JP6192253B1 - Cubic boron nitride particle-containing single crystalline diamond particles and method for producing the same - Google Patents
Cubic boron nitride particle-containing single crystalline diamond particles and method for producing the same Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 227
- 239000010432 diamond Substances 0.000 title claims abstract description 180
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 177
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 53
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000013078 crystal Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000010586 diagram Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000007858 starting material Substances 0.000 description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 17
- 229910052796 boron Inorganic materials 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000879 optical micrograph Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003082 abrasive agent Substances 0.000 description 5
- 239000006061 abrasive grain Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
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- 230000002195 synergetic effect Effects 0.000 description 5
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- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
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- 238000007561 laser diffraction method Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 nucleation Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
熱的安定性に優れる単結晶質ダイヤモンド粒子を提供する。単結晶質ダイヤモンド粒子は、立方晶窒化ホウ素粒子を含有する。好ましくは、立方晶窒化ホウ素粒子が立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の内部及び／又は表面に存し、単結晶質ダイヤモンド粒子の平均粒子径が５００μｍ以下であり、立方晶窒化ホウ素粒子の平均粒径は０．０５〜１００μｍである。Provided is a single crystalline diamond particle having excellent thermal stability. Single crystalline diamond particles contain cubic boron nitride particles. Preferably, the cubic boron nitride particles are present in and / or on the surface of the cubic boron nitride particles-containing single crystalline diamond particles, and the average particle diameter of the single crystalline diamond particles is 500 μm or less, and the cubic boron nitride particles The average particle size is 0.05 to 100 μm.
Description
本発明は、熱的安定性に優れる立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子、およびその製造方法に関する。 The present invention relates to cubic boron nitride particle-containing single crystalline diamond particles having excellent thermal stability, and a method for producing the same.
ダイヤモンドは物質上最高の硬度を持ち、超硬合金などの種々の材料を研磨する研磨材や、集積回路の切断に用いる研削材等、幅広く利用されている。ダイヤモンドを用いた研磨材や研削材は、単位時間当たりの被削材除去量が大きく、加工面の面粗さが小さいことが要求されている。一般には、研削精度が向上するように、多結晶質のタイヤモンド砥粒が用いられている。しかし、多結晶質のダイヤモンド砥粒は、多量の爆薬を用いる動的加圧によって製造される他、ダイヤモンド粒子を出発原料として焼結して製造されるため、製造工程が制約され、高価でもある。 Diamond has the highest hardness in terms of substance, and is widely used, such as abrasives for polishing various materials such as cemented carbide and abrasives for cutting integrated circuits. Abrasives and abrasives using diamond are required to have a large amount of workpiece removal per unit time and a small surface roughness of the processed surface. In general, polycrystalline tiremond abrasive grains are used so as to improve grinding accuracy. However, polycrystalline diamond abrasive grains are manufactured by dynamic pressurization using a large amount of explosives, and are manufactured by sintering using diamond particles as a starting material, which limits the manufacturing process and is also expensive. .
そこで、近年では、単結晶質ダイヤモンドを用いた砥粒が注目されている。単結晶質ダイヤモンドには、天然ダイヤモンドや合成ダイヤモンドがある。天然ダイヤモンドは、そのほとんどがＩａ型であり、格子もしくは格子間位置に窒素を有する。また、天然ダイヤモンドは、不純物の含有量や結晶組織のばらつきが大きく、品質や性能が安定しない。さらに、天然ダイヤモンドは、採掘量に応じて価格が変動するため、安定供給に課題を残し、高価でもある。一方、合成ダイヤモンドは、天然ダイヤモンドよりも一定品質のものを安定供給することができる。 In recent years, therefore, attention has been focused on abrasive grains using single crystalline diamond. Single crystalline diamond includes natural diamond and synthetic diamond. Natural diamonds are mostly type Ia and have nitrogen at the lattice or interstitial positions. Natural diamond has large variations in impurity content and crystal structure, and quality and performance are not stable. Furthermore, since the price of natural diamond varies depending on the amount of mining, it remains a problem in stable supply and is expensive. On the other hand, synthetic diamond can be stably supplied with a certain quality than natural diamond.
ところで、一般に、ダイヤモンドは、天然あるいは合成に関わらず、大気中での熱的安定性に劣ることが知られている。具体的には、ダイヤモンドは、大気中６００〜７００℃で酸化が始まり、９００℃程度で焼失してしまう。このため、ダイヤモンドを用いて加工用工具または研削研磨切断砥石（以下、「加工用工具」という。）を製造する際、大気中高温での焼成が困難である。耐久性のある工具を製造するためには高温での耐酸化性が要求されていた。 Incidentally, it is generally known that diamond is inferior in thermal stability in the atmosphere, whether natural or synthetic. Specifically, diamond begins to oxidize in the atmosphere at 600 to 700 ° C. and burns out at about 900 ° C. For this reason, when manufacturing a processing tool or a grinding / polishing / cutting grindstone (hereinafter referred to as “processing tool”) using diamond, firing at high temperature in the atmosphere is difficult. In order to produce durable tools, oxidation resistance at high temperatures has been required.
そこで、大気中における高温熱酸化を抑制する手段として、例えば特許文献１には、ダイヤモンド合成時にホウ素をドープすることによって、高温での耐酸化性が改善された発明が記載されている。特許文献１には、ホウ素源として、非晶質のホウ素粉末、炭化ホウ素（Ｂ４Ｃ）、ホウ化鉄（ＦｅＢ）合金、金属ホウ素が挙げられている。また、同文献には、８５０℃での損耗率が毎秒０．２５％未満であり、７００℃以上の温度で損耗が開始することも記載されている。Therefore, as means for suppressing high-temperature thermal oxidation in the atmosphere, for example, Patent Document 1 describes an invention in which oxidation resistance at high temperature is improved by doping boron during diamond synthesis. Patent Document 1 includes amorphous boron powder, boron carbide (B 4 C), iron boride (FeB) alloy, and metal boron as a boron source. The document also describes that the wear rate at 850 ° C. is less than 0.25% per second, and wear starts at a temperature of 700 ° C. or higher.
特許文献１に記載のように、ホウ素をドープするダイヤモンドは、ドープしないダイヤモンドと比較して高温での耐酸化性に優れるとされている。 As described in Patent Literature 1, diamond doped with boron is said to be superior in oxidation resistance at high temperatures compared to undoped diamond.
しかし、特許文献１に記載のホウ素ドーピングされたダイヤモンドは、合成時に炭素がダイヤモンドに変化すると同時に炭化ホウ素を析出させる反応も伴う場合がある。このような反応を伴う合成では、特許文献２に記載のように、ダイヤモンドと炭化ホウ素が競合して析出しようとする過程でダイヤモンド粒子の粒成長が阻害されてしまい、所望のダイヤモンド粒子を得ることができないことがある。また、従来のホウ素含有ダイヤモンドは格子欠陥が著しく、ノンドープダイヤモンドと比較して粒子の強度が劣るためにある程度の自生発刃性を有するものの、十分な加工速度であるとは言い難く、更なる改善が必要である。 However, the boron-doped diamond described in Patent Document 1 may be accompanied by a reaction of depositing boron carbide at the same time that carbon is changed to diamond during synthesis. In the synthesis involving such a reaction, as described in Patent Document 2, in the process where diamond and boron carbide compete and precipitate, the grain growth of diamond particles is hindered to obtain desired diamond particles. May not be possible. In addition, the conventional boron-containing diamond has remarkable lattice defects, and the particle strength is inferior to that of non-doped diamond. is necessary.
