WO2019098172A1 - ダイヤモンド多結晶体及びその製造方法 - Google Patents
ダイヤモンド多結晶体及びその製造方法 Download PDFInfo
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- WO2019098172A1 WO2019098172A1 PCT/JP2018/041931 JP2018041931W WO2019098172A1 WO 2019098172 A1 WO2019098172 A1 WO 2019098172A1 JP 2018041931 W JP2018041931 W JP 2018041931W WO 2019098172 A1 WO2019098172 A1 WO 2019098172A1
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- Prior art keywords
- diamond
- polycrystalline diamond
- polycrystalline
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- 239000010432 diamond Substances 0.000 title claims abstract description 233
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 227
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000002245 particle Substances 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- 239000003575 carbonaceous material Substances 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 239000012535 impurity Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 16
- 230000000977 initiatory effect Effects 0.000 claims description 14
- 238000005087 graphitization Methods 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron group metals Chemical class 0.000 description 3
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002180 crystalline carbon material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
- B23B27/18—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing
- B23B27/20—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing with diamond bits or cutting inserts
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
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- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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- C04B2235/767—Hexagonal symmetry, e.g. beta-Si3N4, beta-Sialon, alpha-SiC or hexa-ferrites
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Definitions
- the present disclosure relates to a polycrystalline diamond and a method of manufacturing the same.
- This application claims the priority based on Japanese Patent Application No. 2017-221932 which is a Japanese patent application filed on November 17, 2017. The entire contents of the description of the Japanese patent application are incorporated herein by reference.
- a polycrystalline diamond has excellent hardness and has no directionality or cleavage of hardness, and thus is widely used as a cutting tool, a tool such as a dresser or a die, an excavating bit or the like.
- diamond powder which is a raw material, together with a sintering aid and a binder, diamond is thermodynamically stable high pressure and high temperature (generally, the pressure is about 5 to 8 GPa and the temperature is It is obtained by sintering under the conditions of about 1300 to 2200.degree.
- iron group metals such as Fe, Co, Ni, etc., carbonates such as CaCO 3 etc.
- ceramics such as SiC etc.
- the sintering aid and binder used are contained in the polycrystalline diamond.
- the sintering aid and the binder have a considerable influence on the mechanical properties such as hardness and strength of the polycrystalline diamond and the heat resistance.
- non-diamond carbon materials such as graphite, glassy carbon, amorphous carbon, etc. can be directly converted to diamond under ultra-high pressure and high temperature without using a sintering aid and the like. Direct conversion from the non-diamond phase to the diamond phase and simultaneous sintering result in a polycrystalline single phase diamond.
- Non-Patent Document 1 M. Wakatsuki, K. Ichinose, T. Aoki, Japan. J. Appl. Phys., 11 (1972), pp 578-590 (non-patent document 2), S. Naka, K. Horii, Y. Takeda, T. Hanawa, Nature 259 (1976), p 38 (non-patent document 3), using graphite as a raw material It is disclosed that a polycrystalline diamond can be obtained by direct conversion under ultrahigh pressure and high temperature of 14 GPa to 18 GPa and 3000 K or more.
- Non-Patent Document 5 Discloses a method for obtaining a dense and high purity polycrystalline diamond by direct conversion sintering by indirect heating under high pressure and high pressure of 12 GPa or more and 2200 ° C. or more using high purity and high crystalline graphite as a starting material There is.
- the polycrystalline diamond according to an aspect of the present disclosure is a polycrystalline diamond having a basic composition of [1] single diamond phase, and the polycrystalline diamond has a plurality of diamond particles having an average particle diameter of 30 nm or less.
- the diamond polycrystal is a diamond polycrystal having a carbon dangling bond density of 10 ppm or more.
- a method for producing a polycrystalline diamond according to another aspect of the present disclosure comprising the steps of: [2] preparing a non-diamond carbon material having a degree of graphitization of 0.2 or less; Diamond is converted to cubic diamond and hexagonal diamond directly and sintered under the conditions of thermodynamically stable pressure and temperature without adding any sintering aid and binder. Obtaining a polycrystalline body, and a method of producing a polycrystalline diamond body.
- Non-Patent Documents 1 to 3 are all unconverted because they are manufactured by direct current heating method in which heating is carried out by passing a current directly to a conductive non-diamond carbon material such as graphite. Residual graphite is inevitable.
- the particle size of the diamond is not uniform, and partial sintering tends to be insufficient. For this reason, mechanical properties such as hardness and strength are insufficient, and furthermore, only a piece-like polycrystal can be obtained, so that it has not been put to practical use.
