CN113403602B - 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
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- CN113403602B CN113403602B CN202110687456.XA CN202110687456A CN113403602B CN 113403602 B CN113403602 B CN 113403602B CN 202110687456 A CN202110687456 A CN 202110687456A CN 113403602 B CN113403602 B CN 113403602B
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- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002113 nanodiamond Substances 0.000 title claims abstract description 52
- 238000009501 film coating Methods 0.000 title claims abstract description 48
- 239000007888 film coating Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000010432 diamond Substances 0.000 claims abstract description 67
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 57
- 238000000151 deposition Methods 0.000 claims abstract description 34
- 230000008021 deposition Effects 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 24
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000005137 deposition process Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000005498 polishing Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 28
- 239000011248 coating agent Substances 0.000 abstract description 27
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 49
- 239000007789 gas Substances 0.000 description 22
- 239000013078 crystal Substances 0.000 description 18
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 description 16
- 238000005520 cutting process Methods 0.000 description 15
- 238000004050 hot filament vapor deposition Methods 0.000 description 10
- 238000010899 nucleation Methods 0.000 description 8
- 238000010900 secondary nucleation Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 206010028980 Neoplasm Diseases 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
- 239000002156 adsorbate Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 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
- 238000005336 cracking Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 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
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 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
- 238000012797 qualification Methods 0.000 description 1
- 238000006467 substitution reaction 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
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
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: the PCBN cutter after pretreatment is dried and polished in nano diamond powder until the PCBN cutter is bright, then the PCBN cutter is placed on a base station, placed in a microwave plasma chemical vapor deposition system for vacuumizing, and then the PCBN cutter is introduced with first reaction source gas after vacuumizing; starting a microwave plasma chemical vapor deposition system, exciting a first reaction source gas by microwaves to generate plasma balls, then introducing a second reaction source gas to start deposition, and obtaining the PCBN tool with the nano-diamond film coating on the surface after the deposition is completed; 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, as a novel superhard material, a polycrystalline cubic boron nitride (Polycrystalline Cubic Boron Nitride, PCBN) cutter is increasingly applied to modern precision machining, and particularly shows incomparable superiority in the fields of high-speed cutting, hard cutting, dry cutting and the like. PCBN is an artificially synthesized substance with hardness inferior to that of diamond, but unlike a diamond cutter, the PCBN cutter has poor affinity with Fe and is particularly suitable for cutting processing of ferrous metals; compared with a hard alloy cutter, the durability of the PCBN cutter is more than 10 times that of the PCBN cutter, the cutting force is small when the ultra-high strength material and the chemical active material are cut at high speed, and no accumulated chip tumor is generated in the cutting process; compared with a ceramic cutter, the PCBN cutter has higher hardness, wear resistance and heat conductivity, better chemical stability, thermal stability and processing red hardness, and can realize turning instead of grinding under specific cutting conditions, so that the processed workpiece has higher processing precision and surface quality, and meanwhile, the production efficiency is greatly improved. However, because the PCBN cutter has higher cost, if the PCBN cutter cannot ensure that the PCBN cutter has longer service life in the processing process, the production cost is increased, and meanwhile, the workpiece is scrapped and needs to be reprocessed due to severe abrasion of the cutter, so that the production efficiency and economic benefit are seriously affected. Therefore, it is of great practical importance to find a method of improving the wear resistance and the service life of a tool.
Covering a layer of diamond film on the surface of PCBN tool is an effective means of prolonging the service life. The existing chemical vapor deposition diamond film coating technology is mainly based on a hot filament chemical vapor deposition (Hot Filament Chemical Vapor Deposition, HFCVD) method, but the HFCVD method is complex in process, and the prepared diamond film has the pollution of a filament and has 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 volatilizes into the reaction chamber, thereby introducing impurities into the thin film, reducing the purity of the diamond film, resulting in lower reproducibility and yield. In addition, the matrix material is mainly concentrated on diamond tools, hard alloy tools and ceramic tools, and the diamond film on the surface of the coated tools is mostly in the micron order. However, the micro diamond film has coarse and uneven grains, the surface of the coating is rough, surface polishing treatment is difficult to carry out, and meanwhile, larger abrasion and higher cutting force are generated when the cutter is contacted with a workpiece, so that the service life of the coated cutter is seriously influenced.