また、研削研磨切断加工において、精度の高い仕上がり面と、大きな加工速度とを同時に達成する加工砥粒の要求は常である。このような状況下において、最近では、加工材料の化合物化および複雑化に伴い、加工用工具の高い硬度や靭性、耐磨耗、耐熱特性が要求されるようになってきており、加工用工具作成時の焼成温度を更に高温に設定し、より硬度化し耐磨耗化を実現する必要が生じてきた。 Further, in grinding / polishing / cutting processes, there is a constant demand for processing abrasive grains that simultaneously achieve a highly accurate finished surface and a high processing speed. Under such circumstances, recently, along with compounding and complication of processing materials, high hardness, toughness, wear resistance, and heat resistance characteristics of processing tools have been required. There has been a need to set the firing temperature at the time of preparation to a higher temperature to make it harder and more wear resistant.
特許文献１に記載のホウ素ドープダイヤモンドは、前述のように８５０℃程度ではある程度の酸化は抑制できるが、大気中で１０００℃を超える場合には酸化を抑制することは困難であると考えられる。酸化を抑制するために不活性雰囲気中で各種焼成を行うことも考えられるが、焼成装置や製造コストを考慮すると、大気中での焼成が不可欠である。 The boron-doped diamond described in Patent Document 1 can suppress oxidation to some extent at about 850 ° C. as described above, but it is considered difficult to suppress oxidation when it exceeds 1000 ° C. in the atmosphere. Various firings may be performed in an inert atmosphere to suppress oxidation, but firing in the air is indispensable in view of firing equipment and manufacturing costs.
このように、従来のダイヤモンド粒子では、近年の焼成温度の高温化に対応することができないため、加工用工具作成時の焼成温度を上げることができるダイヤモンド粒子を得ることが強く望まれている。 Thus, since conventional diamond particles cannot cope with the recent increase in firing temperature, it is strongly desired to obtain diamond particles capable of raising the firing temperature when forming a working tool.
本発明の課題は、熱的安定性に優れる単結晶質ダイヤモンド粒子およびその製造方法を提供することである。 An object of the present invention is to provide single crystalline diamond particles having excellent thermal stability and a method for producing the same.
本発明者らは、ダイヤモンドの耐酸化性を向上させるため、まずは、ダイヤモンドと比較して同等以上の熱的安定性を有する物質をダイヤモンドと共存させる点に着目して検討を行った。立方晶窒化ホウ素は、１３００℃程度まで熱的に安定であり、ダイヤモンドのＨＶ８６００に次ぐＨＶ５０００という高い硬度を有し、格子定数が０．３６２ｎｍでダイヤモンドの０．３５７に非常に近い。また、立方晶窒化ホウ素は、ダイヤモンド構造でありヘテロエピタキシャルが可能な物質であることが知られている。 In order to improve the oxidation resistance of diamond, the present inventors first studied by focusing on the fact that a substance having thermal stability equal to or higher than that of diamond coexists with diamond. Cubic boron nitride is thermally stable up to about 1300 ° C., has a hardness as high as HV5000 after HV8600 of diamond, has a lattice constant of 0.362 nm, and is very close to 0.357 of diamond. Cubic boron nitride is known to be a substance having a diamond structure and capable of heteroepitaxial.
ここで、黒鉛と触媒金属を主成分とした反応物質にダイヤモンド結晶の成長核となるダイヤモンド粒子を添加すると、核形成が容易になり黒鉛を出発原料としたダイヤモンドへの成長が促進され、ダイヤモンド結晶の収穫量が画期的に上がることが知られている。このように種結晶を用い、成長粒子の核形成を容易にする方法は、化学気相法では頻繁に用いられている技術である。 Here, the addition of diamond particles, which are the growth nuclei of diamond crystals, to the reactants composed mainly of graphite and catalytic metal facilitates the nucleation and promotes the growth of diamonds starting from graphite. It is known that the yield of rice will increase dramatically. The method of using seed crystals and facilitating nucleation of grown particles is a technique frequently used in chemical vapor deposition.
そこで、本発明者らは、立方晶窒化ホウ素とダイヤモンドを有する物質について、製造方法の観点も含めて検討を重ねた。ダイヤモンドの合成方法としては、まず、化学気相法が挙げられる。化学気相法では、格子定数がダイヤモンドに近い立方晶窒化ホウ素を種結晶として、ダイヤモンドをヘテロエピタキシャル成長させてダイヤモンドを得ることができる。しかし、化学気相法は、立方晶窒化ホウ素の層上にタイヤモンド層をヘテロエピタキシャル成長させる方法である。得られた層はダイヤモンド層と立方晶窒化ホウ素層の積層構造となるため、両者の相乗効果を発揮することができず、熱的安定性の向上には繋がらない。また、得られた積層体を粉砕して研磨材としての粒子を得ることも考えられなくはないが、得られた粒子はダイヤモンド多結晶質である場合がほとんどであって、研磨材として工業用および産業用用途に必要な大量生産は困難である。 Therefore, the present inventors have repeatedly studied a substance having cubic boron nitride and diamond, including a manufacturing method. As a method for synthesizing diamond, first, a chemical vapor phase method is exemplified. In the chemical vapor deposition method, diamond can be obtained by heteroepitaxially growing diamond using cubic boron nitride having a lattice constant close to that of diamond as a seed crystal. However, the chemical vapor deposition method is a method in which a tiremond layer is heteroepitaxially grown on a cubic boron nitride layer. Since the obtained layer has a laminated structure of a diamond layer and a cubic boron nitride layer, the synergistic effect of the two cannot be exhibited and the thermal stability is not improved. In addition, it is not unthinkable to pulverize the obtained laminate to obtain particles as an abrasive, but the obtained particles are mostly polycrystalline diamond, and are used as an abrasive for industrial purposes. And the mass production required for industrial applications is difficult.
本発明者らは、工業用または産業用用途を前提に、大量にしかも安価にダイヤモンド研磨材粒子が得られる高温高圧法によりダイヤモンドを合成する方法に関して検討を行った。通常、高温高圧法によるダイヤモンド粒子研磨材を合成する場合、触媒または溶媒に用いた金属化合物もしくは炭化物がダイヤモンド結晶内に混入し、ダイヤモンドの強度低下が問題になる。合成温度および合成圧力を調整することによって、触媒または溶媒に用いた金属化合物または炭化物の混入が低減された高品質のダイヤモンド研磨材を合成することは可能であるが、高品質のダイヤモンド粒子を得ようとするとその収穫量は少なくなる。しかし、前述のように、高温高圧法を用いたダイヤモンド粒子の合成時にダイヤモンド粒子を予め種結晶として添加すると、核発生が容易になりダイヤモンド粒子の収穫量が向上する。ただ、核発生が容易であるため、ダイヤモンド粒子が至る所で成長し、双晶が発生し多結晶質となりやすい。このため、単結晶質ダイヤモンド粒子研磨材を合成する場合、種結晶を用いることは考え難い。 The present inventors have studied a method for synthesizing diamond by a high-temperature and high-pressure method capable of obtaining diamond abrasive particles in large quantities and at low cost on the premise of industrial use or industrial use. Usually, when synthesizing a diamond particle abrasive by a high-temperature and high-pressure method, a metal compound or carbide used as a catalyst or a solvent is mixed in the diamond crystal, which causes a problem of a decrease in diamond strength. By adjusting the synthesis temperature and pressure, it is possible to synthesize high-quality diamond abrasives with reduced contamination of metal compounds or carbides used in the catalyst or solvent, but high-quality diamond particles are obtained. If you try to do so, the yield will decrease. However, as described above, when diamond particles are added as seed crystals in advance during the synthesis of diamond particles using a high-temperature and high-pressure method, nucleation is facilitated and the yield of diamond particles is improved. However, since nucleation is easy, diamond particles grow everywhere, twins are generated, and it tends to be polycrystalline. For this reason, when synthesizing a single crystalline diamond particle abrasive, it is difficult to consider using a seed crystal.
