CN110257681A - A kind of polycrystalline cubic boron nitride compound sheets and preparation method thereof - Google Patents
A kind of polycrystalline cubic boron nitride compound sheets and preparation method thereof Download PDFInfo
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- CN110257681A CN110257681A CN201910538131.8A CN201910538131A CN110257681A CN 110257681 A CN110257681 A CN 110257681A CN 201910538131 A CN201910538131 A CN 201910538131A CN 110257681 A CN110257681 A CN 110257681A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/003—Cubic boron nitrides only
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Abstract
The present invention provides a kind of polycrystalline cubic boron nitride compound sheets and preparation method thereof, belong to super-hard compound material cutter preparation field.Polycrystalline cubic boron nitride compound sheets provided by the invention are prepared by the component comprising following mass percentage: 55%~95% cubic boron nitride, 4%~38% bonding agent and 1%~7% sintering aid；The bonding agent is boron carbide and titanium valve, and the sintering aid includes aluminium nitride, aluminium oxide and cobalt powder.The present invention adds the cubic boron nitride and bonding agent of special ratios dosage, makes cubic boron nitride and bonding agent new object phase TiN, TiB of in-situ preparation during the sintering process2And cubic boron nitride secure bond is effectively raised the bending strength and hardness of polycrystalline cubic boron nitride compound sheets by TiC.Embodiment the result shows that, the hardness of polycrystalline cubic boron nitride compound sheets provided by the invention is 3500~4400HV, and bending strength is 900~1180MPa.
Description
Technical field
The present invention relates to super-hard compound material cutter preparation field more particularly to a kind of polycrystalline cubic boron nitride compound sheets and
Preparation method.
Background technique
Polycrystalline cubic boron nitride, refer to using many fine cubic boron nitrides as raw material, participated in or without additive, it is high
Under warm condition of high voltage, agglomerate made of sintering.Polycrystalline cubic boron nitride overcome monocrystalline be easy to cleavage and it is anisotropic lack
It falls into；Meanwhile the excellent properties such as hardness also with higher and wearability, good chemical stability and thermal stability.Plycrystalline diamond is vertical
Square boron nitride relies on the advantage in these performances, very widely used, sends out in terms of machining especially as cutter material
Great effect has been waved, such as has been applied in the processing of processing cast iron, ferrous based powder metallurgical metal, hardened steel, stainless steel material.
But most of polycrystalline cubic boron nitride can have bending strength difference, and polycrystalline cubic boron nitride is caused to be made
For cutter material using when be easy to appear " crushing knife " phenomenon, there are security risks.
Summary of the invention
In consideration of it, the present invention provides a kind of polycrystalline cubic boron nitride compound sheets and preparation method thereof.It is provided by the invention
The bending strength of polycrystalline cubic boron nitride compound sheets is high.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of polycrystalline cubic boron nitride compound sheets, is prepared by the component comprising following mass percentage
It arrives:
55%~95% cubic boron nitride, 4%~38% bonding agent and 1%~7% sintering aid；
The bonding agent is boron carbide and titanium valve, and the sintering aid includes aluminium nitride, aluminium oxide and cobalt powder.
Preferably, the mass ratio of the boron carbide and titanium valve is 2~5:10.
Preferably, the mass ratio of the aluminium nitride, aluminium oxide and cobalt powder is 1:1~3:1.
Preferably, the partial size of the cubic boron nitride is 1~22 μm.
Preferably, the average grain diameter of boron carbide is 5~10 μm in the bonding agent, and the average grain diameter of titanium valve is 1~5 μm.
The present invention also provides the preparation methods of polycrystalline cubic boron nitride compound sheets described in above-mentioned technical proposal, include following step
It is rapid:
After cubic boron nitride, bonding agent and sintering aid are mixed, high temperature and pressure sintering is carried out, obtains polycrystalline cubic nitridation
Boron composite sheet.
Preferably, the pressure of the high temperature and pressure sintering is 4~6GPa, and temperature is 1300~1600 DEG C, soaking time 5
~12min.
It preferably, further include pretreatment before the high temperature and pressure sintering, the pretreatment includes vacuum heat treatment and reduction
Processing.
Preferably, the temperature of the vacuum heat treatment is 800~1200 DEG C, vacuum degree 10-1Pa~10-3Pa, time is
1~3h.
Preferably, the temperature of the reduction treatment is 400~600 DEG C, and the time is 0.5~2h.