CN105861995A discloses a ZrTiN-MoS 2 A Ti/Zr laminated coating cutter and a preparation process thereof, wherein the cutter base material is high-speed steel, hard alloy, cubic boron nitride or diamond, and the cutter surface is MoS 2 The 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 sequence 2 A laminated composite structure of Ti/Zr lubrication coating alternation; the cutter has more coating layers, is prepared by adopting an arc plating and intermediate frequency magnetron sputtering composite coating method, and has more complex process flow and higher cost.
CN106637143a discloses a preparation method of MPCVD diamond film, which adopts inert gas Ar as catalytic gas in the deposition process to refine crystal grains of the diamond film, improve hardness of the diamond film, and improve quality of the diamond film; however, the inert gas Ar can cause the reduction of the hydrogen concentration, so that no enough active hydrogen atoms are used for etching the diamond film, and the non-diamond phase component is increased, thereby affecting the quality of the diamond film.
In summary, how to provide a continuous and compact film coating with a certain thickness on the surface of a PCBN tool, which is simple in process flow, ensures that the bonding force and supporting force between the PCBN tool and a substrate are not changed, and improves cutting performance is a current urgent problem.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide the PCBN cutter with the nano diamond film coating on the surface and the preparation method thereof, wherein the preparation method optimizes the microwave plasma chemical vapor deposition process, and the nano diamond coating is deposited on the surface of the PCBN cutter by regulating and controlling the preparation conditions, so that the film quality and the stability of the diamond coating are effectively improved, the service life of the PCBN cutter is prolonged, and the preparation method has good industrial application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a method for preparing a PCBN tool with a nano-diamond film coating on the surface, the method comprising the following steps:
(1) The PCBN cutter after pretreatment is dried and polished in nano diamond powder until the PCBN cutter is bright, then the PCBN cutter is placed on a base station, placed in a microwave plasma chemical vapor deposition system for vacuumizing, and then the PCBN cutter is introduced with first reaction source gas after vacuumizing;
(2) Starting a microwave plasma chemical vapor deposition system, exciting a first reaction source gas by microwaves to generate plasma balls, then introducing a second reaction source gas to start deposition, and obtaining the PCBN tool with the nano diamond film coating on the surface after the deposition is completed.
According to the preparation method, a microwave plasma chemical vapor deposition (Microwave Plasma Chemical Vapor Deposition, MPCVD) process is adopted and optimized, a transition layer is not required to be prepared on a PCBN tool substrate or surface modification is not required, a nano-scale diamond film coating which is continuous and compact, high in adhesion strength, large in binding force, uniform in coating thickness and smooth in surface can be obtained by deposition, abrasion and cutting force generated when the PCBN tool is contacted with a workpiece can be effectively reduced, and the service life of the coated tool is prolonged; compared with the conventional hot wire chemical vapor deposition (Hot Filament Chemical Vapor Deposition, HFCVD) process, the process flow is simplified, the problem of film growth stability caused by uneven wire drawing is avoided, the problem of pollution to the surface of a product due to hot wire breakage in the preparation process is avoided, and the qualification rate of the product is greatly improved.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferred technical scheme of the invention, the pretreatment in the step (1) comprises ultrasonic cleaning and drying.
Preferably, the cleaning liquid used for ultrasonic cleaning is acetone.
Preferably, the time of the ultrasonic cleaning is 8to 12min, for example, 8min, 9min, 10min, 11min or 12min, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the drying is performed in a thermostatted drying oven.