本発明者らは、通常では出発原料として用いることのない立方晶窒化ホウ素粒子を敢えて高温高圧法によるダイヤモンド合成の種結晶として出発原料に投入した。その結果、予想外にも、添加した立方晶窒化ホウ素粒子を構成するホウ素が、ホウ素ドーパントとしてダイヤモンド単結晶中の格子位置を置換もしくは格子間位置へ拡散しない知見が得られた。また、これと同時に、ダイヤモンド粒子は単結晶質であり、立方晶窒化ホウ素粒子が結晶のまま単結晶質ダイヤモンド中に残存する知見が得られた。 The present inventors dared to introduce cubic boron nitride particles, which are not normally used as a starting material, into the starting material as a seed crystal for diamond synthesis by a high-temperature high-pressure method. As a result, it was unexpectedly found that the boron constituting the added cubic boron nitride particles did not replace the lattice position in the diamond single crystal as a boron dopant or diffuse to the interstitial position. At the same time, it was found that the diamond particles were single crystalline, and the cubic boron nitride particles remained in the single crystalline diamond as crystals.
さらに、立方晶窒化ホウ素粒子を種結晶としても、ダイヤモンド粒子を種結晶とした場合と同様に収穫量が向上する知見も得られた。 Furthermore, the knowledge that the yield was improved even when the cubic boron nitride particles were used as seed crystals was the same as when the diamond particles were used as seed crystals.
この知見により得られた本発明は次の通りである。
（１）立方晶窒化ホウ素粒子を含有する立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子。The present invention obtained from this finding is as follows.
(1) Cubic boron nitride particle-containing single crystalline diamond particles containing cubic boron nitride particles.
（２）立方晶窒化ホウ素粒子が立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の内部及び／又は表面に存する、上記（１）に記載の立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子。 (2) The cubic boron nitride particle-containing single crystalline diamond particles according to (1) above, wherein the cubic boron nitride particles are present inside and / or on the surface of the cubic boron nitride particle-containing single crystalline diamond particles.
（３）単結晶質ダイヤモンド粒子の平均粒子径が５００μｍ以下である、上記（１）または上記（２）に記載の立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子。 (3) The monocrystalline diamond particles containing cubic boron nitride particles according to the above (1) or (2), wherein the single crystalline diamond particles have an average particle size of 500 μm or less.
（４）立方晶窒化ホウ素粒子の平均粒子径が０．０５〜１００μｍである、上記（１）〜上記（３）のいずれか１項に記載の立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子。 (4) The cubic boron nitride particle-containing single crystalline diamond particles according to any one of (1) to (3) above, wherein the average particle diameter of the cubic boron nitride particles is 0.05 to 100 μm.
（５）高温高圧法を用いた立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の製造方法であって、黒鉛及び／又は非ダイヤモンド炭素、触媒金属及び／又は溶媒金属、並びに立方晶窒化ホウ素粒子を、炭素の相平衡図においてダイヤモンドが熱力学的安定領域の圧力および温度に曝すことによって合成することを特徴とする立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の製造方法。 (5) A method for producing cubic boron nitride particle-containing single crystalline diamond particles using a high temperature and high pressure method, wherein graphite and / or non-diamond carbon, catalyst metal and / or solvent metal, and cubic boron nitride particles A process for producing single crystalline diamond particles containing cubic boron nitride particles, characterized in that diamond is synthesized by exposing the diamond to pressure and temperature in a thermodynamically stable region in a carbon phase equilibrium diagram.
（６）前記触媒金属及び／又は溶媒金属は、鉄、ニッケル、コバルト、およびマンガンの少なくとも１種を含有する合金である、上記（５）に記載の立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の製造方法。 (6) The cubic boron nitride particle-containing single crystalline diamond particles according to (5), wherein the catalyst metal and / or solvent metal is an alloy containing at least one of iron, nickel, cobalt, and manganese. Manufacturing method.
（７）熱力学的安定領域の圧力および温度は、各々５〜１０ＧＰａ、１３００〜２０００℃である、上記（５）または上記（６）に記載の立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の製造方法。 (7) The pressure and temperature of the thermodynamically stable region are 5 to 10 GPa and 1300 to 2000 ° C., respectively, and the cubic boron nitride particle-containing single crystalline diamond particles according to (5) or (6) above are used. Production method.
本発明を以下により詳しく説明する。
１．立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子
本発明に係る単結晶質ダイヤモンド粒子は立方晶窒化ホウ素粒子（以下、適宜、「ｃＢＮ粒子」と称する。）を含有する。本発明に係る単結晶質ダイヤモンド粒子は、後述するように、高温高圧法によりｃＢＮ粒子を種結晶として単結晶質ダイヤモンドが成長して得られる。このため、ｃＢＮ粒子がそのまま単結晶質ダイヤモンド中に残存することになる。また、本発明に係るダイヤモンド粒子は単結晶質であるためにダイヤモンドの粒界が存在せず双晶もほとんど存在しない。立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子がｃＢＮ粒子との接合面もしくはｃＢＮ粒子自体を起点として破砕したとしても、高い硬度を有する単結晶質ダイヤモンドが刃となり、単位時間当たりの加工量を維持することができる、自生発刃性にも優れる。このように、本発明では、単結晶質ダイヤモンド粒子がｃＢＮ粒子を含有するため、不純物が少ない高純度の単結晶質ダイヤモンドが有する高い硬度と、ｃＢＮ粒子が有する熱的安定性との相乗効果が発揮される。The invention is described in more detail below.
1. Cubic Boron Nitride Particle-Containing Single Crystal Diamond Particles The single crystal diamond particles according to the present invention contain cubic boron nitride particles (hereinafter, appropriately referred to as “cBN particles”). As will be described later, the single crystalline diamond particles according to the present invention are obtained by growing single crystalline diamond using cBN particles as seed crystals by a high temperature and high pressure method. For this reason, the cBN particles remain in the single crystalline diamond as they are. Further, since the diamond particles according to the present invention are monocrystalline, there are no diamond grain boundaries and almost no twins. Even if cubic boron nitride-containing single crystalline diamond particles are crushed starting from the joint surface with cBN particles or the cBN particles themselves, the single crystalline diamond with high hardness serves as the blade and maintains the processing amount per unit time It is also excellent in spontaneous cutting ability. Thus, in the present invention, since the single crystalline diamond particles contain cBN particles, there is a synergistic effect between the high hardness of the high purity single crystalline diamond with few impurities and the thermal stability of the cBN particles. Demonstrated.