The present invention provides a kind of polycrystalline cubic boron nitride compound sheets, are prepared by the component comprising following mass percentage
It obtains: 55%~95% cubic boron nitride, 4%~38% bonding agent and 1%~7% sintering aid；The bonding agent is carbonization
Boron and titanium valve, the sintering aid include aluminium nitride, aluminium oxide and cobalt powder.Cube that the present invention passes through addition special ratios dosage
Boron nitride and bonding agent make cubic boron nitride and bonding agent new object phase TiN, TiB of in-situ preparation during the sintering process2And TiC,
Reinforcement (TiN, TiB2And TiC) formed and grown up in sintered body internal-response, surface no-pollution.When in use, reinforcement with
The compatibility of matrix is good, and interface bond strength is high.And new object phase (TiN, TiB generated2And TiC) cubic boron nitride is secured
Bonding, and then effectively improve the bending strength and hardness of polycrystalline cubic boron nitride compound sheets.The present invention uses boron carbide and titanium valve
As bonding agent, the advantages of having both metallic bond and vitrified bond, polycrystalline cubic boron nitride compound sheets are effectively increased
Bending strength and hardness；The present invention, as sintering aid, is during the sintering process molten using aluminium nitride, aluminium oxide and cobalt powder
State provides liquid phase for reaction in-situ, improves the sintering character of cubic boron nitride.Embodiment the result shows that, it is provided by the invention poly-
The hardness of brilliant cubic boron nitride composite piece is 3500~4400HV, and bending strength is 900~1180MPa.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the XRD spectrum for the polycrystalline cubic boron nitride compound sheets that embodiment 1 is prepared；
Fig. 2 is the polycrystalline cubic boron nitride compound sheets profile scanning figure that embodiment 1 is prepared.
Specific embodiment
The present invention provides a kind of polycrystalline cubic boron nitride compound sheets, is prepared by the component comprising following mass percentage
It arrives: 55%~95% cubic boron nitride, 4%~38% bonding agent and 1%~7% sintering aid, further preferably 65%~
85% cubic boron nitride, 12.5%~30% bonding agent and 2.5%~5% sintering aid；The bonding agent is boron carbide and titanium
Powder, the sintering aid include aluminium nitride, aluminium oxide and cobalt powder.
In the present invention, the mass ratio of the boron carbide and titanium valve is preferably 2~5:10, further preferably 4:10, institute
The mass ratio for stating aluminium nitride, aluminium oxide and cobalt powder is preferably 1:1~3:1, further preferably 1:2:1.
In the present invention, the partial size of the cubic boron nitride is preferably 1~22 μm, and further preferably 5~12 μm, at this
In one embodiment of invention, the cubic boron nitride is preferably made of the cubic boron nitride of three kinds of different-grain diameters, and described three kinds
The partial size of the cubic boron nitride of different-grain diameter is respectively preferably 3 μm, 6 μm and 8 μm, the cubic boron nitride of three kinds of different-grain diameters
Weight ratio be preferably 5:3:2, in the other three embodiment of the invention, the cubic boron nitride is preferably by two kinds of different grains
The cubic boron nitride of diameter forms, and the partial size of the cubic boron nitride of described two different-grain diameters is respectively preferably 3 μm and 6 μm, described
The weight ratio of the cubic boron nitride of two kinds of different-grain diameters is preferably 1:1；The average grain diameter of the boron carbide is preferably 5~10 μm,
Further preferably 8 μm；The average grain diameter of the titanium valve is preferably 1~5 μm, and further preferably 3 μm；The aluminium nitride is put down
Equal partial size is preferably 50~200nm, further preferably 100~150nm；The average grain diameter of the aluminium oxide is preferably 0.1~1
μm, further preferably 0.5 μm；The average grain diameter of the cobalt powder is preferably 1~5 μm, and further preferably 3 μm.
The present invention does not have special restriction to the specific source of the cubic boron nitride, bonding agent and sintering aid, uses
This field conventional commercial product.In the present invention, the sintering aid is in high temperature and pressure sintering process as offer liquid
Phase is conducive to the progress of sintering process；Aluminium nitride in sintering aid has that thermal conductivity is high, thermal expansion coefficient is low, impact resistance
The good excellent performance of energy, can reduce polycrystalline cubic boron nitride built-in thermal stress, while cBN can also be inhibited to undergo phase transition conversion
For hBN；The addition of cobalt powder can also reinforce electric conductivity in sintering aid, convenient for the following process of product.