Preferably, the drying time is not less than 4 minutes, such as 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, or 9 minutes, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The drying temperature is preferably 45 to 55 ℃, for example, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the cutter pretreatment method comprehensively optimizes the surface purification and crystal planting process, and firstly, the adsorbate and the pollutant on the surface of the cutter are effectively removed by selecting a proper reagent, so that the microscopic quality of the surface is improved; and then adopting nano diamond powder to dry and throw until the nano diamond powder is bright, and increasing the activity and high-energy points of the surface of the cutter. Compared with ultrasonic treatment of diamond powder-containing suspension, the crystal planting process provided by the invention can obtain more defects such as scratches, dislocation and crystal boundaries, the defects provide nucleation work for diamond nucleation, and diamond powder chips remained in the defects on the surface of the cutter provide nucleation points for MPCVD deposited diamond, so that nucleation density is improved. Meanwhile, the nucleation growth mode enables the diamond film and the cutter to act by an anchor chain effect, so that the adhesive force of the film and the matrix is improved.
In a preferred embodiment of the present invention, the nano-diamond powder in the step (1) has a particle size of 10to 500nm, for example, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm or 500nm, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
In a preferred embodiment of the present invention, the dry polishing time in the step (1) is 10to 25min, for example, 10min, 12min, 15min, 18min, 20min, 22min or 25min, but the present invention is not limited to the listed values, and other values not listed in the range of the values are equally 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, 55mm, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are equally 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 is too high, the ionization degree experienced by the sample contacting the center 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, so that the plasma glow cannot completely cover the sample; both of which lead to reduced surface uniformity and film stability of the coating.
In the invention, the vacuumizing in the step (1) is carried out to the limit vacuum, so that the defect that the crystal texture quality of the nano diamond coating is poor due to the fact that the MPCVD system contains impurity gas is avoided, and the impurity content in the film is high.
As a preferable technical scheme of the invention, the first reaction source gas in the step (1) is H 2 。
Preferably, the second reaction source gas in step (1) is CH 4 。
Preferably, the CH 4 And H 2 The gas flow rate ratio is (0.5-8): 50, for example, 1:100, 1:50, 1:25, 3:50, 2:25, 1:10, 3:25, 7:50, or 4:25, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the present invention, the CH 4 And H 2 The units of gas flow are "sccm".
In the invention, the proportion of the reaction source gas in the deposition process is important. If the carbon source (CH) 4 ) When the content is too high, H tends to be reduced 2 Concentration, a large amount of hydrocarbon groups adsorbed to the surface of the cutter, and the non-diamond phase component is increased due to the fact that no enough active hydrogen atoms etch the hydrocarbon groups, so that the purity of diamond in the film is reduced; in addition, too high a carbon source concentration can result in too fast nucleation and growth rates of the diamond grains, and film thickness is not easily controlled. If H 2 When the content is too high, the surface of the tool does not have enough hydrocarbon for forming diamond grainsGroups, resulting in a decrease in the deposition rate of the thin film coating; 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, the power of the microwave in the process of generating the plasma ball in the step (2) is 500 to 700W, for example, 500W, 550W, 600W, 650W or 700W, etc., but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are equally applicable.
Preferably, the pressure of the working chamber during the generation of the plasma ball in the step (2) is 8to 12Torr, for example, 8Torr, 9Torr, 10Torr, 11Torr or 12Torr, etc., but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are equally applicable.
In a preferred embodiment of the present invention, in the deposition process of 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 recited values, and other non-recited values within the range of values are equally applicable.
Preferably, in the deposition process of step (2), the pressure of the working chamber is 20to 60Torr, for example, 20Torr, 30Torr, 40Torr, 50Torr or 60Torr, etc., but the pressure is not limited to the values listed, and other values not listed in the range are equally applicable.