本発明では、前述の相乗効果を十分に発揮する観点から、ｃＢＮ粒子が立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の内部及び／又は表面に存することが望ましく、内部及び表面に存することが特に望ましい。ｃＢＮ粒子が単結晶質ダイヤモンドの内部及び表面に存すると、ダイヤモンド粒子が研磨や研削により摩耗した場合であっても、ｃＢＮ粒子が内部から表面に順次露出するため、加工点に発生する熱に対してｃＢＮ粒子の熱的安定性を発揮することもできる。本発明において、「内部」とは、ｃＢＮ粒子が単結晶質ダイヤモンド内に内包されていることを表す。「表面」とは、ｃＢＮ粒子の一部が単結晶質ダイヤモンドの表面に露出していることを表す。 In the present invention, from the viewpoint of sufficiently exerting the above-mentioned synergistic effect, it is desirable that the cBN particles are present in and / or on the surface of the cubic boron nitride particle-containing single crystalline diamond particles, and particularly present in the interior and the surface. desirable. If cBN particles are present inside and on the surface of the single crystalline diamond, even if the diamond particles are worn by polishing or grinding, the cBN particles are sequentially exposed from the inside to the surface. In addition, the thermal stability of the cBN particles can be exhibited. In the present invention, “internal” means that cBN particles are encapsulated in single crystalline diamond. “Surface” means that a part of cBN particles is exposed on the surface of single-crystal diamond.
本発明に係る立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子は、上述した相乗効果を発揮する観点から、立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の質量に対して１〜１０質量％のｃＢＮ粒子を含有することが望ましい。１質量％以上であるとｃＢＮの熱的安定性が出現しやすい。一方、１０質量％以下であるとダイヤモンド合成時に双晶が発生し難く単結晶粒子を得ることが容易になる。 From the viewpoint of exhibiting the above-mentioned synergistic effect, the cubic boron nitride particle-containing single crystalline diamond particle according to the present invention has 1 to 10% by mass of cBN based on the mass of the cubic boron nitride particle-containing single crystalline diamond particle. It is desirable to contain particles. If it is 1% by mass or more, the thermal stability of cBN tends to appear. On the other hand, when the content is 10% by mass or less, twin crystals hardly occur during diamond synthesis, and it becomes easy to obtain single crystal particles.
さらに、本発明では、ダイヤモンド粒子がどの方向から摩耗してもｃＢＮ粒子を順次表面に露出させる観点から、ｃＢＮ粒子が単結晶質ダイヤモンド中に均一に分散していることが望ましい。 Furthermore, in the present invention, it is desirable that the cBN particles are uniformly dispersed in the single crystalline diamond from the viewpoint of sequentially exposing the cBN particles to the surface even if the diamond particles are worn from any direction.
本発明に係る単結晶質ダイヤモンド粒子の平均粒子径は５００μｍ以下であることが望ましい。５００μｍ以下であれば、粒子が大きすぎないために幅広い用途に使用できる。下限は特に限定されないが、一定以上の研削量を確保する観点から、０．２５μｍ以上であることが望ましい。 The average particle size of the single crystalline diamond particles according to the present invention is desirably 500 μm or less. If it is 500 micrometers or less, since particle | grains are not too large, it can be used for a wide use. Although a minimum is not specifically limited, From a viewpoint of ensuring the grinding amount more than fixed, it is desirable that it is 0.25 micrometer or more.
なお、合成後のダイヤモンド粒子が大きい場合には、所望の粒子径を得るために、本発明に係るダイヤモンド粒子を粉砕し、粒子径を調整した粉砕粉粒子を用いることもできる。本発明に係る立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子は、ｃＢＮ粒子が単結晶質ダイヤモンド中にある程度均一に分散している為、粉砕粒子でも熱的安定性を維持することができる。 In addition, when the synthesized diamond particles are large, in order to obtain a desired particle size, pulverized powder particles in which the diamond particles according to the present invention are pulverized and the particle size is adjusted may be used. The cubic boron nitride particle-containing single crystalline diamond particles according to the present invention can maintain thermal stability even with pulverized particles because the cBN particles are uniformly dispersed in the single crystalline diamond.
本発明の単結晶質ダイヤモンド粒子は、ｃＢＮ粒子を含有する。ｃＢＮは、格子定数が０．３６２ｎｍでダイヤモンドの０．３５７に非常に近く、ｃＢＮは高温高圧法によるダイヤモンド合成において種結晶として機能する。また、ｃＢＮは１３００℃程度まで熱的に安定であり、砥石を作製する際の焼結温度を高くしてもダイヤモンド粒子の酸化による焼失を抑制することができる。さらに、ｃＢＮはダイヤモンドのＨＶ８６００に次ぐＨＶ５０００の硬度を示すため、同一単結晶粒子内で硬度差が発生する。この硬度差は、単結晶質ダイヤモンドとｃＢＮ粒子との界面が粒子自体の破砕の起点となる要因である。また、硬度差は、加工時の砥粒の目潰れを防止することができるだけでなく、加工時の自生発刃の起点、研削研磨切断時の切れ刃の生成の要因でもある。この結果、切れ刃の増大すなわち単位時間当たりの加工量の増大につながる。 The single crystalline diamond particles of the present invention contain cBN particles. cBN has a lattice constant of 0.362 nm and is very close to 0.357 of diamond, and cBN functions as a seed crystal in diamond synthesis by a high-temperature high-pressure method. Moreover, cBN is thermally stable up to about 1300 ° C., and even if the sintering temperature at the time of producing a grindstone is increased, it is possible to suppress burning due to oxidation of diamond particles. Furthermore, since cBN shows the hardness of HV5000 after HV8600 of diamond, a hardness difference occurs within the same single crystal particle. This hardness difference is a factor in which the interface between the single crystalline diamond and the cBN particles becomes the starting point of the crushing of the particles themselves. In addition, the hardness difference can not only prevent crushing of abrasive grains during processing, but also causes the starting point of a self-generated blade during processing and the generation of a cutting edge during grinding and polishing cutting. As a result, the number of cutting edges increases, that is, the processing amount per unit time increases.
本発明においてｃＢＮを含有する効果が発揮されるためには、ｃＢＮが不純物程度の量を含有する程度では発揮されず、ｃＢＮが粒子として存在する程度の量を含有する必要がある。一方、ダイヤモンド粒子としての性質を維持するためには、ｃＢＮ粒子の粒径が大きすぎず適正な範囲である必要がある。本発明において、ｃＢＮ粒子の平均粒子径は、０．０５〜１００μｍであることが望ましく、０．１〜５０μｍであることがより望ましい。 In order to exhibit the effect of containing cBN in the present invention, it is necessary to contain an amount of cBN present as particles, not to the extent that cBN contains an amount of impurities. On the other hand, in order to maintain the properties as diamond particles, the particle size of the cBN particles is not too large and needs to be in an appropriate range. In the present invention, the average particle size of the cBN particles is desirably 0.05 to 100 μm, and more desirably 0.1 to 50 μm.
