CN115896736A - Diamond coating micro-drill bit and preparation method and application thereof - Google Patents
Diamond coating micro-drill bit and preparation method and application thereof Download PDFInfo
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- CN115896736A CN115896736A CN202211432194.3A CN202211432194A CN115896736A CN 115896736 A CN115896736 A CN 115896736A CN 202211432194 A CN202211432194 A CN 202211432194A CN 115896736 A CN115896736 A CN 115896736A
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- 238000000576 coating method Methods 0.000 title claims abstract description 101
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 97
- 239000010432 diamond Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005530 etching Methods 0.000 claims abstract description 85
- 239000002253 acid Substances 0.000 claims abstract description 52
- 238000000151 deposition Methods 0.000 claims abstract description 35
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 4
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 42
- 230000008021 deposition Effects 0.000 claims description 30
- 238000011282 treatment Methods 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 19
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- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000013081 microcrystal Substances 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002159 nanocrystal Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002113 nanodiamond Substances 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 27
- 238000005553 drilling Methods 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 18
- 238000002791 soaking Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000010410 layer Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
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- 239000002356 single layer Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B51/00—Tools for drilling machines
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a diamond coating micro-drill bit and a preparation method and application thereof, belonging to the technical field of micro-drill bits. The method comprises the following steps: chemically pretreating the micro-drillbit before depositing the diamond coating; the diameter of the micro drill bit is 0.35-0.75mm, the grain size is 0.3-1.0 μm, and the cobalt content is 4-8wt%; the chemical pretreatment comprises first acid etching, alkali etching and second acid etching; the acid etching liquid comprises nitric acid, hydrochloric acid and water with the volume ratio of 1-4; the alkali etching solution comprises potassium ferricyanide, potassium nitrate and water in a volume ratio of 1; the three times of etching time are respectively 10-30s, 2-6min and 10-50s. The method can obviously reduce the influence of chemical pretreatment on the fracture strength of the micro-drill and the preparation effect of the diamond coating, has good Co removal effect and high etching efficiency, and the obtained micro-drill can be used for processing circuit boards.
Description
Technical Field
The invention relates to the technical field of micro-drills, in particular to a diamond coating micro-drill and a preparation method and application thereof.
Background
With the advent of the 5G communication era, base stations are being miniaturized, light-weighted, and highly integrated. The 5G cavity filter generally needs a 1PCS micro-strip PCB (Printed Circuit Board) Circuit inside due to the requirements of volume and performance. The PCB facing 5G is a laminated composite material consisting of copper foil, resin, ceramic filler or a plurality of special woven glass fiber cloths. One of the key processing steps in the manufacture of PCB boards is the drilling of through holes, which require the use of carbide micro-drills to process a large number of through holes with a diameter of 0.2-0.8 mm. Because the PCB is a fiber-reinforced composite material containing multiple layers of copper foils, the micro-drill bit is easy to wear out and lose efficacy quickly after a short drilling period, and the short working life of the micro-drill bit and frequent replacement of the micro-drill bit are difficult problems facing the high-efficiency manufacturing of the PCB industry.
In order to prolong the service life of the PCB micro-drill, the Chemical Vapor Deposition (CVD) method is adopted to deposit the diamond coating on the surface of the PCB micro-drill, which is an effective solution. The diamond has extremely high hardness, excellent wear resistance and lower friction coefficient, and can improve the chip removal capability and effectively protect the cutting edge. When the diamond coating micro drill bit is applied to the ceramic base PCB, the service life of the cutter can be prolonged by times, and compared with the same uncoated cutter, the drilling quality of the diamond coating micro drill bit is also greatly improved.
However, the presence of Co as a binder in the tungsten-cobalt cemented carbide of the micro drill promotes the formation of a graphite phase during the deposition of diamond, greatly reducing the adhesion of the diamond coating. Thus, specific pre-treatments of the cemented carbide surface are required before the diamond coating is deposited.
The related pretreatment mode in the prior art can cause a large amount of pores and cavities on the surface of the substrate, damage is caused to the surface of the substrate, the Co removing effect is poor, the fracture strength of the micro drill bit is reduced, and the phenomenon of cutter breakage is easy to occur in the drilling process.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
An object of the present invention is to provide a method for manufacturing a diamond coated micro-drill to solve the above problems.
The invention also aims to provide the diamond coating micro-drill prepared by the preparation method.
The invention also aims to provide application of the diamond coating micro-drill.
The application can be realized as follows:
in a first aspect, the present application provides a method of making a diamond coated micro-drillbit, comprising the steps of:
chemically pretreating the micro-drillbit before depositing the diamond coating;
the diameter of the micro drill bit is 0.35-0.75mm, the grain size is 0.3-1.0 mu m, and the cobalt content is 4-8wt%;
the chemical pretreatment comprises a first acid etching, an alkali etching and a second acid etching which are sequentially carried out;
wherein, the acid etching solution used for the first acid etching and the acid etching solution used for the second acid etching both independently comprise nitric acid, hydrochloric acid and water with the volume ratio of 1-4; the alkaline etching solution used for alkaline etching comprises potassium ferricyanide, potassium nitrate and water in a volume ratio of 1;
the first acid etching time is 10-30s; the alkali etching time is 2-6min; the second acid etching time is 10-50s.