According to the preparation method, the volume and the density of the generated plasma ball are further controlled by cooperatively regulating and controlling the microwave power and the air pressure of the working cavity, so that the uniformity of the temperature field on the surface of the cutter matrix and the deposition rate and the growth quality of the 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 severely by ions, and the temperature of a cutter matrix is increased; if the microwave power is too small during deposition, the volume of the plasma ball is reduced, and the plasma density is reduced; both cannot obtain a high quality nanodiamond film with a uniform surface. If the working cavity air pressure during deposition is too large, the average free path of molecules is reduced, the average free path Cheng Bianduan of hydrogen atoms and carbon-containing groups is not easy to generate secondary nucleation when colliding with a cutter matrix, and diamond particles are easy to grow; if the air pressure of the working cavity is too small during deposition, 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 diamond is reduced, and simultaneously, more graphite and amorphous carbon in the film and the adhesive force between the coating and the cutter substrate are reduced, so that the cutting performance of the diamond coated cutter is finally affected.
Preferably, in the deposition process of step (2), the temperature of the susceptor is 600 to 900 ℃, for example 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or the like, but not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the time of the deposition in step (2) is 6 to 12 hours, for example 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally 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 nano-diamond thin film coating in the step (2) is 5 to 15. Mu.m, for example, 5 μm, 6 μm, 7 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Firstly ultrasonically cleaning a PCBN cutter by using acetone for 8-12 min, then drying at 45-55 ℃ for not less than 4min, then dry-polishing in diamond powder with the particle size of 10-500 nm for 10-25 min, then placing the PCBN cutter on a base with the height of 40-55 mm, placing the base into a microwave plasma chemical vapor deposition system, vacuumizing to limit vacuum, and introducing 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 to be 600-900 ℃, and depositing for 6-12 h to obtain the PCBN cutter with the surface of the 5-15 mu m nano diamond film coating after the deposition is completed.
On the other hand, the invention provides a PCBN tool, and the surface of the PCBN tool 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) According to the preparation method, the MPCVD technology is adopted and optimized, a transition layer or surface modification is not required to be prepared on a PCBN tool substrate in advance, and the nano-scale diamond film coating which is continuous and compact, high in adhesive strength, large in bonding force, uniform in coating thickness, flat and smooth in surface can be directly deposited, so that the problems that the preparation process is complex, crystal grains on the surface of the coating are in a micron scale, the bonding force between the film and the tool is poor, the later polishing is difficult and the like in the technology for preparing the diamond coating by the conventional HFCVD technology are solved; the height of a base station, microwave power, air pressure of a working cavity and gas proportion in the MPCVD process are further controlled, so that the grain size and film uniformity are further controlled, abrasion and cutting force generated when a cutter is contacted with a workpiece are reduced, and the service life of the cutter is further prolonged;
(2) The preparation method has the advantages of simple process flow, no internal electrode in MPCVD, capability of avoiding electrode discharge, no contact between axisymmetric plasma balls and the wall of the vacuum vessel, pollution reduction, high ionization degree, wide operating air pressure range, high energy conversion efficiency, good film coating quality and the like, and is favorable for realizing industrial application.
Drawings
Fig. 1 is a process flow diagram of a tool with a nanodiamond film coating on the surface prepared in example 1 of the present invention.
Fig. 2 is a surface topography of a nano diamond film coating on a surface of a tool according to example 1 of the present invention.
Fig. 3 is a graph of the morphology of the crystal grains of the nano diamond film coating on the surface of the cutter provided in the embodiment 1 of the present invention.
Fig. 4 is a cross-sectional morphology diagram of the nano diamond film coating on the surface of the cutter provided in the embodiment 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 tool provided in example 1 of the present invention.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The following are exemplary but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of a cutter with a nano diamond film coating on the surface, and a process flow chart of the preparation method is shown in fig. 1.
The preparation method comprises the following steps:
(1) Ultrasonically cleaning PCBN cutter with acetone for 10min, drying at 50deg.C for 4min, dry polishing with diamond powder with particle size of 100nm for 15min to brightness, placing on a base with height of 40mm, vacuum-pumping in MPCVD system to limit vacuum, and introducing H 2 ；
(2) Starting MPCVD system, setting microwave power to 600W, setting air pressure of working cavity to 10Torr, exciting H 2 Generating plasma balls and then introducing CH 4 Beginning deposition of the CH 4 And H 2 The gas flow ratio of (2) is 1:50, the microwave power is adjusted to 1500W in the deposition process, the gas pressure of the working cavity is 40Torr,and the temperature of the base is 700 ℃, the deposition is carried out for 10 hours, and the PCBN cutter with the nano diamond film coating on the surface is obtained after the deposition is completed.