The present invention also provides the preparation methods of polycrystalline cubic boron nitride compound sheets described in above-mentioned technical proposal, include following step
It is rapid:
After cubic boron nitride, bonding agent and sintering aid are mixed, high temperature and pressure sintering is carried out, obtains polycrystalline cubic nitridation
Boron composite sheet.
In the present invention, the mixed mode is preferably ball milling, and the ball milling carries out preferably in ball grinder.In this hair
In bright, the blending agent of the ball milling is preferably ethyl alcohol, the decentralized medium of the ball milling preferably include kayexalate and/
Or polyethyleneimine, the ball milling ratio of grinding media to material of the ball milling is preferably 3~5:1, and the revolving speed of more preferably 4:1, the ball milling are preferred
It is further preferably 250r/min, the time of the ball milling is preferably 4~6h for 200~300r/min.
After the completion of the mixing, preferably material resulting after mixing is successively dried the present invention, is sieved and die-filling.?
In the present invention, the temperature of the drying is preferably 70~100 DEG C, and further preferably 80 DEG C, the time of the drying is preferably
10~16h, further preferably 12h.In the present invention, the partial size of the screening is preferably 50~200 mesh, further preferably
100 mesh.In the present invention, it is described it is die-filling preferably carried out in high-pressure synthesis in molybdenum cup mold, it is in embodiments of the present invention, described
The diameter of molybdenum cup mold is preferably 14mm.The present invention does not have special restriction to the die-filling concrete operations, using this field
Technical staff's routinely die-filling operation.
Before the high temperature and pressure sintering, it is also preferable to include the mixed of cubic boron nitride, bonding agent and sintering aid by the present invention
It closes material to be pre-processed, the pretreatment preferably includes vacuum heat treatment and reduction treatment.
In the present invention, the temperature of the vacuum heat treatment is preferably 800~1200 DEG C, further preferably 900~
1000 DEG C, the vacuum degree of the vacuum heat treatment is preferably 10-1~10-3Pa, further preferably 10-2Pa, at the Vacuum Heat
The time of reason is preferably 1~3h.The present invention does not have special restriction to the concrete operations of the vacuum heat treatment, using this field
Technical staff's conventional vacuum heat treatment operation.In the present invention, the vacuum heat treatment is miscellaneous in component in order to remove
Matter and moisture, it is ensured that the purity of powder, to guarantee the performance of polycrystalline cubic boron nitride compound sheets.
In the present invention, the temperature of the reduction treatment is preferably 400~600 DEG C, and further preferably 450~500 DEG C,
The reducing atmosphere of the reduction treatment is preferably hydrogen, and the time of the reduction treatment is preferably 0.5~2h, further preferably
1h.The present invention does not have special restriction to the concrete operations of the reduction treatment, at those skilled in the art's conventional reduction
Reason operation.In the present invention, the reduction treatment is to restore the metal powder being oxidized, it is ensured that the purity of powder,
To guarantee the performance of polycrystalline cubic boron nitride compound sheets.
In the present invention, the high temperature and pressure sintering carries out preferably in cubic hinge press, the high temperature and pressure sintering
Pressure is preferably 4~6GPa, further preferably 5.5GPa, and the temperature of the high temperature and pressure sintering is preferably 1300~1600
DEG C, further preferably 1400~1500 DEG C, the soaking time of the high temperature and pressure sintering is preferably 5~12min, further excellent
It is selected as 6min.
The present invention occurs between boron carbide, titanium valve and boron nitride particle inside sintered body by using in-situ synthesis
Chemically react in-situ preparation various reinforced phase (such as TiB2, TiC, TiN etc.), improve PCBN compact mechanical property to reach
Purpose.And reinforced phase is formed and is grown up in sintered body internal-response, surface no-pollution, the compatibility of matrix and reinforcement is good
Good, interface bond strength is higher, and the intensity and hardness of PCBN compact can be improved.