本発明において、平均粒子径は以下の通りである。平均粒子径が０．２５μｍ以上の粒子では、レーザ回折散乱方式の粒度分布測定機（例えば、Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ社製、型式：Ｍａｓｔｅｒｓｉｚｅｒ２０００、マイクロトラックベル社製、型式：ＭｉｃｒｏｔｒａｃＭＴ３０００など）の体積平均径Ｄ５０値を平均粒子径とする。一方、平均粒子径が０．２５μｍ以下の粒子では、レーザ回折散乱方式での測定が困難であるため、動的光散乱方式もしくは円心沈降式の粒度分布測定機（例えば、マイクロトラックベル社製、型式ＭｉｃｒｏｔｒａｃＵＰＡ、ＮａｎｏｔｒａｃＵＰＡーＥＸなど）の体積平均径Ｄ５０値を平均粒子径とする。 In the present invention, the average particle size is as follows. For particles having an average particle diameter of 0.25 μm or more, a volume average diameter D50 value of a particle size distribution analyzer of a laser diffraction / scattering method (for example, Malvern Instruments, model: Mastersizer 2000, Microtrack Bell, model: MicrotracMT3000, etc.) Is the average particle size. On the other hand, particles having an average particle diameter of 0.25 μm or less are difficult to measure by the laser diffraction scattering method, so a dynamic light scattering method or a circular sedimentation type particle size distribution measuring machine (for example, manufactured by Microtrack Bell) The volume average diameter D50 value of model MicrotracUPA, NanotracUPA-EX, etc.) is defined as the average particle diameter.
２．立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の製造方法
本発明に係る立方晶窒化ホウ素粒子含有単結晶質ダイヤモンド粒子の製造方法は、高温高圧法を用い、黒鉛及び／又は非ダイヤモンド炭素、触媒金属及び／又は溶媒金属、並びに立方晶窒化ホウ素粒子を、炭素の相平衡図においてダイヤモンドが熱力学的に安定する領域の圧力および温度に曝すことによって合成する。2. Method for Producing Cubic Boron Nitride Particle-Containing Single Crystal Diamond Particles The method for producing cubic boron nitride particle-containing single crystal diamond particles according to the present invention uses a high-temperature and high-pressure method, using graphite and / or non-diamond carbon, catalytic metal. And / or solvent metals and cubic boron nitride particles are synthesized by exposing them to pressures and temperatures in the region where the diamond is thermodynamically stable in the carbon phase equilibrium diagram.
本発明に係る製造方法は、高温高圧法では不純物として取り扱われているとともにダイヤモンドへの混入が避けられていたｃＢＮを、敢えて、粒子としてダイヤモンド合成の出発原料に投入することによって完成されたものであり、単結晶質ダイヤモンドの製造においては画期的な方法である。 The production method according to the present invention was completed by introducing cBN, which was handled as an impurity in the high-temperature and high-pressure method and was prevented from being mixed into diamond, into a diamond synthesis starting material. Yes, it is an epoch-making method in the production of single crystalline diamond.
なお、従来技術として、ダイヤモンド粒子とｃＢＮを焼結した焼結材は存在するが、得られたものは単結晶質のダイヤモンドとｃＢＮの複合体であり、本発明のダイヤモンド粒子と比較して、その組織が異なる。この複合体は、結合に用いた金属が粒界へ混入することによる強度低下が著しい。このため、加工時の自生発刃をしたとしても刃となる複合体は強度が低く、加工量が増加しない。 As a conventional technique, there is a sintered material obtained by sintering diamond particles and cBN, but the obtained material is a composite of single crystalline diamond and cBN, and compared with the diamond particles of the present invention, The organization is different. This composite has a remarkable decrease in strength due to the metal used for bonding entering the grain boundary. For this reason, even if it carries out the self-generated blade at the time of a process, the composite used as a blade has low intensity | strength and a processing amount does not increase.
また、焼結時にｃＢＮ粒子がタイヤモンド結晶中に分散することがないため、本発明のようにダイヤモンド粒子とｃＢＮ粒子との相乗効果を発揮することができない。さらに、化学気相法では前述のように単結晶質ダイヤモンド粒子中にｃＢＮ粒子を含有することができない。したがって、ｃＢＮ粒子を含有する単結晶質ダイヤモンド粒子を製造するためには、高温高圧法が最適である。 Further, since the cBN particles are not dispersed in the tiremond crystal during sintering, the synergistic effect of the diamond particles and the cBN particles cannot be exhibited as in the present invention. Further, in the chemical vapor deposition method, as described above, the single crystalline diamond particles cannot contain cBN particles. Therefore, the high-temperature and high-pressure method is most suitable for producing single crystalline diamond particles containing cBN particles.
本発明の製造方法は、（１）黒鉛、ｃＢＮ粒子、および触媒金属を有する出発原料を混合する工程、（２）混合原料をプレスして所定の形状に成形する工程、（３）プレス後の成形体を所定の圧力および温度の条件に曝して合成を行う工程である。これらについて以下に詳述する。 The production method of the present invention includes (1) a step of mixing a starting material having graphite, cBN particles, and a catalytic metal, (2) a step of pressing the mixed material to form it into a predetermined shape, and (3) after pressing. This is a step of performing synthesis by exposing the molded body to predetermined pressure and temperature conditions. These are described in detail below.
（１）黒鉛、ｃＢＮ粒子、および触媒金属を有する出発原料を混合する工程
本発明に係る製造方法に用いる黒鉛は、不純物濃度が３０ｐｐｍ未満であり、平均粒子径が１００メッシュ（目開き：１２７μｍ）以下であることが望ましい。ｃＢＮ粒子も同様である。これより大きいと、黒鉛の再結晶化および触媒金属の溶融に時間がかかる上、温度プロファイル及び圧力プロファイルが複雑になる。(1) Step of mixing starting material having graphite, cBN particles, and catalytic metal Graphite used in the production method according to the present invention has an impurity concentration of less than 30 ppm and an average particle size of 100 mesh (aperture: 127 μm) The following is desirable. The same applies to cBN particles. If it is larger than this, it takes time to recrystallize graphite and melt the catalyst metal, and the temperature profile and pressure profile become complicated.
本発明に係る製造方法に用いる触媒金属は、鉄、ニッケル、コバルト、およびマンガンの少なくとも１種を含有する混合物もしくは合金であることが望ましい。混合物もしくは合金の組成は、黒鉛からダイヤモンドへの変換効率を向上させるため、Ｎｉ：２５〜３０重量％、Ｃｏ：３〜５重量％、Ｍｎ：３〜５重量％、および残部がＦｅおよび不可避的不純物であることが望ましい。平均粒子径は黒鉛と同程度でよい。なお、「混合物」とは、各元素の金属（粉末）を混合したもの、もしくは２以上の元素の合金（粉末）を混合したものを表す。 The catalyst metal used in the production method according to the present invention is preferably a mixture or alloy containing at least one of iron, nickel, cobalt, and manganese. The composition of the mixture or alloy improves the conversion efficiency from graphite to diamond, so that Ni: 25-30 wt%, Co: 3-5 wt%, Mn: 3-5 wt%, and the balance is Fe and inevitable An impurity is desirable. The average particle size may be about the same as graphite. The “mixture” represents a mixture of metals (powder) of each element or a mixture of alloys (powder) of two or more elements.
黒鉛と触媒金属およびｃＢＮ粒子との混合比は、黒鉛からダイヤモンドへの転換時の体積収縮による圧力減衰の観点から、（黒鉛粉末）：（触媒金属＋ｃＢＮ粒子）＝１１：８〜１１が望ましい。触媒金属とｃＢＮ粒子の混合比は、核発生密度の観点から、（触媒金属）：（ｃＢＮ粒子）＝９９：１〜９０：１０が望ましい。 The mixing ratio of graphite to the catalytic metal and cBN particles is preferably (graphite powder) :( catalytic metal + cBN particles) = 11: 8 to 11 from the viewpoint of pressure decay due to volume shrinkage at the time of conversion from graphite to diamond. The mixing ratio of the catalyst metal and the cBN particles is preferably (catalyst metal) :( cBN particles) = 99: 1 to 90:10 from the viewpoint of the nucleus generation density.
上記範囲で秤量した出発原料を混合する。混合方法は一般的な方法でよい。例えば、上記出発原料を粉体混合機に投入し、２５０〜３００ＭＰａの減圧下で３０分以上混合することが望ましい。これによって、１００メッシュ（目開き：１４９μｍ）以下の混合粉末が得られる。 The starting materials weighed in the above range are mixed. The mixing method may be a general method. For example, it is desirable to put the starting material into a powder mixer and mix it for 30 minutes or more under a reduced pressure of 250 to 300 MPa. Thereby, a mixed powder of 100 mesh (aperture: 149 μm) or less is obtained.
（２）混合粉末をプレスして所定の形状に成形する工程
上記混合粉末を通常使用されるプレス機にて２２０〜２８０ＭＰａの加圧力で３〜１０秒間保持して、所望の円柱状原料を得る。(2) Step of pressing the mixed powder into a predetermined shape The above mixed powder is held for 3 to 10 seconds at a pressure of 220 to 280 MPa with a press machine usually used to obtain a desired cylindrical raw material. .
この円柱状原料をパイロフェライト製の圧力媒体容器に詰め出発原料とする。
This columnar raw material is packed in a pyroferrite pressure medium container and used as a starting raw material.
（３）プレス後の成形体を所定の圧力および温度に曝して合成を行う工程
上記の工程にて得られた出発原料を超高圧装置に導入し、所定の圧力プロファイルおよび温度プロファイルに従いダイヤモンドの合成を行う。圧力プロファイルおよび温度プロファイルは、図１に示す炭素の相平衡図において、最終的にはダイヤモンドが熱力学的に安定である領域の圧力および温度に設定する。また、両プロファイルは、特に限定されないが、出発原料の温度および圧力の均一化、黒鉛の再結晶化、触媒金属の溶融と黒鉛の濡れ、および核発生、粒子成長を考慮した上で各種条件を決定し多段階で操作することが望ましい。例えば図２に示すような圧力および温度操作である。(3) Step of synthesizing the pressed compact after exposure to a predetermined pressure and temperature The starting material obtained in the above step is introduced into an ultrahigh pressure apparatus, and diamond is synthesized according to the predetermined pressure profile and temperature profile. I do. The pressure profile and temperature profile are finally set to the pressure and temperature in the region where diamond is thermodynamically stable in the carbon phase equilibrium diagram shown in FIG. In addition, both profiles are not particularly limited, but various conditions are considered in consideration of uniform temperature and pressure of starting materials, recrystallization of graphite, melting of catalyst metal and wetting of graphite, nucleation, and particle growth. It is desirable to determine and operate in multiple stages. For example, pressure and temperature operations as shown in FIG.
圧力プロファイルの一例としては、まず、出発原料を超高圧装置に導入後、大気圧で６０〜１２０秒間保持する。次に、２０〜３０秒で最終設定圧力の２０〜２５％まで昇圧し、さらに３０〜１２０秒で最終設定圧力の６０〜７０％まで昇圧し、６０〜１２０秒間保持する。次いで、３０〜６０秒で最終設定圧力の８０〜９０％まで昇圧し、６０〜１８０秒間保持する。次に、最終設定圧力である５〜１０ＧＰａ好ましくは５．５〜６．３ＧＰａまで３００〜６００秒間かけて加圧し、３００〜１２００秒保持する。最後に、１２０〜６００秒で大気圧まで減圧する。 As an example of the pressure profile, first, the starting material is introduced into the ultrahigh pressure apparatus and then held at atmospheric pressure for 60 to 120 seconds. Next, the pressure is increased to 20 to 25% of the final set pressure in 20 to 30 seconds, further increased to 60 to 70% of the final set pressure in 30 to 120 seconds, and held for 60 to 120 seconds. Next, the pressure is increased to 80 to 90% of the final set pressure in 30 to 60 seconds and held for 60 to 180 seconds. Next, pressurization is performed over 300 to 600 seconds up to 5 to 10 GPa, preferably 5.5 to 6.3 GPa, which is a final set pressure, and is maintained for 300 to 1200 seconds. Finally, the pressure is reduced to atmospheric pressure in 120 to 600 seconds.
温度プロファイルの一例としては、まず、出発原料を超高圧装置に導入後、室温〜２００℃で６０〜１２０秒間保持する。次に、昇温速度を２５〜６０℃／秒で設定し、室温から１３００〜２０００℃、好ましくは１３５０〜１５５０℃の初期温度域まで昇温して３０〜１２０秒間保持する。次に、１０秒以内に初期温度から４〜７％低い温度に下げ、その温度域で３０〜１２０秒間保持する。その後、７００〜１２００秒かけてさらに２．５〜３．５％低い温度に下げ、その温度域で２４０〜１２００秒間保持する。最後に、３００秒以内に室温まで冷却を開始する。 As an example of the temperature profile, first, the starting material is introduced into the ultrahigh pressure apparatus and then held at room temperature to 200 ° C. for 60 to 120 seconds. Next, the rate of temperature increase is set at 25 to 60 ° C./second, the temperature is raised from room temperature to an initial temperature range of 1300 to 2000 ° C., preferably 1350 to 1550 ° C., and held for 30 to 120 seconds. Next, the temperature is lowered to 4 to 7% lower than the initial temperature within 10 seconds, and the temperature is maintained for 30 to 120 seconds. Thereafter, the temperature is further lowered to 2.5 to 3.5% over 700 to 1200 seconds, and the temperature is maintained for 240 to 1200 seconds. Finally, start cooling to room temperature within 300 seconds.
また、圧力と温度のタイミングは、昇温による触媒金属の溶融および黒鉛の再結晶化の観点から、最大加圧力の２０〜２２％まで昇圧すると同時に最高温度まで昇温し、最大加圧力に昇圧後、減圧の開始と同時もしくは減圧開始後であって減圧完了前までに冷却を開始することが望ましく、最大加圧力に昇圧し３００〜１２００秒で黒鉛がダイヤモンドに十分に変換した後、ダイヤモンドから黒鉛への再転移を防止するためにも減圧完了前もしくは減圧の開始と同時に冷却を開始することが望ましい。 The pressure and temperature timing is increased to 20-22% of the maximum applied pressure and simultaneously increased to the maximum temperature from the viewpoint of melting of the catalyst metal and recrystallization of the graphite by increasing the temperature. Thereafter, it is desirable to start cooling at the same time as the start of pressure reduction or after the start of pressure reduction and before the completion of pressure reduction. After the pressure is increased to the maximum pressure and graphite is sufficiently converted into diamond in 300 to 1200 seconds, In order to prevent re-transition to graphite, it is desirable to start cooling before completion of decompression or at the same time as decompression is started.
上記のような条件で出発原料を高温高圧に曝すことによって、ｃＢＮ粒子を含有する単結晶ダイヤモンドを製造することができる。 A single crystal diamond containing cBN particles can be produced by exposing the starting material to high temperature and high pressure under the above conditions.
１．発明例のダイヤモンド粒子の作製
まず、微細黒鉛粉末、および体積平均粒子径Ｄ５０値が３．５μｍのｃＢＮ粉末とＦｅ系合金触媒金属粉末（Ｎｉ：２８重量％、Ｃｏ：５重量％、Ｍｎ：３重量％、残部Ｆｅおよび不可避的不純物）の混合粉末（ｃＢＮ粒子：Ｆｅ系合金触媒金属粉末＝９７：３）であって、４００メッシュ以下の粉末を用意した。黒鉛粉末と混合粉末の混合比は、（黒鉛粉末）：（ｃＢＮ粒子とＦｅ系合金触媒粉末の混合粉末）＝１１：９とした。1. Preparation of Diamond Particles of Invention Example First, fine graphite powder, cBN powder having a volume average particle diameter D50 value of 3.5 μm and Fe-based alloy catalyst metal powder (Ni: 28 wt%, Co: 5 wt%, Mn: 3 A mixed powder (cBN particles: Fe-based alloy catalyst metal powder = 97: 3) of 400 wt.% Or less was prepared. The mixing ratio of the graphite powder and the mixed powder was (graphite powder) :( mixed powder of cBN particles and Fe-based alloy catalyst powder) = 11: 9.
これを出発原料として粉体混合機に投入し、２８０ＭＰａの減圧下で１２０分間混合し、１００メッシュ以下の微細な混合粉末を得た。 This was put into a powder mixer as a starting material and mixed for 120 minutes under a reduced pressure of 280 MPa to obtain a fine mixed powder of 100 mesh or less.
そして、混合粉末をプレス金型内に投入し、２３０ＭＰａ、２５℃、５秒間の条件で加圧成形し、φ５５ｍｍ×４３ｍｍの円柱状原料を作製した。得られた円柱状原料を７５ｍｍ３のパイロフェライト製の圧力媒体容器に詰め出発原料とした。Then, the mixed powder was put into a press mold and pressure-molded under the conditions of 230 MPa, 25 ° C., and 5 seconds to produce a cylindrical raw material of φ55 mm × 43 mm. The obtained cylindrical raw material was packed in a pressure medium container made of 75 mm 3 pyroferrite and used as a starting raw material.
圧力および温度を６.２ＧＰａ１３５０℃に設定し、出発原料を中国製キュービックアンビル型超高圧装置に導入し、ダイヤモンド安定領域に曝した。 The pressure and temperature were set to 6.2 GPa 1350 ° C., and the starting material was introduced into a cubic anvil type ultra-high pressure apparatus made in China and exposed to the diamond stable region.
圧力プロファイルは図２に示すとおりである。具体的には、超高圧装置に出発原料をセットし大気圧で９０秒間保持した。次に、３０秒で設定圧力の２０％である１．２４ＧＰａまで昇圧し、さらに６５％である４．０ＧＰａまで６０秒で昇圧し、６０秒間保持した。次いで、３０秒で設定圧力の８５％である５．３ＧＰａまで昇圧し１２０秒間保持した。さらに６００秒で設定圧力の６．２ＧＰａまで昇圧し、３００秒間保持した。最後に、１８０秒で大気圧まで減圧した。 The pressure profile is as shown in FIG. Specifically, the starting material was set in an ultrahigh pressure apparatus and held at atmospheric pressure for 90 seconds. Next, the pressure was increased to 1.24 GPa, which is 20% of the set pressure, in 30 seconds, and further increased to 4.0 GPa, which is 65%, in 60 seconds and held for 60 seconds. Next, the pressure was increased to 5.3 GPa, which is 85% of the set pressure, in 30 seconds, and held for 120 seconds. Further, the pressure was increased to a set pressure of 6.2 GPa in 600 seconds and held for 300 seconds. Finally, the pressure was reduced to atmospheric pressure in 180 seconds.
また、温度プロファイルは図２に示すとおりである。具体的には、超高圧装置に出発原料をセットし１５０℃で９０秒間保持した。初期温度を８％高い１４５０℃に設定し、５２℃／秒の昇温速度で１５０℃から約２５秒で１４５０℃に昇温して９０秒間保持した。次に、１０秒以内に４％低い１３９０℃まで温度を下げて６０秒間保持した。その後、７２０秒でさらに３％低い１３５０℃まで温度を下げて３００秒間保持した後、冷却を開始した。 The temperature profile is as shown in FIG. Specifically, the starting material was set in an ultrahigh pressure apparatus and held at 150 ° C. for 90 seconds. The initial temperature was set to 1450 ° C., which was 8% higher, and the temperature was increased from 150 ° C. to 1450 ° C. in about 25 seconds at a temperature increase rate of 52 ° C./second and held for 90 seconds. Next, the temperature was lowered to 1390 ° C. 4% lower within 10 seconds and held for 60 seconds. Thereafter, the temperature was lowered to 1350 ° C., which was 3% lower in 720 seconds, and maintained for 300 seconds, and then cooling was started.
圧力と温度のタイミングは、１．２４ＧＰａまで昇圧するとほぼ同時に１４５０℃まで昇温し、６.２ＧＰａに昇圧時の温度は１３５０℃であり３００秒後に冷却を開始した。 When the pressure and temperature were increased to 1.24 GPa, the temperature increased to 1450 ° C. almost simultaneously. The temperature at the time of pressure increase to 6.2 GPa was 1350 ° C., and cooling was started after 300 seconds.
２．比較例であるホウ素含有ダイヤモンド粒子の作製
上記「１．」において、ｃＢＮ粒子に代えてホウ素粉末を用いたことを除いて、上記「１．」と同様の方法で作製した。2. Preparation of Boron-Containing Diamond Particles as a Comparative Example In the above “1.”, the boron-containing diamond particles were prepared by the same method as “1.” except that boron powder was used instead of the cBN particles.
３．比較例であるノンドープダイヤモンド粒子の作製
上記「１．」において、ｃＢＮ粒子を投入しなかったことを除いて、上記「１．」と同様の方法で作製した。3. Production of Non-Doped Diamond Particles as Comparative Example Production was performed in the same manner as in “1.” except that cBN particles were not added in “1.”.
４．評価
（１）衝撃強度
ポットミル衝撃破砕性試験による破砕値（Ｔｏｕｇｈｎｅｓｓ Ｉｎｄｅｘ（Ｔｉ）値）による評価を行った。内径１２．５ｍｍ深さ２５ｍｍの円筒状のスチールカプセルに、あらかじめサイズ分けされた試料２ｃｔ（４００ｍｇ）と、直径８ｍｍ重量２ｇのスチールボール１個とを封入した。封入後のスチールカプセルを、ＲＥＴＥＫ社製Ｆｒｉａｂｉｌｉｔｙ ｔｅｓｔｅｒにて２分間２８３０回揺動させ試料を粉砕した。揺動後の試料において、粉砕された試料の質量に対する試料全体の質量の割合を算出し１００分率で示した。4). Evaluation (1) Impact strength Evaluation was performed based on a crush value (Toughness Index (Ti) value) by a pot mill impact crushability test. In a cylindrical steel capsule having an inner diameter of 12.5 mm and a depth of 25 mm, a pre-sized sample 2ct (400 mg) and a steel ball having a diameter of 8 mm and a weight of 2 g were enclosed. The encapsulated steel capsule was rocked 2830 times for 2 minutes on a friability tester manufactured by RETEK, and the sample was pulverized. In the sample after rocking, the ratio of the mass of the entire sample to the mass of the crushed sample was calculated and indicated as 100 minutes.
結果を表１に示す。
（１）熱的安定性
熱重量分析装置（Ｒｉｇａｋｕ社製、型番：Ｔｈｅｒｍｏ ｐｌｕｓ ＥＶＯ２）を用い、大気雰囲気下で１０℃／ｍｉｎの条件で室温から１３００℃まで昇温した場合におけるサンプル重量の減少率を測定した。The results are shown in Table 1.
(1) Thermal stability Decrease in sample weight when the temperature is raised from room temperature to 1300 ° C under the condition of 10 ° C / min in an air atmosphere using a thermogravimetric analyzer (manufactured by Rigaku, model number: Thermo plus EVO2). The rate was measured.
結果を図４に示す。
（２）ダイヤモンド粒子の平均粒子径
得られたダイヤモンド粒子はＪＩＳＢ４１３０（１９９８）による篩分け法によってサイズ分けした。The results are shown in FIG.
(2) Average particle diameter of diamond particles The obtained diamond particles were sized by a sieving method according to JISB4130 (1998).
（３）ダイヤモンド粒子中のｃＢＮ粒子の平均粒子径、個数
出発原料として用いたｃＢＮ粒子の平均粒子径は３０μｍ以下であるため、ＪＩＳＢ４１３０（１９９８）篩分け法による粒度測定は困難である。そこで、粉体粒子径測定で一般的に用いられているレーザ回折式粒度分布測定機（Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ社製、型式：Ｍａｓｔｅｒｓｉｚｅｒ２０００）を用い平均粒子径を測定した。ダイヤモンド結晶内に取り込まれたｃＢＮ粒子は光学顕微鏡下でミクロンスケールによって採寸し、用いた平均粒子径と差異がほとんど無いことを確認した。結晶内に取り込まれた個数に関してはカウントすることが困難であるため、均一性を目視で確認した。(3) Average particle diameter and number of cBN particles in diamond particles Since the average particle diameter of cBN particles used as a starting material is 30 μm or less, particle size measurement by JISB4130 (1998) sieving method is difficult. Then, the average particle diameter was measured using the laser diffraction type particle size distribution analyzer (Malvern Instruments company make, Mastersizer2000) generally used by powder particle diameter measurement. The cBN particles taken into the diamond crystal were measured on a micron scale under an optical microscope, and it was confirmed that there was almost no difference from the average particle diameter used. Since it was difficult to count the number of crystals taken into the crystal, the uniformity was visually confirmed.
表１から明らかなように、発明例のダイヤモンド粒子は、比較例のダイヤモンド粒子より衝撃強度が低い結果が得られた。これは、発明例のダイヤモンド粒子では、粒子中のダイヤモンドとｃＢＮとの粒界が起点となり、ノンドープダイヤモンド、ホウ素含有ダイヤモンドより破砕性が向上したためである。換言すれば、発明例は破砕による自生発刃性が優れていると言える。 As is apparent from Table 1, the diamond particles of the inventive example had a lower impact strength than the diamond particles of the comparative example. This is because in the diamond particles of the invention example, the grain boundary between diamond and cBN in the particles is the starting point, and the crushability is improved compared to non-doped diamond and boron-containing diamond. In other words, it can be said that the invention example is excellent in the spontaneous cutting ability by crushing.
図３は、発明例のダイヤモンド粒子の光学顕微鏡写真であり、図３（ａ）は倍率が１０００倍の光学顕微鏡写真であり、図３（ｂ）は倍率が１００倍の光学顕微鏡写真である。
図３から明らかなように、ｃＢＮ粒子が単結晶ダイヤモンド粒子の内部に概ね均一に分散していることがわかる。また、ｃＢＮ粒子の平均粒子径は、ミクロンスケールによって採寸したところ３．５μｍ程度であり、あらかじめ測定した体積平均粒子径Ｄ５０値である３．５μｍと同一であった。また、図３のカラー写真から、ダイヤモンド粒子の色は高温高圧合成ダイヤモンド合成によく見られるノンドープダイヤモンド特有色の黄色よりも緑色を帯びており、さらにｃＢＮ粒子のアンバー色が混ざることで濃い緑色であることを確認した。このことから、本実施例の単結晶ダイヤモンド粒子は、ホウ素ドープダイヤモンド特有の青色〜青黒色の結晶を有していないことが明らかになった。FIG. 3 is an optical micrograph of the diamond particles of the inventive example, FIG. 3 (a) is an optical micrograph with a magnification of 1000 times, and FIG. 3 (b) is an optical micrograph with a magnification of 100 times.
As is apparent from FIG. 3, it can be seen that the cBN particles are substantially uniformly dispersed inside the single crystal diamond particles. The average particle size of the cBN particles was about 3.5 μm when measured on a micron scale, and was the same as the previously measured volume average particle size D50 value of 3.5 μm. Also, from the color photograph in FIG. 3, the color of the diamond particles is more green than the yellow color unique to non-doped diamonds often seen in high-temperature and high-pressure synthetic diamond synthesis, and the amber color of the cBN particles is mixed with a dark green color. I confirmed that there was. From this, it became clear that the single crystal diamond particles of this example did not have the blue to blue-black crystals peculiar to boron-doped diamond.
図４は、ホウ素がドープされていない比較例のダイヤモンド粒子、ホウ素がドープされた比較例のダイヤモンド粒子、およびｃＢＮ粒子を粒子内に含有する発明例のダイヤモンド粒子における、熱重量分析結果を示すグラフである。図４から明らかなように、ホウ素がドープされていない比較例のノンドープダイヤモンド粒子は、７００℃程度から重量減少が始まり、９００℃程度ですべて焼失した。また、ホウ素がドープされた比較例のダイヤモンド粒子は、８００℃程度で重量減少が始まり、１０００℃では２０％程度減少していることがわかった。一方、ｃＢＮを含有する発明例のダイヤモンド粒子は、９００℃程度で重量減少が始まるが、１０００℃でも重量減少が５％未満であり、高い熱的安定性を示すことがわかった。
FIG. 4 is a graph showing the results of thermogravimetric analysis of the comparative diamond particles not doped with boron, the comparative diamond particles doped with boron, and the inventive diamond particles containing cBN particles. It is. As is apparent from FIG. 4, the non-doped diamond particles of the comparative example not doped with boron started to lose weight from about 700 ° C. and were all burned out at about 900 ° C. In addition, it was found that the diamond particles of the comparative example doped with boron started to decrease in weight at about 800 ° C. and decreased by about 20% at 1000 ° C. On the other hand, the diamond particles of the inventive example containing cBN started to decrease in weight at about 900 ° C., but the weight decrease was less than 5% even at 1000 ° C., and it was found that high thermal stability was exhibited.
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| JP2018008875A (en) * | 2017-06-30 | 2018-01-18 | 燕山大学 | Superhigh hardness nano-twin crystal diamond bulk material |
| CN109078581A (en) * | 2018-08-29 | 2018-12-25 | 中南钻石有限公司 | A kind of catalytic alloy powder and the surface grooves shape diamond using its preparation, preparation method and application |
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