The nano diamond film coating on the PCBN tool surface is characterized, the surface topography diagram is shown in fig. 2, the crystal grain topography diagram is shown in fig. 3, the cross section topography diagram is shown in fig. 4, the XRD diagram is shown in fig. 5, and the Raman spectrum diagram is shown in fig. 6.
As can be seen from fig. 2, the nano-scale diamond coating has been uniformly deposited on the surface of the PCBN tool, and the coated diamond film has the advantages of continuity, compact structure, high surface smoothness, obvious grain boundaries between grains, and obvious secondary nucleation at the grain boundaries, which indicates that the prepared nano-diamond film has higher quality.
As is clear from fig. 3, the diamond grains in the thin film coating layer have good crystallinity, are clustered, are typical nano-sized diamond structures, i.e., so-called diamond flower-like morphology, and have substantially uniform diamond grain sizes with an average size of 50nm or less.
As can be seen from fig. 4, the nanodiamond film does not grow in a columnar shape like a conventional film, but is a growth mode of grain stacking. This is due to the fact that during the growth of the nano diamond film, the secondary nucleation phenomenon appears on the surface of the film, the growth of crystal grains is restrained, the crystal grains are refined, and along with the extension of the deposition time, the diamond crystal grains are accumulated on the surface of the film. In addition, it was also observed from the cross-sectional morphology that the nanodiamond film surface was smooth and flat, which is consistent with the results obtained in fig. 2.
As can be clearly seen from fig. 5, there are two distinct diffraction peaks at 2θ=43.92° and 2θ=75.32°, corresponding to the (111) crystal plane and the (220) crystal plane of the diamond crystal, respectively, indicating that the nanodiamond film has higher crystallinity and grain orientation density.
As can be seen from FIG. 6, at 1332cm -1 A broad raman scattering peak (D peak) appears, indicating that the film contains a diamond phase. The reason for this broader peak is due to the overlapping of the D peak and the diamond characteristic peak in the vicinity thereof. At 1579cm -1 The G peak at corresponds to graphite and amorphous carbonStructure is as follows. At 1150cm -1 The characteristic peaks of the nano diamond which appear nearby show that the diamond components in the film are 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 smaller, which shows that the residual stress in the film coating is smaller, and the quality of the nano diamond film is higher.
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 45deg.C for 5min, dry polishing with diamond powder with particle diameter of 10nm for 20min to brightness, placing on base station with height of 55mm, vacuum-pumping in MPCVD system to limit vacuum, and introducing H 2 ；
(2) Starting MPCVD system, setting microwave power to 500W, setting air pressure of working cavity to 8Torr, exciting H 2 Generating plasma balls and then introducing CH 4 Beginning deposition of the CH 4 And H 2 The gas flow ratio of (2) is 4:25, the microwave power is adjusted to 1000W in the deposition process, the air pressure of the working cavity is 20Torr, the temperature of the base station 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 completed.
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) Ultrasonically cleaning PCBN cutter with acetone for 12min, drying at 45deg.C for 4min, dry polishing with 500nm diamond powder for 18min to brightness, placing on 45mm high base, vacuum-pumping in MPCVD system to limit vacuum, and introducing H 2 ；
(2) Starting MPCVD system, setting microwave power to 700W, setting air pressure of working cavity to 12Torr, exciting H 2 Generating plasma balls and then introducing CH 4 Beginning deposition of the CH 4 And H 2 Is a gas flow of (2)The ratio of the amount is 1:100, the microwave power is adjusted to 2000W in the deposition process, the air pressure of a working cavity is 60Torr, the temperature of a base station is 900 ℃, the deposition is carried out for 6 hours, and the PCBN tool with the nano diamond film coating on the surface is obtained after the deposition is completed.