- Non-Patent Documents 4 and 5 Although the polycrystalline diamond obtained by the methods of Non-Patent Documents 4 and 5 has very high hardness, there is a problem that the characteristics such as wear resistance, fracture resistance, crack propagation resistance and the like are insufficient and unstable. there were.
- the polycrystalline diamond according to an aspect of the present disclosure is (1) a polycrystalline diamond having a basic composition of single diamond phase, and the polycrystalline diamond has a plurality of diamond particles having an average particle diameter of 30 nm or less.
- the diamond polycrystal is a diamond polycrystal having a carbon dangling bond density of 10 ppm or more.
- the polycrystalline diamond can have excellent strength while maintaining high hardness.
- the polycrystalline diamond includes, as impurities, at least one element selected from the group consisting of hydrogen, oxygen and nitrogen, and the concentration of the hydrogen, the oxygen and the nitrogen in the polycrystalline diamond Is preferably at most 1 ppm.
- the polycrystalline diamond can have particularly excellent strength.
- concentration of the said nitrogen in the said diamond polycrystal is less than 0.1 ppm.
- the polycrystalline diamond can have particularly excellent strength.
- the polycrystalline diamond has a crack generation load of 10 N or more in a fracture strength test in which a spherical diamond indenter with a tip radius of 50 ⁇ m is pressed against the surface of the polycrystalline polycrystalline body at a loading rate of 1 N / sec. Is preferred.
- Such polycrystalline diamond can have excellent breaking strength and fracture resistance.
- a method for producing a polycrystalline diamond according to another aspect of the present disclosure includes: (5) preparing a non-diamond carbon material having a degree of graphitization of 0.2 or less; Diamond is converted to cubic diamond and hexagonal diamond directly and sintered under the conditions of thermodynamically stable pressure and temperature without adding any sintering aid and binder. Obtaining a polycrystalline body, and a method of producing a polycrystalline diamond body.
- the notation of the form “A to B” means the upper and lower limit (ie, A or more and B or less) of the range, and when there is no description of a unit in A and only a unit is described in B, The unit of and the unit of B are the same.
- the atomic ratio is not particularly limited, it is intended to include all conventionally known atomic ratios and is not necessarily limited to only those in the stoichiometric range.
- the polycrystalline diamond according to the present embodiment is a polycrystalline diamond having a basic composition of single diamond phase, and the polycrystalline polycrystalline body is composed of a plurality of diamond particles having an average particle diameter of 30 nm or less.
- the polycrystalline diamond is a polycrystalline diamond having a carbon dangling bond density of 10 ppm or more.
- the polycrystalline diamond according to the present embodiment has a single phase of diamond as a basic composition, and therefore does not contain a binder phase (binder) formed by one or both of a sintering aid and a binder, and the high temperature condition Even under the bottom, there is no occurrence of shattering due to the difference in the thermal expansion coefficient.
- having a single diamond phase as the basic composition means that the diamond component is at least 99% by volume in the polycrystalline diamond.
- the polycrystalline diamond includes hydrogen, oxygen, nitrogen, and other unavoidable impurities other than the diamond component (eg, Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, Fe, Mo, etc.) May be contained in a total of 1% by volume or less.
- the fact that the polycrystalline diamond contains 99% by volume or more of the diamond component and that it does not contain a bonding phase can be confirmed by observing the surface of the polycrystalline diamond with an optical microscope or an electron microscope.
- the polycrystalline diamond is polycrystalline formed of a plurality of crystal grains, and the average grain size of the diamond particles constituting the polycrystalline diamond is 30 nm or less, the directionality like a single crystal and There is no cleavage and has isotropic hardness and wear resistance in all directions.
- the average particle diameter of the diamond particles is preferably 20 nm or less, and preferably 10 nm or less, from the viewpoint that the polycrystalline diamond can exhibit isotropic hardness and wear resistance in all directions. More preferable.
- the lower limit of the average particle diameter of the diamond particles is preferably 1 nm or more from the viewpoint of obtaining mechanical strength unique to diamond.
- the polycrystalline diamond of the present embodiment is composed of diamond particles having such a small particle diameter, and therefore, can be applied to tools in a wide range of applications such as high load processing and fine processing. .
- the average particle size of the diamond particles can be determined by a cutting method using a scanning electron microscope (SEM). Specifically, first, the polycrystalline diamond is observed at a magnification of 1000 to 100000 times using a scanning electron microscope to obtain a SEM image.
- SEM scanning electron microscope
- a circle is drawn on the SEM image, and eight straight lines are drawn radially from the center of the circle (so that the crossing angles between the straight lines are substantially equal) to the outer periphery of the circle.
- the observation magnification and the diameter of the circle are preferably set so that the number of diamond particles (crystal particles) placed per one straight line is about 10 to 50.
- the aspect ratio (a / b) between the major diameter a and the minor diameter b of the diamond particle is preferably 1 ⁇ a / b ⁇ 4 from the viewpoint of suppressing the occurrence of micro cracks.
- the major axis means the distance between the two most distant points on the outline of the diamond particle.
- the minor diameter means the distance of a straight line which is orthogonal to the straight line defining the major diameter and in which the distance between two points of intersection with the outline of the diamond particle is the shortest.
- the polycrystalline diamond according to the present embodiment has a carbon dangling bond density of 10 ppm or more, and has excellent strength. Although the reason for this is not clear, the present inventors speculate as follows.
- a carbon dangling bond is a bond pair among carbon atom bonds, which has no bonding partner and exists as an unpaired electron, and is present near the surface of a covalent bond crystal or in the vicinity of a lattice defect inside. Carbon dangling bonds have high chemical activity and are in an unstable state.
- the carbon dangling bond density refers to the number of carbon dangling bonds (carbon dangling bonds) present mainly on the surface of the diamond particle based on the total amount of carbon atoms constituting the diamond particle. Is a value indicating the ratio of
- a polycrystalline diamond having a carbon dangling bond density of 10 ppm or more has excellent strength.
- the carbon dangling bond density in the polycrystalline diamond is preferably 30 ppm or more, and more preferably 40 ppm or more, from the viewpoint of improving the bonding strength between diamond particles.
- the upper limit of the carbon dangling bond density is not particularly limited, but is preferably 1000 ppm or less from the viewpoint of production.
- the carbon dangling bond density in the polycrystalline diamond can be measured by electron spin resonance (ESR). Specifically, the derivative curve of the ESR spectrum corresponding to the unpaired spin of carbon dangling bond is measured, the signal intensity is determined from the double integration, and the carbon dangling bond density is calculated from the intensity.
- ESR electron spin resonance
- the polycrystalline diamond according to the present embodiment contains, as an impurity, at least one element selected from the group consisting of hydrogen, oxygen and nitrogen, and the concentrations of hydrogen, oxygen and nitrogen in the polycrystalline diamond are as follows. It is preferable that it is 1 ppm or less.
- the concentrations of hydrogen, oxygen and nitrogen are values indicating the ratio of the numbers of atoms of hydrogen, oxygen and nitrogen, respectively, based on the total number of atoms of the polycrystalline diamond. According to this, the polycrystalline diamond has excellent strength. Although the reason for this is not clear, the present inventors speculate as follows.
- the polycrystalline diamond impurities such as nitrogen which are dissolved in the raw material particles such as graphite are present.
- the adsorption gas consisting of hydrogen, oxygen and nitrogen, etc. present on the surface of the raw material particles, the adsorbed water and the air existing in the voids of the raw material particles are taken into the inside of the polycrystalline diamond in the process of producing the polycrystalline diamond.
- impurities such as hydrogen, oxygen, and nitrogen.
- the concentrations of hydrogen, oxygen and nitrogen in the polycrystalline diamond are as small as 1 ppm or less, respectively, these impurities bond to carbon dangling bonds.
- the possibility of reducing the bonding strength between diamond particles through carbon dangling bonds is low. Therefore, it is speculated that the polycrystalline diamond can have excellent strength.
- the concentration of each of hydrogen, oxygen and nitrogen in the polycrystalline diamond is preferably 1 ppm or less, more preferably 0.1 ppm or less, from the viewpoint of improving the strength. Also, the total impurity concentration in the polycrystalline diamond is preferably 3 ppm or less, more preferably 0.3 ppm or less.
- the lower limit value of each concentration of hydrogen, oxygen and nitrogen in the polycrystalline diamond is not particularly limited, but is preferably 0.001 ppm or more from the viewpoint of production.
- the concentration of nitrogen in the polycrystalline diamond is preferably less than 0.1 ppm. According to this, nitrogen has little influence on the bonding strength between the diamond particles, and the polycrystalline diamond can maintain excellent strength.
- the concentration of nitrogen in the polycrystalline diamond is more preferably 0.01 ppm or less, still more preferably 0.001 ppm or less, from the viewpoint of improving the strength.
- the concentrations of hydrogen, oxygen and nitrogen in the polycrystalline diamond can be measured by secondary ion mass spectrometry (SIMS).
- the polycrystalline diamond according to the present embodiment has a crack generation load of 10 N in a fracture strength test in which a spherical diamond indenter with a tip radius (R) of 50 ⁇ m is pressed onto the surface of the polycrystalline polycrystalline body at a loading rate of 1 N / sec. It is preferable that it is more than.
- the crack initiation load is 10 N or more, the polycrystalline diamond has excellent fracture strength and fracture resistance, and when used as a tool material, cuts hard hard-to-cut materials without causing chipping of the cutting edge. be able to.
- the crack initiation load is more preferably 15 N or more, further preferably 18 N or more.
- the upper limit of the crack initiation load is not particularly limited, but from the viewpoint of production, 50 N or less is preferable.
- the specific method of the breaking strength test is as follows. Prepare a spherical diamond indenter with a tip radius of R 50 ⁇ m, load each sample at a load rate of 1 N / s at room temperature (23 ° C ⁇ 5 ° C), and load the moment the crack occurs in the sample (cracking Measure the load). The moment the crack occurs is measured by the AE sensor. This measurement is performed three times, the average value of the three values is determined, and this value is taken as the crack initiation load. The larger the crack initiation load, the higher the strength of the sample and the better the fracture resistance.
- an indenter with a tip radius (R) of less than 50 ⁇ m is used as the measurement indenter, the sample plastically deforms before the occurrence of a crack, and the accurate strength against the crack can not be measured.
- measurement is possible using an indenter with a tip radius (R) of more than 50 ⁇ m, the load required for the occurrence of cracking increases, and the contact area between the indenter and the sample increases, and the measurement accuracy based on the surface accuracy of the sample There are problems such as the influence on the surface and the influence of the crystal orientation of the single crystal becoming remarkable. Therefore, it is preferable to use an indenter with a tip radius (R) of 50 ⁇ m in the fracture strength test of a polycrystalline diamond.
- the polycrystalline diamond according to the present embodiment preferably has a Knoop hardness of 120 GPa or more.
- the polycrystalline diamond having a Knoop hardness of 120 GPa or more has high hardness and excellent wear resistance.
- the Knoop hardness is more preferably 130 GPa or more.
- the upper limit of the Knoop hardness is not particularly limited, but is preferably 300 GPa or less from the viewpoint of production.
- HK The evaluation method of the Knoop hardness (hereinafter, also referred to as HK, where the unit is GPa) will be described.
- a load F (N) is applied for 10 seconds to make an indentation on the surface of the polycrystalline diamond.
- the width a ( ⁇ m) of the obtained indentation is measured, and the Knoop hardness (HK) is calculated from the following equation (1).
- HK 14229 ⁇ F / a 2 equation (1).
- the polycrystalline diamond according to the present embodiment can be suitably used as a cutting tool, a tool such as a dresser or a die, or a material for a drilling bit.
- a method of producing a polycrystalline diamond according to another embodiment of the present disclosure includes the steps of preparing a non-diamond carbon material having a degree of graphitization of 0.2 or less; Directly converting and sintering to cubic and hexagonal diamonds under mechanically stable pressure and temperature conditions without adding any sintering aids and binders. .
- the method for producing a polycrystalline diamond according to the present embodiment includes the step of preparing a non-diamond-like carbon material having a degree of graphitization of 0.2 or less.
- the non-diamond-like carbon material prepared in the preparation step is not particularly limited as long as it has a degree of graphitization of 0.2 or less and is not a diamond.
- a non-diamond-like carbon material when produced by a thermal decomposition method from a high purity gas, it has a graphitization degree of 0.2 or less and a non-diamond shape having an impurity concentration of hydrogen, oxygen, nitrogen, etc. of 1 ppm or less. Carbon materials can be obtained.
- the non-diamond carbon material is not limited to one prepared by a thermal decomposition method from high purity gas, and it is possible to use amorphous carbon, glassy carbon, etc. even if it is a graphite having a low degree of graphitization such as finely ground graphite. It may be a non-crystalline carbon material or a mixture thereof.
- the degree of graphitization P of the non-diamond carbon material is determined as follows.
- the spacing d 002 of the (002) plane of the non-diamond carbon material is measured by X-ray diffraction of the non-diamond carbon material, and the following equation (2) is obtained.
- d 002 3.440-0.086 x (1-p 2 )
- the non-diamond carbon material does not contain an iron-group metal element as an impurity.
- the non-diamond-like carbon material preferably has a low concentration of impurities such as hydrogen, oxygen, and nitrogen from the viewpoint of suppressing the growth of crystal grains and promoting the conversion to diamond.
- concentration of hydrogen, oxygen and nitrogen in the non-diamond carbon material is preferably 1 ppm or less, more preferably 0.1 ppm or less.
- the total impurity concentration in the non-diamond carbon material is preferably 3 ppm or less, more preferably 0.3 ppm or less.
- the concentration of impurities such as hydrogen, oxygen and nitrogen in the non-diamond carbon raw material can be measured by secondary ion mass spectrometry (SIMS).
- the method for producing a polycrystalline diamond according to the present embodiment is the non-diamond-like carbon material described above under the pressure and temperature conditions under which the diamond is thermodynamically stable, both the sintering aid and the binder.
- the method is provided with the steps of directly converting into cubic diamond and hexagonal diamond and sintering without addition, to obtain a polycrystalline diamond.
- the non-diamond-like carbon material described above By placing the non-diamond-like carbon material described above under pressure and temperature conditions of thermodynamically stable diamond without adding any sintering aid and binder, the non-diamond-like carbon material can be directly It is converted to cubic diamond and hexagonal diamond and sintered together to obtain a polycrystalline diamond of high hardness and high strength.
- the sintering aid is a catalyst that promotes the sintering of the material serving as the raw material, and examples thereof include iron group metals such as Co, Ni and Fe, carbonates such as CaCO 3 and the like.
- the bonding material is a material for bonding the material serving as the raw material, and examples thereof include ceramics such as SiC.
- the pressure and temperature conditions at which the diamond is thermodynamically stable refer to the pressure and temperature conditions at which the diamond phase is a thermodynamically stable phase in the carbon-based material.
- the temperature is 1500 ° C. to 2000 ° C.
- the pressure is 10 GPa
- the temperature is 1500 ° C. to 2300 ° C.
- the pressure is 15 GPa
- the temperature is 1500 ° C. to 2400 ° C.
- the temperature exceeds 2400 ° C., the particle size of the diamond particles becomes coarse regardless of the pressure, and there is a possibility that a high-strength polycrystalline diamond can not be obtained.
- the temperature is lower than 1500 ° C., the sinterability is reduced, and the bonding strength between the diamond particles may be reduced regardless of the pressure.
- the high-pressure high-temperature generator used in the method for producing a polycrystalline diamond according to this embodiment is not particularly limited as long as it can obtain pressure and temperature conditions in which the diamond phase is a thermodynamically stable phase.
- a belt type or multi-anvil type is preferable from the viewpoint of enhancing productivity and workability.
- the container for containing the non-diamond-like carbon material, which is a raw material is not particularly limited as long as it is a material having high pressure resistance and high temperature resistance, and, for example, Ta or Nb is suitably used.
- a non-diamond-like carbon material which is a raw material is put in a capsule made of high melting point metal such as Ta or Nb, heated in vacuum and sealed. It is preferable to remove the adsorbed gas and air from the non-diamond carbon material and directly convert it into cubic diamond and hexagonal diamond under ultrahigh pressure and high temperature (pressure 6 to 20 GPa, temperature 1500 to 2400 ° C.).
- Production Examples 1 to 7 A non-diamond-like carbon material having a degree of graphitization and an impurity concentration shown in Table 1 is prepared.
- Production Example 6 a normal isotropic graphite produced by firing a graphite powder is prepared.
- Production Example 7 a high purity and highly oriented pyrolytic graphite (HOPG) is prepared in which a high purity carbon material synthesized by thermal decomposition of high purity methane gas is heat-treated at a high temperature exceeding 2000 ° C.
- HOPG highly oriented pyrolytic graphite
- the non-diamond-like carbon material is put in a capsule made of Ta, heated and sealed in vacuum, and a pressure of 16 GPa and a temperature of 2200 ° C. (diamond is thermodynamically stable using a high-pressure high-temperature generator) High pressure and high temperature treatment under the conditions of pressure and temperature). Note that neither a sintering aid nor a binder is added to the non-diamond carbon material.
- the average grain size, the morphology of the diamond particles, the impurity concentration, the carbon dangling bond density, the crack initiation load, and the Knoop hardness of the obtained polycrystalline diamond are measured.
- the average particle diameter of the diamond particles contained in each polycrystalline diamond is determined by a cutting method using a scanning electron microscope (SEM).
- a polycrystalline diamond is observed using a scanning electron microscope to obtain a SEM image.
- a circle is drawn on the SEM image, and eight straight lines are drawn radially from the center of the circle (so that the crossing angles between the straight lines are substantially equal) to the outer periphery of the circle.
- the observation magnification and the diameter of the circle are set so that the number of diamond particles placed per one straight line is about 10 to 50.
- the magnification of the above-mentioned SEM image is set to 30,000.
- the reason is that with a magnification smaller than this, the number of grains in the circle increases, grain boundaries become difficult to see and counting errors occur, and there is a high possibility of including a plate-like structure when drawing a line. It is. Moreover, it is because the number of the grains in a circle is too small, and an accurate average particle diameter can not be calculated by magnification more than this.
- the surface of the polycrystalline diamond is observed at three places in an area of 0.01 cm 2 or more using SEM or TEM (transmission electron microscope).
- SEM transmission electron microscope
- TEM transmission electron microscope
- the surface of the polycrystalline diamond is composed of particles having an aspect ratio of diamond particles of 3 or less, it is evaluated as “homogeneous”, and when the aspect ratio of diamond particles is composed of particles larger than 3, it is evaluated as “lamellae”.
- the area of “homogeneous” and the area of “lamella” are mixed on the surface of one polycrystalline diamond, it is evaluated as “homogeneous + lamella”.
- the results are shown in the column of "organizational form" in Table 1.
- Carbon dangling bond density The carbon dangling bond density in the polycrystalline diamond is measured by electron spin resonance (ESR). Specifically, the derivative curve of the ESR spectrum corresponding to the unpaired spin of carbon dangling bond is measured, the signal intensity is determined from the double integration, and the carbon dangling bond density is calculated from the intensity. The results are shown in the column of "carbon dangling bond density" in Table 1.
- the respective concentrations of nitrogen, hydrogen and oxygen are less than 1 ppm, and the carbon dangling bond density is 10 ppm or more, and the grain boundary strength between diamond particles Is high. Furthermore, since the polycrystalline diamonds of Preparation Examples 1 to 4 are composed of a plurality of diamond particles having an average particle diameter of 30 nm or less, there are many areas of grain boundaries having high grain boundary strength. Therefore, the polycrystalline diamonds of Preparation Examples 1 to 4 have a large crack initiation load and have excellent strength and fracture resistance while maintaining high hardness.
- the polycrystalline diamond of Preparation Example 5 has a concentration of each of nitrogen, hydrogen and oxygen of less than 1 ppm, but has a structure including a lamellar structure, a carbon dangling bond density of 8 ppm, and grain boundaries between diamond particles.
- the strength is somewhat weak, the crack activation load is small, and the strength and fracture resistance are low.
- the polycrystalline diamond body of Production Example 6 has a lamellar structure including a lamellar structure, the concentration of each of nitrogen, hydrogen and oxygen is 10 ppm or more, and the amount of impurities present at grain boundaries between diamond particles is More than Production Examples 1-4. Therefore, the grain boundary strength decreases, so the crack initiation load is small, and the strength and fracture resistance are low.
- the reason that the crack generation load in Production Example 6 has a width of 6 to 8 N is because the texture state is highly anisotropic.
- each of the polycrystalline diamonds of Production Example 7 the concentration of each of nitrogen, hydrogen and oxygen is less than 1 ppm.
- graphite having a high degree of graphitization and ultrahigh purity and high crystallinity (with orientation) is used as a starting material, it is composed of lamellar particles having a large particle size.
- the polycrystalline diamond of Production Example 7 has large anisotropy in strength, a small grain boundary area, and a small dangling bond density. Therefore, the polycrystalline diamond of Production Example 7 has a small crack initiation load and low strength and fracture resistance.
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Abstract
Description
しかし、非特許文献1~3のダイヤモンド多結晶体は、いずれもグラファイト等の導電性のある非ダイヤモンド炭素材料に直接電流を流すことで加熱する直接通電加熱法によって作製されているため、未変換グラファイトが残留することは避けられない。また、ダイヤモンドの粒子径が不均一であり、また、部分的に焼結が不十分となりやすい。このため、硬度や強度等の機械的特性が不十分であり、更に、欠片状の多結晶体しか得られないことから、実用化には至っていない。
[本開示の効果]
上記態様によれば、高い硬度を維持したまま、優れた強度を有するダイヤモンド多結晶体及びその製造方法を提供することが可能となる。
[本開示の実施形態の説明]
最初に本開示の実施態様を列記して説明する。
[本開示の実施形態の詳細]
本開示の一実施形態に係るダイヤモンド多結晶体の具体例を以下に説明する。本明細書において「A~B」という形式の表記は、範囲の上限下限(すなわちA以上B以下)を意味し、Aにおいて単位の記載がなく、Bにおいてのみ単位が記載されている場合、Aの単位とBの単位とは同じである。
本実施形態に係るダイヤモンド多結晶体は、ダイヤモンド単相を基本組成とするダイヤモンド多結晶体であって、前記ダイヤモンド多結晶体は、平均粒径が30nm以下の複数のダイヤモンド粒子から構成され、前記ダイヤモンド多結晶体は、炭素ダングリングボンド密度が10ppm以上である、ダイヤモンド多結晶体である。
ダイヤモンド粒子の平均粒径は、ダイヤモンド多結晶体が全方位に対して等方的な硬度及び耐摩耗性を示すことができるという観点から、20nm以下であることが好ましく、10nm以下であることが更に好ましい。一方、ダイヤモンド粒子の平均粒径の下限値は、ダイヤモンド特有の機械的強度を得られるという観点から、1nm以上が好ましい。
本実施形態に係るダイヤモンド多結晶体は、炭素ダングリングボンド密度が10ppm以上であり、優れた強度を有する。この理由は明らかでないが、本発明者らは以下の通り推察する。
本実施形態に係るダイヤモンド多結晶体は、不純物として、水素、酸素及び窒素からなる群から選択される少なくとも1種の元素を含み、ダイヤモンド多結晶体中の水素、酸素及び窒素の濃度は、それぞれ1ppm以下であることが好ましい。ここで、水素、酸素及び窒素の濃度は、ダイヤモンド多結晶体の全体の原子数を基準とした場合の水素、酸素、及び窒素のそれぞれの原子数の割合を示す値である。これによると、ダイヤモンド多結晶体は優れた強度を有する。この理由は明らかでないが、本発明者らは以下の通り推察する。
本実施形態に係るダイヤモンド多結晶体は、ダイヤモンド多結晶体の表面に先端半径(R)が50μmの球状のダイヤモンド圧子を1N/秒の負荷速度で押し当てる破壊強度試験において、亀裂発生荷重が10N以上であることが好ましい。亀裂発生荷重が10N以上であると、ダイヤモンド多結晶体は、優れた破壊強度及び耐欠損性を有し、工具材料として用いた場合に、刃先の欠損を生じることなく硬質難削材を切削することができる。亀裂発生荷重は、15N以上がより好ましく、18N以上がさらに好ましい。亀裂発生荷重の上限値は特に限定されないが、製造上の観点からは、50N以下が好ましい。
本実施形態に係るダイヤモンド多結晶体は、ヌープ硬度が120GPa以上が好ましい。ヌープ硬度が120GPa以上であるダイヤモンド多結晶体は、硬度が高く、耐摩耗性が優れている。ヌープ硬度は、130GPa以上が更に好ましい。ヌープ硬度の上限値は特に限定されないが、製造上の観点から300GPa以下が好ましい。
HK=14229×F/a2 式(1)。
本開示の他の実施形態であるダイヤモンド多結晶体の製造方法は、グラファイト化度が0.2以下である非ダイヤモンド状炭素材料を準備する工程と、前記非ダイヤモンド状炭素材料を、ダイヤモンドが熱力学的に安定な圧力及び温度の条件下で、焼結助剤及び結合材のいずれも添加することなく、直接的に立方晶ダイヤモンド及び六方晶ダイヤモンドに変換させるとともに焼結させる工程と、を備える。
本実施形態のダイヤモンド多結晶体の製造方法は、まず、グラファイト化度が0.2以下の非ダイヤモンド状炭素材料を準備する工程を備える。本準備工程において準備される非ダイヤモンド状炭素材料は、グラファイト化度が0.2以下でありダイヤモンドでない炭素材料であれば特に制限はない。
d002=3.440-0.086×(1-p2) 式(2)
非ダイヤモンド状炭素材料の乱層構造部の比率pが算出される。こうして得られた乱層構造部の比率pから、以下の式(3)により、
P=1-p 式(3)
グラファイト化度Pが算出される。
本実施形態のダイヤモンド多結晶体の製造方法は、次いで、上記の非ダイヤモンド状炭素材料を、ダイヤモンドが熱力学的に安定な圧力及び温度の条件下で、焼結助剤及び結合材のいずれも添加することなく、直接的に立方晶ダイヤモンド及び六方晶ダイヤモンドに変換させるとともに焼結させてダイヤモンド多結晶体を得る工程と、工程を備える。
表1に示されるグラファイト化度、及び、不純物濃度を有する非ダイヤモンド状炭素材料を準備する。なお、製造例6では、グラファイト粉末を焼成して作製した通常の等方性グラファイトを準備する。製造例7では、高純度メタンガスの熱分解により合成した高純度炭素材料を、2000℃を超える高温で熱処理した高純度高配向性熱分解グラファイト(HOPG)を準備する。
各ダイヤモンド多結晶体に含まれるダイヤモンド粒子の平均粒径を、走査電子顕微鏡(SEM)を用いた切断法により求める。
次にそのSEM画像に円を描き、その円の中心から8本の直線を放射状(各直線間の交差角度がほぼ等しくなるよう)に円の外周まで引く。この場合、上記の観察倍率及び円の直径は、上記の直線1本あたりに載るダイヤモンド粒子の個数が10~50個程度になるように設定する。
ダイヤモンド多結晶体の表面を、SEMもしくはTEM(透過型電子顕微鏡)を用いて、0.01cm2以上の領域で3箇所観察する。ダイヤモンド多結晶体の表面が、ダイヤモンド粒子のアスペクト比が3以下の粒子からなる場合は「均質」と評価し、ダイヤモンド粒子のアスペクト比が3を超える粒子からなる場合は「ラメラ」と評価する。また、1つのダイヤモンド多結晶体の表面に「均質」の領域と「ラメラ」の領域が混在する場合は、「均質+ラメラ」と評価する。結果を表1の「組織形態」の欄に示す。
SIMSを用いて以下の条件により、ダイヤモンド多結晶体中の窒素(N)、水素(H)、酸素(O)の各濃度を測定する。結果を表1の「不純物濃度」の欄に示す。
ダイヤモンド多結晶体中の炭素ダングリングボンド密度は、電子スピン共鳴装置(ESR)で測定する。具体的には、炭素ダングリングボンドの不対スピンに相当するESRスペクトルの微分曲線を計測し、その2回積分よりシグナル強度を求め、その強度から炭素ダングリングボンド密度を算出する。結果を表1の「炭素ダングリングボンド密度」の欄に示す。
各ダイヤモンド多結晶体について、亀裂発生荷重を測定するために、以下の条件で破壊強度試験を実施する。
ヌープ硬度計を用いて、ダイヤモンド多結晶体のヌープ硬度を測定する。具体的には、ダイヤモンド多結晶体の表面に、荷重4.9Nを10秒間負荷して圧痕をつける。得られた圧痕の幅aを測定し、下記式(1)によりヌープ硬度(HK)を算出した。結果を表1の「ヌープ硬度」の欄に示す。
HK=14229×4.9/a2 式(1)。
製造例1~4のダイヤモンド多結晶体は、いずれも、窒素、水素、酸素のそれぞれの濃度が1ppm未満であり、かつ、炭素ダングリングボンド密度が10ppm以上であり、ダイヤモンド粒子間の粒界強度が高い。更に、製造例1~4のダイヤモンド多結晶体は、平均粒径が30nm以下の複数のダイヤモンド粒子から構成されているため、高い粒界強度を有する粒界の面積が多い。したがって、製造例1~4のダイヤモンド多結晶体は、高い硬度を維持したまま、亀裂発生荷重が大きく、優れた強度及び耐欠損性を有している。
Claims (5)
- ダイヤモンド単相を基本組成とするダイヤモンド多結晶体であって、
前記ダイヤモンド多結晶体は、平均粒径が30nm以下の複数のダイヤモンド粒子から構成され、
前記ダイヤモンド多結晶体は、炭素ダングリングボンド密度が10ppm以上である、
ダイヤモンド多結晶体。 - 前記ダイヤモンド多結晶体は、不純物として、水素、酸素及び窒素からなる群より選択される少なくとも1種の元素を含み、
前記ダイヤモンド多結晶体中の前記水素、前記酸素及び前記窒素の濃度は、それぞれ1ppm以下である、
請求項1に記載のダイヤモンド多結晶体。 - 前記ダイヤモンド多結晶体中の前記窒素の濃度は、0.1ppm未満である、
請求項2に記載のダイヤモンド多結晶体。 - 前記ダイヤモンド多結晶体の表面に先端半径が50μmの球状のダイヤモンド圧子を1N/秒の負荷速度で押し当てる破壊強度試験において、亀裂発生荷重が10N以上である、
請求項1~請求項3のいずれか1項に記載のダイヤモンド多結晶体。 - グラファイト化度が0.2以下である非ダイヤモンド状炭素材料を準備する工程と、
前記非ダイヤモンド状炭素材料を、ダイヤモンドが熱力学的に安定な圧力及び温度の条件下で、焼結助剤及び結合材のいずれも添加することなく、直接的に立方晶ダイヤモンド及び六方晶ダイヤモンドに変換させるとともに焼結させてダイヤモンド多結晶体を得る工程と、を備える、
ダイヤモンド多結晶体の製造方法。
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