transition layer or modifying the surface on the PCBN tool substrate in advance, and solves the problems of complex preparation process, micron-sized grains on the surface of the coating, poor bonding force between the film and the tool, difficult post-polishing, etc. existing in the existing HFCVD process for preparing diamond coatings; the height of a base table, the microwave power, the air pressure of a working cavity and the gas ratio in the MPCVD process are further controlled, so that the grain size and the film uniformity are further controlled, the abrasion and the cutting force generated when the tool is in contact with a workpiece are reduced, and the service life of the PCBN tool is further prolonged; the preparation method has simple process flow, the MPCVD has no internal electrode, can avoid electrode discharge, and the axisymmetric plasma sphere is not contacted with the wall of the vacuum vessel, thereby reducing pollution.
The applicant states that the present invention is illustrated by the above examples to show the product and detailed method of the present invention, but the present invention is not limited to the above products and detailed method, i.e. it is not meant that the present invention must rely on the above products and detailed method to be carried out. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents thereof, additions of additional operations, selection of specific ways, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of PCBN cutter with a nano-diamond film coating on the surface is characterized by comprising the following steps:
(1) dry polishing the pretreated PCBN cutter in nano diamond powder to brightness, then placing the PCBN cutter on a base station, placing the PCBN cutter in a microwave plasma chemical vapor deposition system for vacuumizing, and introducing a first reaction source gas after vacuumizing;
(2) and starting a microwave plasma chemical vapor deposition system, exciting a first reaction source gas by microwave to generate a plasma ball, introducing a second reaction source gas to start deposition, and obtaining the PCBN cutter with the surface provided with the nano-diamond film coating after the deposition is finished.
2. The method according to claim 1, wherein the pretreatment of step (1) comprises ultrasonic cleaning and drying;
preferably, the cleaning solution adopted by the ultrasonic cleaning is acetone;
preferably, the ultrasonic cleaning time is 8-12 min;
preferably, the drying is carried out in a constant temperature drying oven;
preferably, the drying time is not less than 4 min;
preferably, the drying temperature is 45-55 ℃.
3. The method according to claim 1 or 2, wherein the nano-diamond powder of step (1) has a particle size of 10to 500 nm.
4. The method according to any one of claims 1to 3, wherein the dry polishing time in the step (1) is 10to 25 min.
5. The production method according to any one of claims 1to 4, wherein the first precursor gas of step (1) is H2；
Preferably, the second precursor gas of step (1) is CH4；
Preferably, the CH4And H2The gas flow rate ratio of (0.5-8): 50.
6. The method according to any one of claims 1to 5, wherein in the step (2), the power of the microwave is 500 to 700W;
preferably, the pressure of the working chamber in the process of generating the plasma ball in the step (2) is 8-12 Torr.
7. The method according to any one of claims 1to 6, wherein the power of the microwave is adjusted to 1000 to 2000W during the deposition in step (2);
preferably, in the deposition process in the step (2), the pressure of the working chamber is 20to 60 Torr;
preferably, in the deposition process in the step (2), the temperature of the base station is 600-900 ℃;
preferably, the deposition time in the step (2) is 6-12 h.
8. The method according to any one of claims 1to 7, wherein the thickness of the nanodiamond thin film coating of step (2) is 5 to 15 μm.
9. The method of any one of claims 1to 8, comprising the steps of:
(1) ultrasonically cleaning a PCBN cutter for 8-12 min by using acetone, drying for not less than 4min at 45-55 ℃, then dry-polishing in diamond powder with the particle size of 10-500 nm for 10-25 min, then placing on a base station with the height of 40-55 mm, placing in a microwave plasma chemical vapor deposition system, vacuumizing to the limit vacuum, and introducing a first reaction source gas after vacuumizing;
(2) starting a microwave plasma chemical vapor deposition system, setting the microwave power to be 500-700W, setting the air pressure of a working cavity to be 8-12 Torr, exciting a first reaction source gas to generate a plasma ball, then introducing a second reaction source gas to start deposition, wherein the gas flow ratio of the second reaction source gas to the first reaction source gas is (0.5-8): 50, adjusting the microwave power to be 1000-2000W in the deposition process, setting the air pressure of the working cavity to be 20-60 Torr, setting the temperature of a base station to be 600-900 ℃, depositing for 6-12 h, and obtaining the PCBN cutter with the nano diamond film coating of 5-15 mu m on the surface after deposition is finished.