Example 4:
this example provides a method for preparing a PCBN tool with a nanodiamond film coating on the surface, the method being different from the method of example 1 only in that: the height of the base in the step (1) is 35mm.
Example 5:
the present example provides a method for preparing a PCBN tool having a nanodiamond film coating on the surface, the method being different from the method of example 2 only in that: the height of the base in the step (1) is 60mm.
Example 6:
the present example provides a method for preparing a PCBN tool having a nanodiamond film coating on the surface, the method being different from the method of example 2 only in that: and (3) adjusting the microwave power to 800W in the deposition process of the step (2).
Example 7:
this example provides a method for preparing a PCBN tool with a deep sub-micron diamond film coating on the surface, the method being as described in example 3, with the only difference that: and (3) adjusting the microwave power to 2200W in the deposition process of the step (2).
Example 8:
the present example provides a method for preparing a PCBN tool having a nanodiamond film coating on the surface, the method being different from the method of example 2 only in that: the pressure of the working chamber during the deposition in step (2) was 10Torr.
Example 9:
this example provides a method for preparing a PCBN tool with a deep sub-micron diamond film coating on the surface, the method being as described in example 3, with the only difference that: the pressure of the working chamber in the deposition process of the step (2) is 70Torr.
Comparative example 1:
this comparative example provides a method of manufacturing PCBN tools having a coating of submicron diamond film on the surface, the method of manufacturing being distinguished only by the following with reference to the method of manufacturing in example 1: in the step (1), the PCBN cutter is not subjected to nano diamond powder dry polishing treatment, but is subjected to ultrasonic treatment by adopting an alcohol suspension containing diamond powder.
The surface quality, diamond grain size, film thickness, uniformity, etc. of the tools having diamond film coatings obtained in examples 1to 9 and comparative example 1 were observed, and the results are shown in table 1.
TABLE 1
The embodiment 1-3 adopts a microwave plasma chemical vapor deposition technology, optimizes PCBN cutter pretreatment and a crystal planting process, further controls reaction conditions in the deposition process, enables the cutter surface to obtain a nano diamond film coating which is continuous and compact, has uniform coating thickness and smooth surface, is not easy to cause stress concentration, effectively reduces abrasion and cutting force generated when the cutter is contacted with a workpiece, and prolongs the service life of the coated cutter; in the embodiments 4-5, the height of the base station is respectively reduced and increased in the preparation process, so that the distance between the cutter matrix and the plasma ball is obviously changed, the smoothness of the obtained coating and the stability of the film are reduced, and particularly when the height of the base station is too low, the plasma glow is easy to be caused to be incapable of completely covering the sample, and the quality of the film is seriously reduced; example 6 reduced microwave power during deposition during the fabrication process, resulting in reduced plasma density, reduced thickness and uniformity of the resulting film, and cracking of the coating surface; in the embodiment 7, the microwave power during deposition is improved in the preparation process, so that the temperature of a matrix is increased, the energy of active groups is reduced, the probability of secondary nucleation is reduced, the grain size of the obtained diamond film is increased to submicron level, and the surface roughness of a coating is obviously increased; example 8 reduced working chamber air pressure during preparation, reduced diamond growth rate, and affected cutting performance of diamond coated tools; example 9 increases working chamber pressure during preparation, and the average free Cheng Bianduan of hydrogen atoms and carbon-containing groups, which is not prone to secondary nucleation upon impact with the tool substrate, results in easy growth of diamond particles.
In contrast, in comparative example 1, the conventional seeding 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 poor.
It can be seen from the above examples and comparative examples that the preparation method of the present invention can deposit and obtain a continuous compact nano-scale diamond film coating with high adhesion strength, large binding force, uniform coating thickness and smooth surface by adopting and optimizing MPCVD process without preparing a transition layer or surface modification on a PCBN tool substrate in advance, and solves the problems of complex preparation process, micron-scale crystal grains on the surface of the coating, poor binding force between the film and the tool, difficult post polishing, etc. existing in the technology of preparing diamond coating by using the existing HFCVD process; the height of a base station, microwave power, air pressure of a working cavity and gas proportion in the MPCVD process are further controlled, so that the grain size and film uniformity are further controlled, abrasion and cutting force generated when a cutter contacts a workpiece are reduced, and the service life of the PCBN cutter is further prolonged; the preparation method has the advantages of simple process flow, no internal electrode in MPCVD, capability of avoiding electrode discharge, no contact between axisymmetric plasma balls and the wall of the vacuum vessel, pollution reduction, high ionization degree, wide operating air pressure range, high energy conversion efficiency, good film coating quality and the like, and is favorable for realizing industrial application.
The applicant states that the invention is illustrated by the above examples as a product and a detailed method of the invention, but the invention is not limited to the above product and detailed method, i.e. it is not meant that the invention must rely on the above product and detailed method to practice. It should be apparent to those skilled in the art that any modifications, equivalent substitutions for operation of the present invention, addition of auxiliary operations, selection of specific modes, etc., are intended to fall within the scope of the present invention and the scope of the disclosure.
Claims (9)
1. The preparation method of the PCBN cutter with the nano-diamond film coating on the surface is characterized by comprising the following steps of:
(1) The PCBN cutter after pretreatment is dried and polished in nano diamond powder until the PCBN cutter is bright, then the PCBN cutter is placed on a base station, placed in a microwave plasma chemical vapor deposition system for vacuumizing, and then the PCBN cutter is introduced with first reaction source gas after vacuumizing; the pretreatment comprises ultrasonic cleaning and drying; the grain diameter of the nano diamond powder is 10-500 nm, and the time is 10-25 min;
(2) Starting a microwave plasma chemical vapor deposition system, exciting a first reaction source gas by microwaves to generate plasma balls, then introducing a second reaction source gas to start deposition, and obtaining the PCBN tool with the nano-diamond film coating on the surface after the deposition is completed; the thickness of the nano diamond film coating is 5-15 mu m;
the first reaction source gas is H 2 The method comprises the steps of carrying out a first treatment on the surface of the The second reaction source gas is CH 4 The method comprises the steps of carrying out a first treatment on the surface of the The CH is 4 And H 2 The gas flow ratio of (5) to (8) is 50;
in the process of generating the plasma ball, the power of the microwaves is 500-700W, and the air pressure of the working cavity is 8-12 Torr;
in the deposition process of the step (2), the power of the microwaves is adjusted to 1000-2000W, the air pressure of the working cavity is 20-60 Torr, the temperature of the base station is 600-900 ℃, and the height of the base station is 40-55 mm.
2. The method according to claim 1, wherein the cleaning liquid used for ultrasonic cleaning is acetone.
3. The method according to claim 1, wherein the ultrasonic cleaning time is 8to 12 minutes.
4. The method of claim 1, wherein the drying is performed in a constant temperature oven.
5. The method according to claim 1, wherein the drying time is not less than 4 minutes.
6. The method according to claim 1, wherein the drying temperature is 45 to 55 ℃.
7. The method of claim 1, wherein the time of the deposition in step (2) is 6 to 12 hours.
8. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Firstly ultrasonically cleaning a PCBN cutter by using acetone for 8-12 min, then drying at 45-55 ℃ for not less than 4min, then dry-polishing in diamond powder with the particle size of 10-500 nm for 10-25 min, then placing the PCBN cutter on a base with the height of 40-55 mm, placing the base into a microwave plasma chemical vapor deposition system, vacuumizing to limit vacuum, and introducing 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 to be 600-900 ℃, and depositing for 6-12 h to obtain the PCBN cutter with the surface of the 5-15 mu m nano diamond film coating after the deposition is completed.
9. A PCBN cutter, characterized in that the surface of the PCBN cutter is provided with a nano diamond film coating prepared by the preparation method as claimed in any one of claims 1to 8.
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| 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 |
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| 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 |
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