In the present invention, the in-situ preparation various reinforced phase between boron carbide, titanium valve and boron nitride particle inside the sintered body
TiB2, TiC, TiN reaction equation as shown in formula 1~2:
2BN+3Ti=2TiN+TiB2Formula 1
B4C+3Ti=2TiB2+ TiC formula 2
Polycrystalline cubic boron nitride compound sheets provided by the invention and preparation method thereof are carried out below with reference to embodiment detailed
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
CBN, B are prepared according to following ratio4C, Ti powder, AlN, Al2O3With Co powder:
Cubic boron nitride micro mist is by three granularmetric compositions, respectively 8 μm, 6 μm and 3 μm, and three's weight ratio is 2:3:5, and three
Person accounts for the 85% of gross weight；Boron carbide powder average particle size is 10 μm, and titanium valve average particle size is 5 μm, and the two accounts for powder gross weight
12.5%；Aluminum nitride powder average particle size is 50nm, and alumina powder average particle size is 0.5 μm, and cobalt powder average particle size is 1 μm, three
Account for the 2.5% of powder gross weight.
Said components are subjected to ball milling on ball mill, ethyl alcohol is added as blending agent；By kayexalate and
Polyethyleneimine is added in ethanol solution as decentralized medium, and ball milling ratio of grinding media to material is 4:1, revolving speed 250r/min, time 6h；?
80 DEG C of dry 12h are sieved with 100 mesh sieve after dry.
Mixed material is fitted into the molybdenum cup mold for the high-pressure synthesis that diameter is 14mm, is 1000 DEG C in temperature,
Vacuum degree is 10-2Mixed material is vacuum-treated under the conditions of Pa, the time 1 hour.
Temperature be 500 DEG C, atmosphere be hydrogen under conditions of to sample carry out hydrogen reduction processing, time 0.5h.
By treated, sample synthesizes polycrystalline cubic boron nitride compound sheets through high temperature and pressure in cubic hinge press, pressure
5.5GPa, 1500 DEG C of temperature, soaking time 5min.Mechanical property survey is carried out to the polycrystalline cubic boron nitride compound sheets being prepared
Examination, test result is referring to table 1.
Fig. 1 is the XRD spectrum that polycrystalline cubic boron nitride compound sheets are prepared in embodiment 1, it can be seen from the figure that each group
Divide and in-situ synthesized reaction occurs during the sintering process, is given birth in situ between boron carbide, titanium valve and boron nitride particle inside sintered body
At various reinforced phase TiB2、TiC、TiN。
Fig. 2 is the polycrystalline cubic boron nitride compound sheets profile scanning figure that embodiment 1 is prepared, it can be seen from the figure that
Newly-generated reinforced phase is evenly distributed in around cBN particle, and cBN particle is combined well.
Embodiment 2
CBN, B are prepared according to following ratio4C, Ti powder, AlN, Al2O3With Co powder:
Cubic boron nitride micro mist is by two granularmetric compositions, and respectively 3 μm and 6 μm, the two weight ratio is 1:1, and the two Zhan is total
The 65% of weight；Boron carbide powder average particle size is 10 μm, and titanium valve average particle size is 5 μm, and the two accounts for the 30% of powder gross weight；Aluminium nitride
Powder average particle size is 50nm, and alumina powder average particle size is 0.5 μm, and cobalt powder average particle size is 1 μm, and three accounts for powder gross weight
5%.
Said components are subjected to ball milling on ball mill, ethyl alcohol is added as blending agent；By kayexalate and
Polyethyleneimine is added in ethanol solution as decentralized medium, and ball milling ratio of grinding media to material is 3:1, revolving speed 200r/min, time 6h；?
80 DEG C of dry 12h are sieved with 100 mesh sieve after dry.
Mixed material is fitted into the molybdenum cup mold for the high-pressure synthesis that diameter is 14mm, is 900 DEG C in temperature, very
Reciprocal of duty cycle is 10-2Mixed material is vacuum-treated under the conditions of Pa, the time 1 hour.
Temperature be 450 DEG C, atmosphere be hydrogen under conditions of to sample carry out hydrogen reduction processing, time 0.5h.
By treated, sample synthesizes polycrystalline cubic boron nitride compound sheets through high temperature and pressure in cubic hinge press, pressure
5.5GPa, 1400 DEG C of temperature, soaking time 5min.Mechanical property survey is carried out to the polycrystalline cubic boron nitride compound sheets being prepared
Examination, test result is referring to table 1.
Embodiment 3
CBN, B are prepared according to following ratio4C, Ti powder, AlN, Al2O3With Co powder:
Cubic boron nitride micro mist is by two granularmetric compositions, and respectively 3 μm and 6 μm, the two weight ratio is 1:1, and the two Zhan is total
The 55% of weight；Boron carbide powder average particle size is 10 μm, and titanium valve average particle size is 5 μm, and the two accounts for the 38% of powder gross weight；Aluminium nitride
Powder average particle size is 50nm, and alumina powder average particle size is 0.5 μm, and cobalt powder average particle size is 1 μm, and three accounts for powder gross weight
7%.
Said components are subjected to ball milling on ball mill, ethyl alcohol is added as blending agent；By kayexalate and
Polyethyleneimine is added in ethanol solution as decentralized medium, and ball milling ratio of grinding media to material is 3:1, revolving speed 200r/min, time 6h；?
80 DEG C of dry 12h are sieved with 100 mesh sieve after dry.
Mixed material is fitted into the molybdenum cup mold for the high-pressure synthesis that diameter is 14mm, is 800 DEG C in temperature, very
Reciprocal of duty cycle is 10-3Mixed material is vacuum-treated under the conditions of Pa, the time 1 hour.
Temperature be 600 DEG C, atmosphere be hydrogen under conditions of to sample carry out hydrogen reduction processing, time 0.5h.
By treated, sample synthesizes polycrystalline cubic boron nitride compound sheets through high temperature and pressure in cubic hinge press, pressure
4GPa, 1600 DEG C of temperature, soaking time 5min.Mechanical property survey is carried out to the polycrystalline cubic boron nitride compound sheets being prepared
Examination, test result is referring to table 1.
Embodiment 4
CBN, B are prepared according to following ratio4C, Ti powder, AlN, Al2O3With Co powder:
Cubic boron nitride micro mist is by two granularmetric compositions, and respectively 3 μm and 6 μm, the two weight ratio is 1:1, and the two Zhan is total
The 95% of weight；Boron carbide powder average particle size is 10 μm, and titanium valve average particle size is 5 μm, and the two accounts for the 4% of powder gross weight；Aluminium nitride
Powder average particle size is 50nm, and alumina powder average particle size is 0.5 μm, and cobalt powder average particle size is 1 μm, and three accounts for powder gross weight
1%.
Said components are subjected to ball milling on ball mill, ethyl alcohol is added as blending agent；By kayexalate and
Polyethyleneimine is added in ethanol solution as decentralized medium, and ball milling ratio of grinding media to material is 3:1, revolving speed 200r/min, time 6h；?
80 DEG C of dry 12h are sieved with 100 mesh sieve after dry.
Mixed material is fitted into the molybdenum cup mold for the high-pressure synthesis that diameter is 14mm, is 1200 DEG C in temperature,
Vacuum degree is 10-1Mixed material is vacuum-treated under the conditions of Pa, the time 1 hour.
Temperature be 400 DEG C, atmosphere be hydrogen under conditions of to sample carry out hydrogen reduction processing, time 0.5h.
By treated, sample synthesizes polycrystalline cubic boron nitride compound sheets through high temperature and pressure in cubic hinge press, pressure
6GPa, 1300 DEG C of temperature, soaking time 5min.Mechanical property survey is carried out to the polycrystalline cubic boron nitride compound sheets being prepared
Examination, test result is referring to table 1.
The polycrystalline cubic boron nitride compound sheets mechanical property parameters that 1 Examples 1 to 2 of table is prepared
| Hardness (HV) | Bending strength (MPa) | Hardness measuring method | Strength test method | |
| Embodiment 1 | 4100~4300 | 950~1000 | Indentation method | Three-point bending resistance method |
| Embodiment 2 | 3750~3900 | 1100~1180 | Indentation method | Three-point bending resistance method |
| Embodiment 3 | 3500~3700 | 950~1100 | Indentation method | Three-point bending resistance method |
| Embodiment 4 | 4200~4400 | 900~1000 | Indentation method | Three-point bending resistance method |
By above-described embodiment, the result shows that, polycrystalline cubic boron nitride compound sheets provided by the invention have good mechanical property
Can, hardness is 3500~4400HV, and bending strength is 900~1180MPa.Polycrystalline cubic nitridation in the prior art can effectively be solved
It is easy to appear " crushing knife " phenomenon when boron is used as cutter material, there is technical issues that.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of polycrystalline cubic boron nitride compound sheets, which is characterized in that be prepared by the component comprising following mass percentage
It arrives:
55%~95% cubic boron nitride, 4%~38% bonding agent and 1%~7% sintering aid；
The bonding agent is boron carbide and titanium valve, and the sintering aid includes aluminium nitride, aluminium oxide and cobalt powder.
2. polycrystalline cubic boron nitride compound sheets according to claim 1, which is characterized in that the matter of the boron carbide and titanium valve
Amount is than being 2~5:10.
3. polycrystalline cubic boron nitride compound sheets according to claim 1, which is characterized in that the aluminium nitride, aluminium oxide and
The mass ratio of cobalt powder is 1:1~3:1.
4. polycrystalline cubic boron nitride compound sheets according to claim 1, which is characterized in that the partial size of the cubic boron nitride
It is 1~22 μm.
5. polycrystalline cubic boron nitride compound sheets according to claim 1, which is characterized in that boron carbide in the bonding agent
Average grain diameter is 5~10 μm, and the average grain diameter of titanium valve is 1~5 μm.
6. the preparation method of any one of Claims 1 to 5 polycrystalline cubic boron nitride compound sheets, which is characterized in that comprising with
Lower step:
After cubic boron nitride, bonding agent and sintering aid are mixed, high temperature and pressure sintering is carried out, it is multiple to obtain polycrystalline cubic boron nitride
Close piece.
7. preparation method according to claim 6, which is characterized in that the pressure of the high temperature and pressure sintering is 4~6GPa,
Temperature is 1300~1600 DEG C, and soaking time is 5~12min.
8. preparation method according to claim 6 or 7, which is characterized in that further include pre- place before the high temperature and pressure sintering
Reason, the pretreatment include vacuum heat treatment and reduction treatment.
9. preparation method according to claim 8, which is characterized in that the temperature of the vacuum heat treatment is 800~1200
DEG C, vacuum degree 10-1Pa~10-3Pa, time are 1~3h.
10. preparation method according to claim 8, which is characterized in that the temperature of the reduction treatment is 400~600 DEG C,
Time is 0.5~2h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635234A (en) * | 2020-06-10 | 2020-09-08 | 中国有色桂林矿产地质研究院有限公司 | Polycrystalline cubic boron nitride composite sheet and preparation method and application thereof |
| GB2591616A (en) * | 2020-01-28 | 2021-08-04 | Element Six Uk Ltd | Polycrystalline cubic boron nitride material |
| CN113999035A (en) * | 2021-11-25 | 2022-02-01 | 桂林特邦新材料有限公司 | Rod crystal/plate crystal ZrB2PCBN composite sheet of (-ZrN) -AlN composite ceramic and preparation method thereof |
| CN115404372A (en) * | 2022-09-06 | 2022-11-29 | 中国有色桂林矿产地质研究院有限公司 | Preparation method of polycrystalline cubic boron nitride composite superhard material |
| CN115594509A (en) * | 2022-09-27 | 2023-01-13 | 中国有色桂林矿产地质研究院有限公司（Cn） | Polycrystalline cubic boron nitride composite material with rod crystal structure and preparation method and application thereof |
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| GB2591616A (en) * | 2020-01-28 | 2021-08-04 | Element Six Uk Ltd | Polycrystalline cubic boron nitride material |
| CN111635234A (en) * | 2020-06-10 | 2020-09-08 | 中国有色桂林矿产地质研究院有限公司 | Polycrystalline cubic boron nitride composite sheet and preparation method and application thereof |
| CN111635234B (en) * | 2020-06-10 | 2022-05-24 | 中国有色桂林矿产地质研究院有限公司 | Polycrystalline cubic boron nitride composite sheet and preparation method and application thereof |
| CN113999035A (en) * | 2021-11-25 | 2022-02-01 | 桂林特邦新材料有限公司 | Rod crystal/plate crystal ZrB2PCBN composite sheet of (-ZrN) -AlN composite ceramic and preparation method thereof |
| CN113999035B (en) * | 2021-11-25 | 2023-03-10 | 桂林特邦新材料有限公司 | Rod crystal/plate crystal ZrB 2 PCBN composite sheet of (-ZrN) -AlN composite ceramic and preparation method thereof |
| CN115404372A (en) * | 2022-09-06 | 2022-11-29 | 中国有色桂林矿产地质研究院有限公司 | Preparation method of polycrystalline cubic boron nitride composite superhard material |
| CN115594509A (en) * | 2022-09-27 | 2023-01-13 | 中国有色桂林矿产地质研究院有限公司（Cn） | Polycrystalline cubic boron nitride composite material with rod crystal structure and preparation method and application thereof |
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