10. A PCBN cutter, wherein the surface of the PCBN cutter has a nano-diamond thin film coating prepared by the method of any one of claims 1to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110687456.XA CN113403602B (en) | 2021-06-21 | 2021-06-21 | PCBN cutter with nano-diamond film coating on surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110687456.XA CN113403602B (en) | 2021-06-21 | 2021-06-21 | PCBN cutter with nano-diamond film coating on surface and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113403602A true CN113403602A (en) | 2021-09-17 |
| CN113403602B CN113403602B (en) | 2023-10-27 |
Family
ID=77682170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110687456.XA Active CN113403602B (en) | 2021-06-21 | 2021-06-21 | PCBN cutter with nano-diamond film coating on surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113403602B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114807907A (en) * | 2022-05-05 | 2022-07-29 | 南方科技大学 | MPCVD carrier and method for depositing diamond coating on surface of cutter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5370912A (en) * | 1988-10-31 | 1994-12-06 | Norton Company | Diamond film deposition with a microwave plasma |
| CN103911596A (en) * | 2014-02-27 | 2014-07-09 | 武汉工程大学 | Preparation apparatus for diamond film and method for preparing diamond film by using apparatus |
| CN111378954A (en) * | 2018-12-27 | 2020-07-07 | 上海征世科技有限公司 | Device and method for preparing diamond film |
-
2021
- 2021-06-21 CN CN202110687456.XA patent/CN113403602B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5370912A (en) * | 1988-10-31 | 1994-12-06 | Norton Company | Diamond film deposition with a microwave plasma |
| CN103911596A (en) * | 2014-02-27 | 2014-07-09 | 武汉工程大学 | Preparation apparatus for diamond film and method for preparing diamond film by using apparatus |
| CN111378954A (en) * | 2018-12-27 | 2020-07-07 | 上海征世科技有限公司 | Device and method for preparing diamond film |
Non-Patent Citations (2)
| Title |
|---|
| 刘洋: ""MPCVD合成聚晶金刚石厚膜生长工艺研究"", 《中国优秀硕士学位论文全文数据库(基础科学辑)》 * |
| 熊礼威 等: ""甲烷体积分数对纳米金刚石薄膜形貌的影响"", 《表面技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114807907A (en) * | 2022-05-05 | 2022-07-29 | 南方科技大学 | MPCVD carrier and method for depositing diamond coating on surface of cutter |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113403602B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6258237B1 (en) | Electrophoretic diamond coating and compositions for effecting same | |
| CN102586777B (en) | Preparation method for CBN (Cubic Boron Nitride) coated cutter based on micrometer/nanometer diamond transition layer | |
| JP5891639B2 (en) | Polycrystalline diamond and manufacturing method thereof, scribe tool, scribe wheel, dresser, rotary tool, water jet orifice, wire drawing die, and cutting tool | |
| CN111482622B (en) | Coated cutting tool and preparation method thereof | |
| CN1219109C (en) | Hard alloy matix complex shape cutter diamond coating preparation method | |
| CN108396309B (en) | Cubic boron nitride coating cutter and preparation method thereof | |
| CN108220916B (en) | A kind of preparation method of the GNCD-cBN nanocomposite laminated coating cutter with toughening mechanisms | |
| US11684981B2 (en) | Ultra-fine nanocrystalline diamond precision cutting tool and manufacturing method therefor | |
| CN113403602B (en) | PCBN cutter with nano-diamond film coating on surface and preparation method thereof | |
| CN114703452B (en) | CoCrFeNi high-entropy alloy doped amorphous carbon film and preparation method thereof | |
| US20210237168A1 (en) | Silicon nitride ceramic tool comprising diamond film and method of preparing the same | |
| Tang et al. | Nanocrystalline diamond films produced by direct current arc plasma jet process | |
| JPS62138395A (en) | Preparation of diamond film | |
| JP3291105B2 (en) | Hard carbon film and hard carbon film coated member | |
| US6500488B1 (en) | Method of forming fluorine-bearing diamond layer on substrates, including tool substrates | |
| KR20150004664A (en) | Pre-processes for diamond film coating and diamond film coating method using the same | |
| CN110629174A (en) | Method for preparing Ti-Al-N hard film by using pull-type nitrogen plasma enhanced reaction atmosphere environment | |
| CN104789937A (en) | Production method for drawing mold with nano-scale diamond coating on inner hole surface | |
| EP0230927B1 (en) | Diamond manufacturing | |
| KR100484263B1 (en) | A deposition method of coating film with fine-crystalline diamond to cutting tool | |
| Zhang et al. | Study on tribology and cutting performance of boron doped diamond composite coated tool | |
| CN114703458B (en) | Application of CoCrFeNi high-entropy alloy doped amorphous carbon film in preparation of material under heavy-load working condition | |
| Jin et al. | Effect of Different Deposition Pressure on Diamond Films Deposited by Hot Filament Chemical Vapor Deposition | |
| KR970001005B1 (en) | Wear resistant components coated with a diamond particle dispersed hard ceramic films and its synthesis methods | |
| CN114807907A (en) | MPCVD carrier and method for depositing diamond coating on surface of cutter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |