CN107820441B - The monocrystalline state diamond particles and its manufacturing method of the particle containing cubic boron nitride - Google Patents
The monocrystalline state diamond particles and its manufacturing method of the particle containing cubic boron nitride Download PDFInfo
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- CN107820441B CN107820441B CN201780001990.2A CN201780001990A CN107820441B CN 107820441 B CN107820441 B CN 107820441B CN 201780001990 A CN201780001990 A CN 201780001990A CN 107820441 B CN107820441 B CN 107820441B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
- B01J3/065—Presses for the formation of diamonds or boronitrides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2203/00—Processes utilising sub- or super atmospheric pressure
- B01J2203/06—High pressure synthesis
- B01J2203/0605—Composition of the material to be processed
- B01J2203/061—Graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2203/00—Processes utilising sub- or super atmospheric pressure
- B01J2203/06—High pressure synthesis
- B01J2203/065—Composition of the material produced
- B01J2203/0655—Diamond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2203/00—Processes utilising sub- or super atmospheric pressure
- B01J2203/06—High pressure synthesis
- B01J2203/065—Composition of the material produced
- B01J2203/066—Boronitrides
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Abstract
The monocrystalline state diamond particles of excellent heat stability are provided.Monocrystalline state diamond particles contain cubic boron nitride particle.Preferably, cubic boron nitride particle is present in the inside and/or surface of the monocrystalline state diamond particles of the particle containing cubic boron nitride, the average grain diameter of monocrystalline state diamond particles is 500 μm hereinafter, the average grain diameter of cubic boron nitride particle is 0.05~100 μm.
Description
Technical field
The present invention relates to the monocrystalline state diamond particles of the particle containing cubic boron nitride of excellent heat stability and its manufactures
Method.
Background technique
Diamond has highest hardness on substance, is widely used in grinding to what a variety of materials such as superhard alloy were ground
Grind removing material used in the cutting of material, integrated circuit etc..Use grinding-material, the removing material requirement of diamond every
The cutting material removal amount of unit time is big, the surface roughness of machined surface is small.In general, in order to improve grinding accuracy, using more
The diamond abrasive grain of crystalline state.But for the diamond abrasive grain of polycrystalline state, due to the dynamic pressurized by using a large amount of explosive
It is manufactured to manufacture, furthermore be sintered using diamond particles as starting material, therefore manufacturing process is restricted, is also high
Expensive.
Therefore, the abrasive grain of monocrystalline state diamond has been used to attract attention in recent years.Monocrystalline state diamond has natural diamond, closes
At diamond.It is essentially Ia type to natural diamond, and position has nitrogen between lattice or lattice.In addition, natural diamond
The content of impurity, the deviation of texture be big, quality, performance are unstable.In turn, due to natural diamond according to digging amount valence
Lattice change, therefore there are problems in terms of stable supplying, also expensive.On the other hand, diamond synthesis being capable of stable supplying
Than the article that natural diamond has certain quality.
Additionally, it is known that usually diamond is either natural or synthesis, thermal stability inequality in an atmosphere.Specifically,
Diamond starts to aoxidize at 600~700 DEG C in an atmosphere, is burned off at 900 DEG C or so.Therefore, it is processed using diamond fabrication
With tool or grinding abrasive cutting-off grinding stone (hereinafter referred to as " machining tool ".) when, the calcining under high temperature is difficult in an atmosphere.
In order to manufacture the tool with durability, it is desirable that the oxidative resistance under high temperature.
Therefore, the method for the high-temperature thermal oxidation as inhibition in an atmosphere, such as describe in patent document 1 by gold
Boron is adulterated when hard rock synthesizes to improve the technical solution of the oxidative resistance under high temperature.In patent document 1, as boron source, it can enumerate
Amorphous boron powder, boron carbide (B out4C), iron boride (FeB) alloy, metal boron.In addition, also being described in the document
That the proportion of goods damageds at 850 DEG C are insufficient is per second 0.25%, 700 DEG C or more at a temperature of start to be lost.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-502955 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2001-170474 bulletin
Summary of the invention
Problems to be solved by the invention
It is as recorded in Patent Document 1, boron-doped diamond and undoped diamond phase ratio, at high temperature resistance to
Oxidisability is excellent.
But that records in patent document 1 has carried out boron doped diamond also to have the carbon variation in synthesis being diamond
While with make boron carbide be precipitated reaction the case where.In the synthesis of adjoint such reaction, as recorded in Patent Document 2
, sometimes during diamond and boron carbide are competed and be precipitated, the particle growth of diamond particles is hindered, and cannot be obtained
To desired diamond particles.In addition, the lattice defect of previous boric diamond is significant, compares particle with undoped with diamond phase
Intensity difference but be difficult to need further for sufficient process velocity thus while having a degree of from hair tonic sword
Improvement.
In addition, in grinding abrasive cutting-off processing, at the same reach polished surface with high accuracy and big process velocity plus
The requirement of work abrasive grain is common.In such a case, it is being wanted recently with the chemical combination materialization and complication of rapidoprint
High rigidity, toughness, abrasion performance, the heat-resistant quality of machining tool are asked, calcination temperature when needing for machining tool to be made is set
It is set to higher temperature, further progress hardness, realizes abrasion performance.
The boron-doped diamond recorded in patent document 1 is able to suppress as previously described in 850 DEG C or so a degree of oxygen
Change, but think in an atmosphere more than 1000 DEG C in the case where be difficult to inhibit to aoxidize.In order to inhibit to aoxidize, it is also considered that in nonactive gas
Various calcinings are carried out in atmosphere, if but consider calciner plant, manufacturing cost, calcining in an atmosphere is indispensable.
In this way, being strongly desired since previous diamond particles cannot cope with the high temperature of calcination temperature in recent years
Obtain can be improved the diamond particles of calcination temperature when machining tool is made.
Problem of the present invention is that providing the monocrystalline state diamond particles and its manufacturing method of excellent heat stability.
The solution to the problem
The inventors of the present invention in order to improve the oxidative resistance of diamond, be conceived to first make to have with diamond phase ratio it is same with
On substance and the diamond of thermal stability this point coexists and is studied.Cubic boron nitride is thermostabilization at 1300 DEG C or so
, there is high rigidity as the HV5000 inferior to the HV8600 of diamond, lattice constant 0.362nm, with diamond
0.357 is very close.Additionally, it is known that cubic boron nitride is the substance of diamond lattic structure and energy hetero-epitaxy.
Herein it is known that if adding in the reactive material using graphite and catalyst metals as principal component as diamond crystal
Growth cores diamond particles, then karyomorphism is at becoming easy, promote to using graphite as the growth of the diamond of starting material, gold
The harvest yield of hard rock crystal improves epoch-makingly.Make the karyomorphism for growing particle at easy way in chemistry using crystal seed in this way
The technology frequently used in vapor phase method.
Therefore, the viewpoint that the inventors of the present invention also include manufacturing method to the substance with cubic boron nitride and diamond exists
It is interior to be studied repeatedly.As the synthetic method of diamond, chemical gas-phase method can be enumerated first.It, will be brilliant in chemical gas-phase method
Lattice constant and the close cubic boron nitride of diamond make diamond heteroepitaxial growth, can obtain diamond as crystal seed.
But chemical gas-phase method is the method for making diamond layer heteroepitaxial growth on cubic boron nitride layer.Due to obtained layer
In the stepped construction of diamond layer and cubic boron nitride layer, therefore the synergy of the two cannot be played, thermostabilization cannot be made
Property is improved.The particle as grinding-material is obtained in addition, though must also consider to crush obtained laminated body, but several
The case where particle for being is polycrystalline diamond, it is a large amount of needed for industrial and industry purposes as grinding-material
Production is difficult.
The inventors of the present invention are premised on industrial or industry purposes, to by largely and inexpensively obtaining diamond lap
The method of the high temperature and high pressure method diamond synthesis of material granule is studied.In general, synthesizing Buddha's warrior attendant using high temperature and high pressure method
In the case where stone particulate abrasive material, metallic compound used in catalyst or solvent or carbide are mixed into diamond crystal
Interior, the strength reduction of diamond becomes problem.By adjusting synthesis temperature and synthesis pressure, make in energy synthetic catalyst or solvent
The diamond lap material for being mixed into the high-quality reduced of metallic compound or carbide, but to obtain high-quality
Diamond particles, then its harvest yield tails off.But as previously mentioned, if in advance in the diamond particles using high temperature and high pressure method
Diamond particles are added when synthesis as crystal seed, then core generation becomes easy, the harvest yield of diamond particles improves.But by
It generates and is easy in core, therefore diamond particles are grown everywhere, generate twin crystal, polycrystalline state easy to form.Synthetic single crystal state gold as a result,
In the case where hard rock particulate abrasive material, it is difficult to expect using crystal seed.
The inventors of the present invention are actually using the cubic boron nitride particle usually used not as starting material as based on high temperature
The crystal seed of the diamond synthesizing of high-pressure process is put into starting material.As a result, surprisingly having obtained following opinion: constituting
The boron of added cubic boron nitride particle does not replace the lattice position in diamond single crystal or Xiang Jing as boron doping object
The diffusion of compartment position.In addition, at the same time, obtain following opinion: diamond particles are monocrystalline state, and cubic boron nitride particle
Remained in monocrystalline state diamond with crystal state.
In turn, following opinion is also obtained: even if harvest yield is also and by diamond using cubic boron nitride particle as crystal seed
The case where particle is as crystal seed similarly improves.
Based on the opinion, the obtained present invention is as follows.
(1) the monocrystalline state diamond particles of a kind of particle containing cubic boron nitride, contain cubic boron nitride particle.
(2) the monocrystalline state diamond particles of the particle containing cubic boron nitride according to above-mentioned (1), wherein cubic crystal
Boron nitride particle is present in the inside and/or surface of the monocrystalline state diamond particles of the particle containing cubic boron nitride.
(3) the monocrystalline state diamond particles of the particle containing cubic boron nitride according to above-mentioned (1) or above-mentioned (2),
In, the average grain diameter of monocrystalline state diamond particles is 500 μm or less.
(4) the monocrystalline state diamond of the particle containing cubic boron nitride according to any one of above-mentioned (1)~above-mentioned (3)
Particle, wherein the average grain diameter of cubic boron nitride particle is 0.05~100 μm.
(5) manufacturing method of the monocrystalline state diamond particles of a kind of particle containing cubic boron nitride, which is characterized in that make
With the manufacturing method of the monocrystalline state diamond particles of the particle containing cubic boron nitride of high temperature and high pressure method, wherein by by stone
Ink and/or non-diamond carbon, catalyst metals and/or solvent metal and cubic boron nitride particle are exposed to the equal of carbon
The pressure and temperature in the Thermodynamically stable region of diamond synthesizes in weighing apparatus figure.
(6) manufacturing method of the monocrystalline state diamond particles of the particle containing cubic boron nitride according to above-mentioned (5),
In, aforementioned catalytic agent metal and/or solvent metal are to contain at least one kind of alloy in iron, nickel, cobalt and manganese.
(7) system of the monocrystalline state diamond particles of the particle containing cubic boron nitride according to above-mentioned (5) or above-mentioned (6)
Make method, wherein the pressure and temperature in Thermodynamically stable region are respectively 5~10GPa, 1300~2000 DEG C.
Detailed description of the invention
Fig. 1 shows the phase equilibrium diagram of carbon.
Fig. 2 be when the monocrystalline state diamond particles for manufacturing the particle of the invention containing cubic boron nitride are shown pressure-when
The figure of half interval contour and temperature-time curve.
Fig. 3 is the optical microscope photograph of the diamond particles of example, and (a) of Fig. 3 is the optics that multiplying power is 1000 times
Microscope photo, (b) of Fig. 3 are the optical microscope photographs that multiplying power is 100 times.
Fig. 4 be the diamond particles for showing boron-undoped comparative example, doped with boron comparative example diamond particles and
The diamond particles of example containing cBN, thermal gravimetric analysis results figure in particle.
Specific embodiment
The present invention will be described in further detail below.
1. the monocrystalline state diamond particles of the particle containing cubic boron nitride
Monocrystalline state diamond particles of the invention contain cubic boron nitride particle (hereinafter, being suitable for being known as " cBN
Grain ".).Monocrystalline state diamond particles of the invention are using cBN particle as crystal seed and to make list by high temperature and high pressure method as described later
Obtained from crystalline diamond growth.CBN particle to remain in monocrystalline state diamond as former state as a result,.In addition, due to the present invention
Diamond particles be monocrystalline state, therefore be not present diamond crystal boundary, also there's almost no twin crystal.Even if being nitrogenized containing cubic crystal
The monocrystalline state diamond particles of boron particles using with cBN particle joint surface or cBN particle itself be crushed as starting point, there is height
The monocrystalline state diamond of hardness also becomes sword, is able to maintain that processing capacity per unit time, is also excellent from hair tonic sword.In this way,
In the present invention, since monocrystalline state diamond particles contain cBN particle, the monocrystalline state Buddha's warrior attendant of the few high-purity of impurity can be played
The synergy of thermal stability possessed by high rigidity possessed by stone and cBN particle.
In the present invention, from the viewpoint of giving full play to synergy above-mentioned, it is generally desirable to which cBN particle is present in containing vertical
The inside and/or surface of the monocrystalline state diamond particles of prismatic crystal boron nitride particle, it is therefore especially desired to exist inside and surface.
If cBN particle is present in the inside and surface of monocrystalline state diamond, even diamond particles abrasion due to grinding, grinding
In the case of, cBN particle also successively exposes from inside to surface, can also play heat of the cBN particle to the heat generated in processing stand
Stability.In the present invention, " inside " indicates that cBN particle is included in monocrystalline state diamond." surface " indicates one of cBN particle
Divide and exposes to the surface of monocrystalline state diamond.
For the monocrystalline state diamond particles of the particle of the invention containing cubic boron nitride, from the above-mentioned synergy of performance
Viewpoint is set out, it is generally desirable to which the quality of the monocrystalline state diamond particles relative to the particle containing cubic boron nitride contains 1~10 matter
Measure the cBN particle of %.If 1 mass % or more, then the thermal stability of cBN is easy to appear.On the other hand, if 10 mass % with
Under, then it is not likely to produce twin crystal in diamond synthesizing, becomes easy to obtain single crystal grain.
In turn, in the present invention, from no matter diamond particles are from which direction abrasion, expose cBN particle successively to table
From the perspective of face, it is generally desirable to which cBN particle is homogeneously dispersed in monocrystalline state diamond.
The average grain diameter of monocrystalline state diamond particles of the invention is preferably 500 μm or less.When being 500 μm or less, by
It is not excessive in particle, therefore can be used for extensive purposes.Lower limit is not particularly limited, from ensuring more than a certain amount of stock removal
From the perspective of, ideal is 0.25 μm or more.
It should be noted that synthesis after diamond particles it is big in the case where, desired partial size, can also make in order to obtain
With the crushing powder particles for diamond particles of the invention being crushed, being had adjusted partial size.Particle containing cubic boron nitride of the invention
Monocrystalline state diamond particles since cBN particle to be homogeneously dispersed in monocrystalline state diamond to a certain degree, even
Pulverized particles are also able to maintain that thermal stability.
Monocrystalline state diamond particles of the invention contain cBN particle.The lattice constant of cBN is 0.362nm, with diamond
0.357 is very close, and cBN works in the diamond synthesizing based on high temperature and high pressure method as crystal seed.In addition, cBN exists
1300 DEG C or so are heat-staple, even if sintering temperature when improving production grinding stone, is also able to suppress the oxidation of diamond particles
Caused burn-up.In turn, since cBN shows the hardness of the HV5000 of the HV8600 inferior to diamond, in same list
Difference of hardness is generated in brilliant particle.The difference of hardness is that monocrystalline state diamond and the interface of cBN particle are risen as what particle itself was crushed
The principal element of point.In addition, the crushing of abrasive grain when difference of hardness can not only prevent processing, and when being also processing from hair tonic
The principal element of the generation of cutting edge when the starting point of sword, grinding abrasive cutting-off.As a result cause the increase i.e. per unit of cutting edge
The increase of the processing capacity of time.
In the present invention, in order to play the effect containing cBN, the degree for containing cBN with the amount of impurity levels cannot be played, be needed
Will the amount of existing degree in granular form contain cBN.On the other hand, it in order to be maintained as the property of diamond particles, needs
Make the partial size of cBN particle in range appropriate without excessive.In the present invention, the average grain diameter of cBN particle preferably 0.05~
100 μm, more preferably 0.1~50 μm.
In the present invention, average grain diameter is as follows.The particle for being 0.25 μm or more for average grain diameter, by laser diffraction and scattering side
Formula size distribution measuring machine (for example, Malvern Instruments corporation, model: Mastersizer2000,
MicrotracBEL Corp. system, model: MicrotracMT3000 etc.) volume mean diameter D50 value as average grain diameter.Separately
It on the one hand, is 0.25 μm of particle below for average grain diameter, since the measurement by laser diffraction and scattering mode is difficult,
By dynamic light scattering mode or the size distribution measuring machine of centrifugal type (for example, MicrotracBEL Corp. system, model
MicrotracUPA, NanotracUPA-EX etc.) volume mean diameter D50 value as average grain diameter.
2. the manufacturing method of the monocrystalline state diamond particles of the particle containing cubic boron nitride
For the manufacturing method of the monocrystalline state diamond particles of the particle of the invention containing cubic boron nitride, by with high temperature
High-pressure process, by graphite and/or the exposure of non-diamond carbon, catalyst metals and/or solvent metal and cubic boron nitride particle
The pressure and temperature in the thermodynamically stable region of diamond synthesizes in the phase equilibrium diagram of carbon.
The manufacturing method of the present invention is by that will be used as impurity treatment in high temperature and high pressure method actually and avoid to diamond
Mixed cBN, which is put into granular form into the starting material of diamond synthesizing, to be completed, in the manufacture of monocrystalline state diamond
In be epoch-making method.
It should be noted that exist as the prior art by agglomerated material made of diamond particles and cBN sintering, but
It obtains being the diamond of monocrystalline state and the complex of cBN, compared with diamond particles of the invention, tissue is different.For
The complex, the metal in conjunction with used in crystal boundary be mixed into caused by strength reduction it is significant.Even if when processing as a result,
From hair tonic sword, the intensity for becoming the complex of sword is also low, processing capacity does not also increase.
In addition, due to sintering when cBN particle be not scattered in diamond crystal, cannot play as in the present invention
The synergy of diamond particles and cBN particle.In turn, chemical gas-phase method is as previously mentioned, in monocrystalline state diamond particles not
CBN particle can be contained.Therefore, in order to manufacture the monocrystalline state diamond particles containing cBN particle, high temperature and high pressure method is optimal.
The manufacturing method of the present invention is that (1) will be mixed with the starting material of graphite, cBN particle and catalyst metals
Process, (2) carry out compacting to mixed raw material to be configured to the process of regulation shape, (3) for pressed formed body and be exposed to
The process synthesized under conditions of defined pressure and temperature.They are described in detail below.
(1) process that will be mixed with the starting material of graphite, cBN particle and catalyst metals
Graphite used in the manufacturing method of the present invention preferably impurity concentration less than 30ppm, average grain diameter be 100 mesh
(opening: 127 μm) is hereinafter, cBN particle is also the same.If bigger than this, the recrystallizationization of graphite and the melting flower of catalyst metals
It is time-consuming, and temperature curve and pressure curve complicate.
Catalyst metals used in the manufacturing method of the present invention are preferably containing at least 1 in iron, nickel, cobalt and manganese
The mixture or alloy of kind.It is ideal in order to improve the transformation efficiency from graphite to diamond for the composition of mixture or alloy
Be weight %, Co:3 of Ni:25~30~5 weight %, Mn:3~5 weight % and surplus be Fe and inevitable impurity.It is flat
Equal partial size is advisable with graphite equal extent.It should be noted that " mixture " indicate to mix on the metal (powder) of each element and
Winner or alloy (powder) person of mixing by two or more element.
For the mixing ratio of graphite and catalyst metals and cBN particle, from volume when conversion from from graphite to diamond
From the perspective of contraction bring decline of pressure, it is generally desirable to (powdered graphite): (catalyst metals+cBN particle)=11:8~
11.From the viewpoint of core generates density, the mixing ratio of catalyst metals and cBN particle preferably (catalyst metals):
(cBN particle)=99:1~90:10.
The starting material weighed in the above range is mixed.Mixed method is advisable for usual way.For example, ideal
It is to put into above-mentioned starting material into powder mixer, is mixed 30 minutes or more under the decompression of 250~300MPa.As a result,
Obtain 100 mesh (opening: 149 μm) mixed-powder below.
(2) process mixed-powder suppressed and be configured to regulation shape
Above-mentioned mixed-powder is kept for 3~10 seconds under the plus-pressure of 220~280MPa with usually used press,
Obtain desired cylindric raw material.
The pressure medium container that the cylindric raw material is filled in pyrophyllite, as starting material.
(3) process for pressed formed body being exposed to defined pressure and temperature and being synthesized
Starting material obtained in above-mentioned operation is directed into ultra-high pressure apparatus, it is bent according to the pressure curve and temperature of regulation
The synthesis of line progress diamond.For pressure curve and temperature curve, it is set as in the phase equilibrium diagram of carbon shown in Fig. 1, most
The pressure and temperature in the whole thermodynamically stable region of diamond.In addition, two curves are not particularly limited, it is desirable to considering
To the temperature and pressure of starting material homogenization, the recrystallizationization of graphite, the melting of catalyst metals and the wetting of graphite and
Core is generated, determines various conditions after particle growth and operated with the multistage.Pressure and temperature for example, as shown in Figure 2
Operation.
As an example of pressure curve, firstly, by starting material import ultra-high pressure apparatus after, under atmospheric pressure keep 60~
120 seconds.Then, to boost to the 20~25% of final setting pressure within 20~30 seconds and then be boosted to 30~120 seconds final
It sets the 60~70% of pressure, kept for 60~120 seconds.Then, with boost within 30~60 seconds final setting pressure 80~
90%, it is kept for 60~180 seconds.Then, pressurization in 300~600 seconds is used until as the 5~10GPa, excellent for finally setting pressure
5.5~6.3GPa is selected, and is kept for 300~1200 seconds.Finally atmospheric pressure was decompressed to 120~600 seconds.
As an example of temperature curve, firstly, being protected at room temperature~200 DEG C after starting material is imported ultra-high pressure apparatus
It holds 60~120 seconds.Then, will heat up speed and be set as 25~60 DEG C/sec, from room temperature to 1300~2000 DEG C, preferably
1350~1550 DEG C of initial temperature region is kept for 30~120 seconds.Then, it is reduced to from initial temperature within 10 seconds
Low 4~7% temperature is kept for 30~120 seconds in the temperature region.Then, it was reduced in turn with 700~1200 seconds low
2.5~3.5% temperature is kept for 240~1200 seconds in the temperature region.Finally, being begun to cool within 300 seconds to room
Temperature.
In addition, for the opportunity of pressure and temperature, from the knot again of melting and graphite by heating bring catalyst metals
From the perspective of crystallization, it is generally desirable to be warming up to maximum temperature while boosting to maximum stressed 20~22%, boost
To maximum plus-pressure, depressurize start while or decompression start after and decompression be over before begin to cool, it is generally desirable to boost
To maximum plus-pressure, after being fully converted into diamond with 300~1200 seconds graphite, turn again from diamond to graphite in order to prevent
Change, is also begun to cool before decompression is over or while decompression starts.
By the way that starting material original is exposed to high temperature and pressure under the conditions of as described above, can manufacture containing cBN particle
Single-crystal diamond.
[embodiment]
1. the production of the diamond particles of example
It is urged firstly, preparing cBN powder that fine graphitic powder and volume average particle size D50 value are 3.5 μm with Fe system alloy
Agent metal powder (Ni:28 weight %, Co:5 weight %, Mn:3 weight %, surplus are Fe and inevitable impurity) mixes
Close powder (cBN particle: Fe system alloy catalyst metal powder=97:3) and fine graphitic powder and mixed-powder be 400 mesh with
Under powder.The mixing ratio of powdered graphite and mixed-powder is (powdered graphite): (cBN particle and Fe system alloy catalyst powder
Mixed-powder)=11:9.
It puts into as starting material to powder mixer, is mixed 120 minutes under the decompression of 280MPa, obtain 100
Mesh fine mixed-powder below.
Then, mixed-powder is put into compacting tool set, is pressurizeed under conditions of 230MPa, 25 DEG C, 5 seconds
Shape, productionCylindric raw material.Obtained cylindric raw material is filled in 75mm3Pyrophyllite pressure
Power media container, as starting material.
Pressure and temperature are set as 6.2GPa, 1350 DEG C, starting material is directed into China system cube anvil (cubic
Anvil) type ultra-high pressure apparatus and it is exposed to diamond stable region.
Pressure curve is as shown in Figure 2.Specifically, starting material is set to ultra-high pressure apparatus, keep under atmospheric pressure
90 seconds.Then, to boost within 30 seconds 20% i.e. 1.24GPa of setting pressure and then boost to 65% i.e. 4.0GPa with 60 seconds
And it is kept for 60 seconds.Then, to boost within 30 seconds 85% i.e. 5.3GPa of setting pressure and be kept for 120 seconds.And then with 600 seconds
It boosts to setting pressure i.e. 6.2GPa and is kept for 300 seconds.Finally atmospheric pressure was decompressed to 180 seconds.
In addition, temperature curve is as shown in Figure 2.Specifically, starting material is set to ultra-high pressure apparatus, at 150 DEG C
It is kept for 90 seconds.Initial temperature is set as 1450 DEG C of high 8%, was risen with 52 DEG C/sec of heating rate from 150 DEG C with about 25 seconds
Temperature is to 1450 DEG C and is kept for 90 seconds.Then, temperature is reduced to 1390 DEG C and holding 60 seconds of low 4% within 10 seconds.
Then, it after 1350 DEG C and holding 300 seconds of low 3% are reduced to 720 seconds and then by temperature, begins to cool.
For the opportunity of pressure and temperature, almost with boost to 1.24GPa and be warming up to 1450 DEG C simultaneously, boost to
Temperature when 6.2GPa is 1350 DEG C, is begun to cool after 300 seconds.
2. the production of the boric diamond particle as comparative example
In above-mentioned " 1. ", replace cBN particle using boron powder, in addition to this, by method same as above-mentioned " 1. " into
Row production.
3. the production of the undoped diamond particles as comparative example
In above-mentioned " 1. ", cBN particle is not put into, in addition to this, is made by method same as above-mentioned " 1. ".
4. evaluation
(1) impact strength
Carry out commenting based on broken value (Toughness Index (Ti) value) tested by ball mill impact cutting fragility
Valence.Internal diameter 12.5mm, depth 25mm cylindric steel capsule in, the enclosed sample 2ct (400mg) for having divided size in advance and
Steel ball 1 of diameter 8mm weight 2g.Steel capsule after will be enclosed carries out 2 points with RETEK corporation Friability tester
Clock 2830 times shakes, sample is crushed.For the sample after shaking, the quality of sample entirety is calculated relative to the sample through crushing
Quality ratio and indicated with 100 points of rates.
Show the result in table 1.
(1) thermal stability
Using Thermgravimetric Analysis Apparatus (Rigaku corporation, model: Thermo plus EVO2), measure in air atmosphere
Under, under conditions of 10 DEG C/min from room temperature to 1300 DEG C when example weight slip.
Show the result in Fig. 4.
(2) average grain diameter of diamond particles
Obtained diamond particles are by carrying out size screening based on the sieve method of JIS B 4130 (1998).
(3) average grain diameter, the number of the cBN particle in diamond particles
Since the average grain diameter of the cBN particle used as starting material is 30 μm hereinafter, being therefore based on JIS B 4130
(1998) granulometry of sieve method is difficult.Therefore, using diameter of particle measure in usually used laser diffraction formula grain
It spends measure of spread machine (Malvern Instruments corporation, model: Mastersizer2000) and measures average grain diameter.For
Incorporation measures size under an optical microscope to the cBN particle in diamond crystal with micron order, it is thus identified that be averaged with what is used
Partial size is almost without difference.Due to being difficult to count to incorporation to brilliant intracorporal number, visual confirmation uniformity.
[table 1]
It can be defined by table 1, the diamond particles of example have obtained diamond particles of the impact strength lower than comparative example
As a result.This is because the crystal boundary of diamond and cBN in particle becomes starting point, brokenness in the diamond particles of example
It is improved than undoped diamond, boric diamond.In other words, it may be said that example is excellent from hair tonic sword by broken bring
It is different.
Fig. 3 is the optical microscope photograph of the diamond particles of example, and (a) of Fig. 3 is the optics that multiplying power is 1000 times
Microscope photo, (b) of Fig. 3 are the optical microscope photographs that multiplying power is 100 times.
It is clear that by Fig. 3, the generally uniform inside for being scattered in single-crystalline diamond of cBN particle.In addition, for cBN
The average grain diameter of particle, with the conduct volume average particle size D50 after micron order measurement size for 3.5 μm or so, with measured in advance
3.5 μm of value are identical.In addition, the photochrome according to Fig. 3 confirmed, the color of diamond particles synthesizes gold in high temperature and pressure
The yellow of the peculiar color of undoped diamond to often see in hard rock synthesis is compared with green, and then passes through the reddish brown of cBN particle
Mixing, be bottle green.Thus it specifies, the single-crystalline diamond of the present embodiment does not have the distinctive indigo plant of boron-doped diamond
Color~blue-black crystal.
Fig. 4 be the diamond particles for showing boron-undoped comparative example, doped with boron comparative example diamond particles and
The diamond particles of example containing cBN particle, thermal gravimetric analysis results figure in particle.It is clear that by Fig. 4, it is undoped
The undoped diamond particles of the comparative example of boron are reduced since 700 DEG C or so weight, in 900 DEG C or so all burn-ups.In addition,
The diamond particles of boron-doped comparative example start to reduce in 800 DEG C or so weight, reduce 20% or so at 1000 DEG C.It is another
The diamond particles of aspect, the example containing cBN start to reduce in 900 DEG C or so weight, even if reducing in 1000 DEG C of weight
Also less than 5%, high thermal stability is shown.
Claims (5)
1. a kind of monocrystalline state diamond particles of particle containing cubic boron nitride, containing cubic boron nitride particle,
Wherein, the average grain diameter of the cubic boron nitride particle is 0.05~100 μm.
2. the monocrystalline state diamond particles of the particle according to claim 1 containing cubic boron nitride, wherein the cubic crystal
Boron nitride particle is present in the inside and/or surface of the monocrystalline state diamond particles of the particle containing cubic boron nitride.
3. the monocrystalline state diamond particles of the particle according to claim 1 or 2 containing cubic boron nitride, wherein the list
The average grain diameter of crystalline diamond particle is 500 μm or less.
4. a kind of manufacturing method of the monocrystalline state diamond particles of particle containing cubic boron nitride, which is characterized in that it is use
The monocrystalline state diamond particles of the particle according to any one of claims 1 to 3 containing cubic boron nitride of high temperature and high pressure method
Manufacturing method, the manufacturing method has following process:
Mixed processes, by graphite and/or non-diamond carbon, catalyst metals and/or solvent metal and cubic boron nitride
Grain is mixed；
The mixed-powder mixed by the mixed processes is formed forming process；
After starting material obtained in the forming process is imported ultra-high pressure apparatus, kept for 60~120 seconds under atmospheric pressure；
First boosting heating process makes the i.e. final setting pressure of the pressure in the Thermodynamically stable region of diamond in the phase equilibrium diagram of carbon
Power and final set temperature are respectively 5~10GPa and 1300~2000 DEG C, the formed body that will be shaped by the forming process
To boost to the 20~25% of the final setting pressure from atmospheric pressure in 20~30 seconds, and finally set from room temperature to described
Determine temperature；
Second boosting process, after the first boosting process, to boost to the 60 of the final setting pressure in 30~120 seconds
~70%, then kept for 60~120 seconds；
Third is boosted process, after the second boosting process, with boost in 30~60 seconds the final setting pressure 89~
90%, then kept for 60~180 seconds；
4th boosting process, to boost to the final i.e. 5~10GPa of setting pressure in 300~600 seconds, then holding 300~
1200 seconds；With,
Cooling process is depressurized, after the 4th boosting process, to be decompressed to atmospheric pressure in 120~600 seconds, and is begun to cool.
5. the manufacturing method of the monocrystalline state diamond particles of the particle according to claim 4 containing cubic boron nitride, wherein
The catalyst metals and/or solvent metal are to contain at least one kind of alloy in iron, nickel, cobalt and manganese.
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| PCT/JP2017/014364 WO2018185909A1 (en) | 2017-04-06 | 2017-04-06 | Monocrystalline diamond particles containing cubic crystalline boron nitride particles and production method therefor |
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| JP7033824B1 (en) * | 2021-06-28 | 2022-03-11 | 株式会社ディスコ | Manufacturing method of single crystal diamond and single crystal diamond |
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| CN1905992A (en) * | 2004-01-28 | 2007-01-31 | 吴诺顿株式会社 | Method for producing vitrified diamond whetstone |
| CN103883257A (en) * | 2014-02-14 | 2014-06-25 | 常州大学 | Method for manufacturing boron nitride toughened polycrystalline diamond |
| CN104941520A (en) * | 2006-12-13 | 2015-09-30 | 戴蒙得创新股份有限公司 | Abrasive compact with improved machinability |
| CN108118234A (en) * | 2016-11-28 | 2018-06-05 | 崔祥仁 | A kind of preparation method of hybrid boric diamonds of CBN and a kind of Fe based alloys catalyst |
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| JPH02192494A (en) * | 1989-01-20 | 1990-07-30 | Sumitomo Electric Ind Ltd | Composite material |
| US5560754A (en) * | 1995-06-13 | 1996-10-01 | General Electric Company | Reduction of stresses in the polycrystalline abrasive layer of a composite compact with in situ bonded carbide/carbide support |
| JP2000296403A (en) * | 1999-04-12 | 2000-10-24 | Sumitomo Electric Ind Ltd | Composite polycrystalline substance cutting tool and manufacture thereof |
| GB201006821D0 (en) * | 2010-04-23 | 2010-06-09 | Element Six Production Pty Ltd | Polycrystalline superhard material |
| JP6173995B2 (en) * | 2014-10-29 | 2017-08-02 | 燕山大学 | Ultra high hardness nano twinned diamond bulk material and method for producing the same |
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|---|---|---|---|---|
| CN1905992A (en) * | 2004-01-28 | 2007-01-31 | 吴诺顿株式会社 | Method for producing vitrified diamond whetstone |
| CN104941520A (en) * | 2006-12-13 | 2015-09-30 | 戴蒙得创新股份有限公司 | Abrasive compact with improved machinability |
| CN103883257A (en) * | 2014-02-14 | 2014-06-25 | 常州大学 | Method for manufacturing boron nitride toughened polycrystalline diamond |
| CN108118234A (en) * | 2016-11-28 | 2018-06-05 | 崔祥仁 | A kind of preparation method of hybrid boric diamonds of CBN and a kind of Fe based alloys catalyst |
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