In an alternative embodiment, the material of the micro-drill is cemented carbide, preferably WC cemented carbide;
and/or the diamond grains contained in the diamond coating comprise micro-crystals, nano-crystals or gradient crystals consisting of the micro-crystals and the nano-crystals.
In an alternative embodiment, the chemical pretreatment further comprises cleaning the micro-drillbit.
In an alternative embodiment, the micro-drillbit is subjected to ultrasonic cleaning in an organic solvent.
In an alternative embodiment, the organic solvent comprises at least one of absolute ethanol, acetone, and isopropanol.
In an alternative embodiment, the ultrasonic cleaning is performed at 40-60 deg.C for 20-40min.
In an alternative embodiment, the chemical pretreatment further comprises drying the ultrasonically cleaned micro-drillbit.
In an alternative embodiment, the drying is performed under a nitrogen atmosphere having a purity of not less than 99.99%.
In an alternative embodiment, before the diamond coating is deposited, the chemically pretreated micro-drill is subjected to a seed planting treatment.
In an alternative embodiment, the seeding process comprises: and (3) carrying out ultrasonic vibration treatment on the micro drill bit after the chemical pretreatment in a treatment solution containing diamond powder.
In an alternative embodiment, the treatment solution is prepared by mixing absolute alcohol and nano diamond powder in a ratio of 1L:0.3-0.5 g.
In an alternative embodiment, the nanodiamond powder has a particle size of 1-4 μm.
In an alternative embodiment, the time for the seeding treatment is 10-15min.
In an alternative embodiment, the deposition of the diamond coating is performed by chemical vapor deposition.
In an alternative embodiment, when the grains of the diamond coating desired to be deposited are microcrystalline, the deposition conditions include: temperature of hot wire2000-2200 deg.C, hot wire-matrix distance of 18-22mm, substrate temperature of 800-850 deg.C, and CH 4 The flow rate of (A) is 50-70sccm 2 The flow rate is 17000-19000sccm, the gas pressure is 5-10mbar, and the deposition time is 8-20h.
In an alternative embodiment, when the grains of the diamond coating desired to be deposited are nanocrystalline, the deposition conditions include: the temperature of the hot wire is 2000-2200 ℃, the distance between the hot wire and the matrix is 18-22mm, the temperature of the substrate is 800-850 ℃, and CH 4 The flow rate of (A) is 20-40sccm 2 The flow rate of the deposition solution is 8000-10000sccm, the air pressure is 1-5mbar, and the deposition time is 8-20h.
In an alternative embodiment, when the grains of the diamond coating desired to be deposited are graded crystals, the deposition conditions include: the temperature of the hot wire is 2000-2200 ℃, the distance between the hot wire and the matrix is 18-22mm, the temperature of the substrate is 800-850 ℃, and the temperature of the substrate is CH 4 The flow rate of (1) is 30-165sccm, H 2 The flow rate of the deposition solution is 8000-10000sccm, the air pressure is 1-5mbar, and the deposition time is 8-20h.
In a second aspect, the present application provides a diamond coated micro-drill produced by the method of any one of the preceding embodiments.
In a third aspect, the present application provides the use of a diamond coated micro-drill as in the previous embodiments for circuit board processing.
In an alternative embodiment, the circuit board is a 5G communication PCB circuit board containing copper foil and/or PTFE and/or ceramic filler.
The beneficial effect of this application includes:
the application provides an above-mentioned chemical pretreatment mode can realize not weakening micro-drill's rupture strength's effect significantly on the basis of effectively shortening acid solution etching time (improving etching efficiency). In addition, the method can improve the surface roughness of the substrate, improve the adhesion property between the substrate and the coating, strengthen the mechanical locking effect between the substrate and the diamond coating and improve the film-substrate binding force. In addition, the Co removing effect of the mode is good, and the etching efficiency is high. The obtained diamond coating micro-drill bit has high breaking strength, the coating and the matrix are well combined, the phenomenon of cutter breakage is not easy to occur in the drilling process, and the diamond coating micro-drill bit can be used for processing circuit boards.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a surface topography of a chemically pretreated micro-drillbit in example 1 of the present application;
FIG. 2 is an enlarged view corresponding to the box area of FIG. 1;
FIG. 3 is a scanning electron microscope image of the diamond coated micro-drill in example 1 of the present application after a drilling test;
FIG. 4 is a scanning electron micrograph of a diamond coated micro-drill according to comparative example 2 of the present application after a drilling test.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The diamond coated micro-drill provided by the present application, and the preparation method and application thereof are specifically described below.
The application provides a preparation method of a diamond coating micro-drill bit, which comprises the following steps:
the micro-drillbit is chemically pretreated prior to depositing the diamond coating on the surface of the micro-drillbit.
It should be noted that the chemical pretreatment conditions applied to different micro-drills are different, and the diameter of the micro-drill aimed at in the application is 0.35-0.75mm, the grain size is 0.3-1.0 μm, and the cobalt content is 4-8wt%.
Illustratively, the diameter of the micro drill may be 0.35mm, 0.4mm, 0.45mm, 0.5mm, 0.55mm, 0.6mm, 0.65mm, 0.7mm, 0.75mm, etc., and may be any other value within the range of 0.35-0.75 mm.
The grain size may be 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, or the like, or may be any other value within the range of 0.3 to 1.0. Mu.m.
The cobalt content may be 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, or the like, or may be any other value within the range of 4 to 8wt%.
The material of the micro-drill is a cemented carbide, for example, a WC cemented carbide.
In the present application, the chemical pretreatment includes a first acid etching, an alkali etching, and a second acid etching, which are performed in sequence.
Wherein, the acid etching solution used in the first acid etching and the acid etching solution used in the second acid etching respectively and independently comprise nitric acid, hydrochloric acid and water with the volume ratio of 1-4. The alkaline etching solution used for alkaline etching comprises potassium ferricyanide, potassium nitrate and water in a volume ratio of 1.
The volume ratio of nitric acid to water in the acid etching solution can be 1.
In reference, the etching can be performed by immersing the micro-drill in the etching solution.
The first acid etching is used for removing Co on the surface of the micro-drill; the function of the alkali etching is to remove WC particles in a matrix (WC-Co matrix), expose Co element in the matrix and coarsen the surface of the hard alloy so as to enhance the contact area of the coating on the substrate material and improve the adhesive force of the coating; the second acid etch serves to remove Co from the substrate to a depth that avoids adverse effects of Co during deposition of the diamond coating.
In the present application, the first acid etching time may be 10 to 30s, such as 10s, 12s, 15s, 18s, 20s, 22s, 25s, 28s, or 30s, and may also be any other value within a range of 10 to 30 s.
If the first acid etching time is shorter than 10s, the removal amount of Co is easily too small, and the subsequent etching of WC is not facilitated; longer than 30 seconds tends to lower the fracture strength of the matrix more.
The alkali etching time can be 2-6min, such as 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, 5min, 5.5min or 6min, or any other value within 2-6 min.
If the alkali etching time is shorter than 2min, co on the surface layer is not completely exposed, so that the Co cannot be completely removed easily; if the time is longer than 6min, the corrosion of the matrix is deeper, and the fracture strength is easily reduced more.
The second acid etching time can be 10-50s, such as 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s or 50s, and the like, and can also be any other value within the range of 10-50s.
If the second acid etching time is shorter than 10s, co still remains on the surface layer of the substrate, so that the quality of the subsequent diamond coating is poor; longer than 50s, brittle layers tend to be produced resulting in poor bonding of the coating to the substrate.
And after the first acid etching, soaking the cleaned micro drill bit in deionized water, and then performing alkali etching. After the alkali etching, the treated micro-drill bit is soaked in deionized water to remove suspended ions on the surface of the matrix, then the micro-drill bit is soaked and cleaned by the deionized water, and then the acid etching is carried out for the second time. And after the second acid etching, soaking and cleaning the treated micro-drill bit by using deionized water, and then carrying out subsequent treatment.
It should be noted that, because the size of the micro drill bit aimed at by the present application is small, the fracture strength of the drill bit is easily reduced greatly by the overlong acid-base pretreatment, so that the cutter breakage phenomenon is easily caused in the drilling process.
The application provides an above-mentioned chemical pretreatment mode can realize weakening micro-drill's breaking strength not significantly on the basis of effectively shortening acid solution etching time (improving etching efficiency). In addition, the method can improve the surface roughness of the substrate, improve the adhesion property between the substrate and the coating, strengthen the mechanical locking effect between the substrate and the diamond coating and improve the film-substrate binding force. In addition, compared with the existing pretreatment mode, the mode can greatly reduce the existence of pores and cavities on the surface of the substrate and reduce the damage to the surface of the substrate.
In some embodiments, prior to the chemical pretreatment, the method further comprises cleaning the micro-drillbit.
For example, the micro-drill may be placed in an organic solvent for ultrasonic cleaning.
For reference, the above organic solvent may include at least one of absolute ethanol, acetone, and isopropanol.
The ultrasonic cleaning can be carried out at 40-60 deg.C (such as 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C or 60 deg.C) for 20-40min (such as 20min, 25min, 30min, 35min or 40 min).
Through the cleaning treatment, partial impurities and oil stains on the surface of the micro drill bit can be removed, and the subsequent etching effect can be improved.
Further, before the chemical pretreatment, drying the micro-drill after ultrasonic cleaning.
It should be noted that the drying may be performed in a nitrogen atmosphere with a purity of not less than 99.99% to prevent water stains left by natural drying from affecting subsequent etching.
Further, before the diamond coating is deposited, the chemically pretreated micro drill bit is subjected to seed crystal planting treatment.
In a referential manner, the seed planting treatment comprises: and (3) carrying out ultrasonic vibration treatment on the micro drill bit after the chemical pretreatment in a treatment solution containing diamond powder.
The above treatment solution was prepared by mixing anhydrous alcohol with nano-diamond powder (particle size about 1-4 μm) in a volume of 1L:0.3-0.5g (for example, 1l.
The seed crystal planting time is 10-15min, such as 10min, 10.5min, 11min, 11.5min, 12min, 12.5min, 13min, 13.5min, 14min, 14.5min or 15min, and can be any value within 10-15min.
Through the seed crystal planting treatment, the diamond seeds can be uniformly distributed on the surface of the substrate, so that a diamond phase is easier to generate during subsequent deposition of the diamond coating.
In the present application, the diamond coating contains diamond grains comprising microcrystals, nanocrystals or gradient crystals composed of both microcrystals and nanocrystals.
Wherein, from one side close to the matrix to one side far away from the matrix, the gradient crystals are in the forms of decreasing gradient of the micro-crystals and increasing gradient of the nano-crystals.
In the present application, the diamond coating may be a single layer, or may be multiple layers (e.g., 2, 3, or 4 layers). The total thickness of the diamond coating may be 2-20 μm, such as 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm or 20 μm, etc., or any other value in the range of 2-20 μm.
When the diamond coating is a single layer, the diamond grains contained in the diamond coating are preferably only nanocrystalline or microcrystalline. When the diamond coating is multilayered, it may consist of alternating nanocrystalline layers (i.e., the diamond grains comprised by the diamond coating are nanocrystalline) and microcrystalline layers (i.e., the diamond grains comprised by the diamond coating are microcrystalline).
In this application, the diamond coating is deposited by chemical vapor deposition.
When the grains of the diamond coating desired to be deposited are microcrystalline, the deposition conditions include: the hot filament temperature is 2000-2200 deg.C (such as 2000 deg.C, 2020 deg.C, 2050 deg.C, 2080 deg.C, 2100 deg.C, 2120 deg.C, 2150 deg.C, 2180 deg.C or 2200 deg.C), the hot filament-substrate distance is 18-22mm (such as 18mm, 18.5mm, 19mm, 19.5mm, 20mm, 20.5mm, 21mm, 21.5mm or 22 mm), the substrate temperature is 800-850 deg.C (such as 800 deg.C, 810 deg.C, 820 deg.C, 830 deg.C, 840 deg.C or 850 deg.C), CH 4 The flow rate of (e.g., 50sccm, 52sccm, 55sccm, 58sccm, 60sccm, 62sccm, 65sccm, 68sccm, or 70 sccm), H 2 The flow rate of the gas is 17000-19000sccm (e.g., 17000sccm, 17200sccm, 17500sccm, 17800sccm, 18000sccm, 18200sccm, 18500sccm,18800sccm or 19000sccm, etc.), a gas pressure of 5-10mbar (e.g., 5mbar, 6mbar, 7mbar, 8mbar, 9mbar, or 10mbar, etc.), and a deposition time of 8-20h (e.g., 8h, 10h, 12h, 15h, 18h, or 20h, etc.).
When the grains of the diamond coating desired to be deposited are nanocrystalline, the deposition conditions include: the hot filament temperature is 2000-2200 deg.C (such as 2000 deg.C, 2020 deg.C, 2050 deg.C, 2080 deg.C, 2100 deg.C, 2120 deg.C, 2150 deg.C, 2180 deg.C or 2200 deg.C), the hot filament-substrate distance is 18-22mm (such as 18mm, 18.5mm, 19mm, 19.5mm, 20mm, 20.5mm, 21mm, 21.5mm or 22 mm), the substrate temperature is 800-850 deg.C (such as 800 deg.C, 810 deg.C, 820 deg.C, 830 deg.C, 840 deg.C or 850 deg.C), CH 4 The flow rate of (1) is 20-40sccm (20 sccm, 22sccm, 25sccm, 28sccm, 30sccm, 32sccm, 35sccm, 38sccm, or 40sccm, etc.), H 2 The flow rate of (a) is 8000-10000sccm (such as 8000sccm, 8200sccm, 8500sccm, 8800sccm, 9000sccm, 9200sccm, 9500sccm, 9800sccm or 10000 sccm), the gas pressure is 1-5mbar (such as 1mbar, 2mbar, 3mbar, 4mbar or 5 mbar), and the deposition time is 8-20h (such as 8h, 10h, 12h, 15h, 18h or 20 h).
When the grains of the diamond coating desired to be deposited are graded, the deposition conditions include: the hot filament temperature is 2000-2200 deg.C (such as 2000 deg.C, 2020 deg.C, 2050 deg.C, 2080 deg.C, 2100 deg.C, 2120 deg.C, 2150 deg.C, 2180 deg.C or 2200 deg.C), the hot filament-substrate distance is 18-22mm (such as 18mm, 18.5mm, 19mm, 19.5mm, 20mm, 20.5mm, 21mm, 21.5mm or 22 mm), the substrate temperature is 800-850 deg.C (such as 800 deg.C, 810 deg.C, 820 deg.C, 830 deg.C, 840 deg.C or 850 deg.C), CH 4 The flow rate of (e.g., 30-165sccm (e.g., 30sccm, 50sccm, 80sccm, 100sccm, 120sccm, 150sccm, or 165 sccm), H 2 The flow rate of (a) is 8000-10000sccm (such as 8000sccm, 8200sccm, 8500sccm, 8800sccm, 9000sccm, 9200sccm, 9500sccm, 9800sccm or 10000 sccm), the gas pressure is 1-5mbar (such as 1mbar, 2mbar, 3mbar, 4mbar or 5 mbar), and the deposition time is 8-20h (such as 8h, 10h, 12h, 15h, 18h or 20 h).
That is, CH 4 And H 2 The flow rate and the pressure of the gas are changed, so that the crystal grains are changed.
By the method, the diamond coating can be uniformly deposited on the surface of the micro-drill, and the diamond coating has good crystallinity and diamond crystals with clear edges and corners.
Correspondingly, the application also provides a diamond coating micro-drill which is prepared by the preparation method.
The diamond coating micro-drill bit has high breaking strength, the coating and the matrix are well combined, and the phenomenon of cutter breakage is not easy to occur in the drilling process.
In addition, the application also provides the application of the diamond coating micro-drill, such as being used for processing circuit boards.
Illustratively, the circuit board can be a 5G communication PCB circuit board containing copper foil and/or PTFE and/or ceramic filler.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Step (1): soaking a fine drill (WC-6wt% Co, drill diameter 0.5mm, grain size 0.3-0.5 μm) in anhydrous ethanol, and ultrasonically cleaning at 50 deg.C for 30min; followed by drying with nitrogen gas having a purity of 99.99%.
Step (2): and (2) soaking the micro-drill treated in the step (1) in an acid etching solution formed by 60mL of nitric acid, 120mL of hydrochloric acid and 600mL of deionized water for 10s, and then soaking in the deionized water for 2 minutes.
And (3): putting the micro-drill treated in the step (2) into a vacuum pump at a volume ratio of V (K) 3 Fe(CN) 6 ):V(KOH):V(H 2 O) = 1.
And (4): and (4) soaking the micro-drill processed in the step (3) in the same acid etching solution as that in the step (2) for 30s, and then soaking in deionized water for 2 minutes.
And (5): and (3) placing the micro drill processed in the step (4) into suspension of 0.35g diamond powder (the grain diameter is about 4 mu m)/1000 mL absolute ethyl alcohol for ultrasonic oscillation, and carrying out seed crystal planting treatment for 10min.
And (6): will be steps (5)The treated micro-drill bit is placed in CVD chemical vapor deposition equipment, the temperature of a hot wire is 2100 ℃, the distance between the hot wire and a matrix is 20 mu m, the temperature of a substrate is 800 ℃, and CH is added 4 And H 2 The micro-drill bit containing the diamond coating (MCD) of the microcrystals is obtained with the flow rates of 60sccm and 18000sccm, the gas pressure of 5mbar and the deposition time of 8 h.
The surface topography of the micro-driller after pretreatment in this example is shown in fig. 1 and 2. As can be seen from fig. 1 and 2: the surface has more holes, which provides nucleation sites for the following diamond coating film plating process, and the Co removing effect of the method is good, thereby improving the binding force between the coating and the substrate.
The micro drill bit containing the diamond coating is observed through a scanning electron microscope, and the coating is found to be uniformly deposited on the surface of the micro drill bit, so that the crystallinity is good, and diamond crystals with clear edges and corners can be clearly seen.
Performing a fracture strength test experiment on the pretreated micro drill bit, and obtaining the fracture strength of 29N through the test; the micro drill was subjected to a drilling test, and when the number of drilled holes was 4000, the flank of the micro drill was observed by a scanning electron microscope to find that the bonding between the coating and the substrate was good, and no sign of the coating peeling was found (as shown in fig. 3).
Example 2
Step (1): soaking a micro-fine drill (WC-8wt% Co, drill diameter 0.75mm, grain size 0.5-0.7 μm) in acetone, and ultrasonically cleaning at 40 deg.C for 40min; followed by drying with nitrogen gas having a purity of 99.99%.
Step (2): and (2) soaking the micro-drill treated in the step (1) in an acid etching solution formed by 60mL of nitric acid, 240mL of hydrochloric acid and 600mL of deionized water for 30s, and then soaking in the deionized water for 2 minutes.
And (3): putting the micro-drill treated in the step (2) into a vacuum pump at a volume ratio of V (K) 3 Fe(CN) 6 ):V(KOH):V(H 2 O) = 1.
And (4): and (3) soaking the micro drill bit treated in the step (3) in the same acid etching solution as that in the step (2) for 50s, and then soaking in deionized water for 2 minutes.
And (5): and (5) placing the micro drill processed in the step (4) into suspension of 0.5g diamond powder (the grain diameter is about 3 mu m)/1000 mL absolute ethyl alcohol in a proportioning concentration for ultrasonic oscillation, and carrying out seed crystal planting treatment for 15min.
And (6): placing the micro-drill processed in the step (5) in CVD chemical vapor deposition equipment, wherein the temperature of a hot wire is 2100 ℃, the distance between the hot wire and a matrix is 20 mu m, the temperature of a substrate is 800 ℃, and CH 4 And H 2 The flow rates were 30sccm and 9000sccm, the gas pressure was 1mbar, and the deposition time was 8h, respectively, to obtain a fine drill bit comprising a nanocrystalline diamond coating (NCD).
The diamond coating micro-drill is observed by a scanning electron microscope, and the coating is found to be uniformly deposited on the surface of the micro-drill, the diamond crystal grains have smaller size and are clustered, namely, the diamond coating has a cauliflower-shaped appearance.
Carrying out a fracture strength test experiment on the micro drill bit to obtain the fracture strength of 25N; and (3) taking another sample for carrying out a micro drill drilling test, and observing the rear cutter face of the micro drill when the number of drilled holes is 4000, so that the coating is well combined with the substrate, and the sign of coating peeling is not found.
Example 3
Step (1): soaking a micro-fine drill bit (WC-4 wt% Co, the diameter of the drill bit is 0.35mm, the grain size is 0.8-1.0 μm) in isopropanol, and ultrasonically cleaning at 60 ℃ for 20min; followed by drying with nitrogen gas having a purity of 99.99%.
Step (2): and (2) soaking the micro-drill treated in the step (1) in an acid etching solution formed by 60mL of nitric acid, 120mL of hydrochloric acid and 900mL of deionized water for 20s, and then soaking in the deionized water for 2 minutes.
And (3): putting the micro-drill treated in the step (2) into a vacuum pump at a volume ratio of V (K) 3 Fe(CN) 6 ):V(KOH):V(H 2 O) = 1.
And (4): and (4) soaking the micro-drill processed in the step (3) in the same acid etching solution as that in the step (2) for 10s, and then soaking in deionized water for 2 minutes.
And (5): and (5) placing the micro drill processed in the step (4) into suspension of 0.4g diamond powder (the grain diameter is about 1 mu m)/1000 mL absolute ethyl alcohol in a proportioning concentration for ultrasonic oscillation, and carrying out seed crystal planting treatment for 15min.
And (6): placing the micro-drill processed in the step (5) in CVD chemical vapor deposition equipment, wherein the temperature of a hot wire is 2100 ℃, the distance between the hot wire and a substrate is 20 mu m, the temperature of a substrate is 800 ℃, the air pressure is 1/5mbar, the deposition time is 8h, and the early stage CH is 4 And H 2 The respective flow rates are 30sccm and 9000sccm, and CH is post-adjusted 4 A micro drill bit containing a gradient diamond coating (GCD) was obtained at a flow rate of 165 sccm.
The micro drill bit containing the diamond coating is observed through a scanning electron microscope, and the coating is uniformly deposited on the surface of the micro drill bit, and the surface of the coating presents a cauliflower-shaped surface appearance.
Carrying out a fracture strength test experiment on the micro drill bit, and obtaining the fracture strength of the micro drill bit to be 26N through the test; and (3) taking another sample for carrying out a micro drill drilling test, and observing the rear cutter face of the micro drill when the number of drilled holes is 4000, so that the coating is well combined with the substrate, and the sign of coating peeling is not found.
Example 4
This example differs from example 1 in that: the volume ratio of nitric acid, hydrochloric acid and water in the acid etching liquid is 1.
The micro drill bit containing the diamond coating is observed through a scanning electron microscope, and the coating is found to be uniformly deposited on the surface of the micro drill bit, so that the crystallinity is good, and diamond crystals with clear edges and corners can be clearly seen.
Performing a fracture strength test experiment on the pretreated micro drill bit, and obtaining the fracture strength of 32N through the test; when the number of drilled holes was 4000, the flank face of the fine drill was observed by a scanning electron microscope to find that the bonding between the coating and the substrate was good and no sign of the coating flaking was found.
Example 5
The present example differs from example 1 in that: the first acid etching time is 20s; the alkali etching time is 2min; the second acid etching time was 40s.
The micro drill bit containing the diamond coating is observed through a scanning electron microscope, and the coating is found to be uniformly deposited on the surface of the micro drill bit, so that the crystallinity is good, and diamond crystals with clear edges and corners can be clearly seen.
Performing a fracture strength test experiment on the pretreated micro drill bit, and obtaining the fracture strength of 25N through the test; when the number of drilled holes was 4000, the flank face of the fine drill was observed by a scanning electron microscope to find that the bonding between the coating and the substrate was good and no sign of the coating flaking was found.
Comparative example 1
The comparative example differs from example 1 in that: the first acid etching time is 1min; the alkali etching time is 4min; the second acid etching time was 2min.
Carrying out a fracture strength test experiment on the micro drill bit, and obtaining the fracture strength of the micro drill bit to be 16N through the test; and taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 600, the needle breakage phenomenon occurs.
Comparative example 2
This comparative example differs from example 1 in that: the alkali etching time is 15min.
Carrying out a fracture strength test experiment on the micro drill bit, and obtaining the fracture strength of the micro drill bit to be 18N through the test; another sample was taken to be tested by a micro drill, and when the number of drilled holes was 1000, the peeling of the coating at the chisel edge and the adhesion of the chips were severe, as shown in fig. 4.
Comparative example 3
The comparative example differs from example 1 in that: the alkali etching time is 1min.
Carrying out a fracture strength test experiment on the micro drill bit, and obtaining the fracture strength of the micro drill bit to be 24N through the test; and (3) taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 2000, the coating at the chisel edge is peeled off.
Comparative example 4
The comparative example differs from example 1 in that: the first acid etching time was 5s.
Carrying out a fracture strength test experiment on the micro-drill bit, and obtaining the fracture strength of the micro-drill bit to be 22N through the test; and (3) taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 2000, the coating at the chisel edge is peeled off.
Comparative example 5
This comparative example differs from example 1 in that: the first acid etching time is 1min.
Carrying out a fracture strength test experiment on the micro-drill bit, and obtaining the fracture strength of the micro-drill bit to be 21N through the test; and (3) taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 2000, the needle breakage phenomenon occurs.
Comparative example 6
This comparative example differs from example 1 in that: the second acid etching time was 5s.
Carrying out a fracture strength test experiment on the micro-drill bit, and obtaining the fracture strength of the micro-drill bit to be 24N through the test; and (3) taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 2000, the coating at the chisel edge is peeled off.
Comparative example 7
This comparative example differs from example 1 in that: the second acid etching time was 2min.
Carrying out a fracture strength test experiment on the micro-drill bit, and obtaining the fracture strength of the micro-drill bit to be 22N through the test; and taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 1000, the needle breakage phenomenon occurs.
Comparative example 8
The comparative example differs from example 1 in that: the diameter of the micro drill is 0.25mm.
Carrying out a fracture strength test experiment on the micro drill bit, and obtaining the fracture strength of the micro drill bit to be 18N through the test; and taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 1000, the needle breakage phenomenon occurs.
Comparative example 9
This comparative example differs from example 1 in that: the diameter of the micro drill is 0.8mm.
Carrying out a fracture strength test experiment on the micro-drill bit, and obtaining the fracture strength of the micro-drill bit to be 24N through the test; and (3) taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 2000, the coating at the chisel edge is peeled off.
Comparative example 10
This comparative example differs from example 1 in that: the grain size of the fine drill was 0.1 μm.
Carrying out a fracture strength test experiment on the micro drill bit, and obtaining the fracture strength of the micro drill bit to be 25N through the test; and (3) taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 2000, the coating at the chisel edge is peeled off.
Comparative example 11
This comparative example differs from example 1 in that: the grain size of the fine drill was 2 μm.
Carrying out a fracture strength test experiment on the micro-drill bit, and obtaining the fracture strength of the micro-drill bit to be 22N through the test; another sample is taken to be tested by a micro drill for drilling, and when the number of the drilled holes is 2000, the phenomenon of coating peeling appears at the chisel edge.
Comparative example 12
This comparative example differs from example 1 in that: the cobalt content of the fine drill was 2wt%.
Carrying out a fracture strength test experiment on the micro drill bit, and obtaining the fracture strength of the micro drill bit to be 16N through the test; and (3) taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 1000, the coating at the chisel edge is peeled off.
Comparative example 13
This comparative example differs from example 1 in that: the cobalt content of the fine drill was 10wt%.
Carrying out a fracture strength test experiment on the micro-drill bit, and obtaining the fracture strength of the micro-drill bit to be 24N through the test; and (3) taking another sample to perform a micro drill drilling test, wherein when the number of drilled holes is 1000, the coating at the chisel edge is peeled off.
In summary, the CVD diamond coating pretreatment process suitable for the micro-drill bit provided by the application can improve the adhesion performance between the micro-drill bit and the coating and enhance the mechanical biting force between the matrix and the diamond coating on the basis of not weakening the breaking strength of the micro-drill bit obviously through the optimized three-step chemical etching process. Compared with the traditional chemical etching method, the optimized three-step etching process can effectively shorten the processing time and improve the etching efficiency.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the diamond coating micro-drill bit is characterized by comprising the following steps:
chemically pretreating the micro-drillbit before depositing the diamond coating;
the diameter of the micro drill bit is 0.35-0.75mm, the grain size is 0.3-1.0 mu m, and the cobalt content is 4-8wt%;
the chemical pretreatment comprises first acid etching, alkali etching and second acid etching which are sequentially carried out;
wherein, the acid etching solution used for the first acid etching and the acid etching solution used for the second acid etching both independently comprise nitric acid, hydrochloric acid and water with the volume ratio of 1-4; the alkaline etching solution used for alkaline etching comprises potassium ferricyanide, potassium nitrate and water in a volume ratio of 1;
the first acid etching time is 10-30s; the alkali etching time is 2-6min; the second acid etching time is 10-50s.
2. The method according to claim 1, wherein the material of the micro drill is cemented carbide, preferably WC cemented carbide;
and/or the diamond coating contains diamond grains comprising micro-crystals, nano-crystals or gradient crystals consisting of the micro-crystals and the nano-crystals together.
3. The method of manufacturing according to claim 1, further comprising, before the chemical pretreatment, cleaning the micro-drillbit;
preferably, the micro-drill is placed in an organic solvent for ultrasonic cleaning;
preferably, the organic solvent includes at least one of absolute ethanol, acetone, and isopropanol;
preferably, the ultrasonic cleaning is carried out for 20-40min at 40-60 ℃;
preferably, before the chemical pretreatment, drying the micro-drill after the ultrasonic cleaning;
preferably, the drying is performed under a nitrogen atmosphere having a purity of not less than 99.99%.
4. The preparation method according to claim 1, further comprising, before depositing the diamond coating, subjecting the chemically pretreated micro-drill to a seed treatment;
preferably, the seeding treatment comprises: carrying out ultrasonic vibration treatment on the chemically pretreated micro-drill in a treatment solution containing diamond powder;
preferably, the treatment solution is prepared by mixing absolute alcohol and nano diamond powder according to the proportion of 1L:0.3-0.5 g;
preferably, the particle size of the nano diamond powder is 1-4 μm;
preferably, the time for planting the seed crystal is 10-15min.
5. A method of manufacturing as claimed in claim 1 or claim 2, wherein the deposition of the diamond coating is carried out by chemical vapour deposition.
6. A method of producing as claimed in claim 5, wherein when it is desired to deposit diamondWhen the crystal grains of the stone coating are micron-sized grains, the deposition conditions comprise: the temperature of the hot wire is 2000-2200 ℃, the distance between the hot wire and the matrix is 18-22mm, the temperature of the substrate is 800-850 ℃, and CH 4 The flow rate of (A) is 50-70sccm 2 The flow rate of (1) is 17000-19000sccm, the gas pressure is 5-10mbar, and the deposition time is 8-20h.
7. The method of claim 5, wherein when the grains of the diamond coating to be deposited are nanocrystalline, the deposition conditions include: the temperature of the hot wire is 2000-2200 ℃, the distance between the hot wire and the matrix is 18-22mm, the temperature of the substrate is 800-850 ℃, and the temperature of the substrate is CH 4 The flow rate of (A) is 20-40sccm 2 The flow rate of the deposition solution is 8000-10000sccm, the air pressure is 1-5mbar, and the deposition time is 8-20h.
8. The method of claim 5, wherein when the grains of the diamond coating desired to be deposited are gradient grains, the deposition conditions include: the temperature of the hot wire is 2000-2200 ℃, the distance between the hot wire and the matrix is 18-22mm, the temperature of the substrate is 800-850 ℃, and the temperature of the substrate is CH 4 The flow rate of (1) is 30-165sccm, H 2 The flow rate of the deposition solution is 8000-10000sccm, the air pressure is 1-5mbar, and the deposition time is 8-20h.
9. A diamond-coated micro drill produced by the production method according to any one of claims 1 to 8.
10. Use of a diamond coated micro-drill according to claim 9, wherein the diamond coated micro-drill is used in circuit board processing;
preferably, the circuit board is a PCB circuit board for 5G communication containing copper foil and/or PTFE and/or ceramic filler.
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| CN202211432194.3A CN115896736A (en) | 2022-11-16 | 2022-11-16 | Diamond coating micro-drill bit and preparation method and application thereof |
| PCT/CN2023/123688 WO2024012611A1 (en) | 2022-11-16 | 2023-10-10 | Diamond coating micro drill bit, and preparation method therefor and use thereof |
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| WO2024012611A1 (en) * | 2022-11-16 | 2024-01-18 | 广东省科学院新材料研究所 | Diamond coating micro drill bit, and preparation method therefor and use thereof |
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| US5560839A (en) * | 1994-06-27 | 1996-10-01 | Valenite Inc. | Methods of preparing cemented metal carbide substrates for deposition of adherent diamond coatings and products made therefrom |
| CN102312215B (en) * | 2011-09-29 | 2016-09-28 | 南通科创晶膜新材料有限公司 | A kind of manufacture method of diamond film coating of microbit |
| CN105803419B (en) * | 2016-04-27 | 2018-12-21 | 富耐克超硬材料股份有限公司 | De- cobalt liquor system and hard alloy take off cobalt method and diamond coatings blade |
| CN110983293A (en) * | 2019-12-26 | 2020-04-10 | 广东省新材料研究所 | Hard alloy part with diamond coating, preparation method and application thereof |
| CN111088445B (en) * | 2019-12-31 | 2022-04-01 | 株洲硬质合金集团有限公司 | Hard alloy and preparation method and application thereof |
| CN114293171A (en) * | 2021-12-29 | 2022-04-08 | 东莞市华升真空镀膜科技有限公司 | Diamond coated tool and method for manufacturing the same |
| CN115896736A (en) * | 2022-11-16 | 2023-04-04 | 广东省科学院新材料研究所 | Diamond coating micro-drill bit and preparation method and application thereof |
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| WO2024012611A1 (en) * | 2022-11-16 | 2024-01-18 | 广东省科学院新材料研究所 | Diamond coating micro drill bit, and preparation method therefor and use thereof |
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