JPH0477396A - Production of diamond particles - Google Patents
Production of diamond particlesInfo
- Publication number
- JPH0477396A JPH0477396A JP2190012A JP19001290A JPH0477396A JP H0477396 A JPH0477396 A JP H0477396A JP 2190012 A JP2190012 A JP 2190012A JP 19001290 A JP19001290 A JP 19001290A JP H0477396 A JPH0477396 A JP H0477396A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- particles
- deposited
- porous carbon
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 97
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 94
- 239000002245 particle Substances 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005240 physical vapour deposition Methods 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- -1 molybudenum Substances 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 239000011162 core material Substances 0.000 abstract 3
- 239000010941 cobalt Substances 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000011224 oxide ceramic Substances 0.000 abstract 1
- 229910052574 oxide ceramic Inorganic materials 0.000 abstract 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract 1
- 239000010937 tungsten Substances 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 239000011733 molybdenum Substances 0.000 description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004880 explosion Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野]
本発明は、ダイヤモンド粒子の製造方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing diamond particles.
従来、ダイヤモンド粒子を析出させる方法としては、例
えば、特開昭59−137311号公報、特開昭61−
168596号公報、特開昭62−216906号公報
等に開示される如く、高圧法、爆発法、低圧法によって
、水素と気体状の炭化水素とから成るダイヤモンド合成
用原料ガスを、プラズマによって化学的に反応性に冨む
励起状態の水素原子と炭化水素分子とに活性化して、流
動層中にある粉末の表面に、ダイヤモンド粒子を析出さ
せることが知られている。Conventionally, methods for precipitating diamond particles include, for example, JP-A-59-137311 and JP-A-61-
As disclosed in Japanese Patent Application Laid-open No. 168596 and Japanese Patent Application Laid-Open No. 62-216906, diamond synthesis raw material gas consisting of hydrogen and gaseous hydrocarbons is chemically processed by plasma using a high-pressure method, an explosion method, and a low-pressure method. It is known that diamond particles are precipitated on the surface of powder in a fluidized bed by activating highly reactive excited hydrogen atoms and hydrocarbon molecules.
特に、工業的に広く使用されているダイヤモンド粉体は
、高圧法による生成粒を粉砕して得られたものである。In particular, diamond powder, which is widely used industrially, is obtained by crushing produced grains using a high-pressure method.
〔発明が解決しようとする課B]
然し、高圧法は、エネルギコストが高い上に、大きく成
長したものを粉砕するので、粒度を揃えるには、歩留ま
りが悪い等の不具合があった。[Problem B to be Solved by the Invention] However, the high-pressure method has high energy costs and also has problems such as poor yields in order to make the particle size uniform because it crushes large grown particles.
又、爆発法は、高圧法の一種であるため、歩留まりが悪
く、爆発の遮音上、工場立地に制約がある等の不具合が
あった。Furthermore, since the explosion method is a type of high-pressure method, it has problems such as poor yield, noise insulation from explosions, and restrictions on factory location.
更に、低圧法は、基板上への析出の場合、粒子析出が表
面に起き、体積的に起こらず、大量の粉体の析出はでき
なかった。Furthermore, in the case of deposition on a substrate, the low-pressure method causes particle precipitation to occur on the surface and not in volume, making it impossible to deposit a large amount of powder.
この低圧法としては、流動層のフリーボードを用いるも
の(特開昭62−216906号公報参照)、気流中に
懸垂するもの(特開昭61−168596号公報参照)
等があるが、100μmオーダは析出できても、数μm
オーダ以下の微小粒の析出は、粒子径が小さいため、気
流に搬送され、反応部に保持できず、為しうることがで
きなかった。又、核成長密度は著しく低く、更に析出さ
せる固体表面(基板)の物質に制約があり、大量生産に
適していなかった。Examples of this low-pressure method include those using a freeboard of a fluidized bed (see JP-A No. 62-216906) and those suspending in an air flow (see JP-A No. 61-168596).
etc., but even if it is possible to deposit on the order of 100 μm, it is only a few μm.
Precipitation of microparticles of the order of magnitude or less could not be carried out because their particle diameters were small, so they were carried by the airflow and could not be retained in the reaction section. In addition, the density of nuclear growth was extremely low, and there were also restrictions on the material on the solid surface (substrate) to be deposited, making it unsuitable for mass production.
本発明は斯かる従来の問題点を解決するために為された
もので、その目的は、ダイヤモンドの析出密度を高める
と共に、ダイヤモンド粒子を効率良く多量に生産するこ
とを可能としたダイヤモンド粒子の製造方法を提供する
ことにある。The present invention was made to solve these conventional problems, and its purpose is to manufacture diamond particles that can increase the density of diamond precipitation and efficiently produce large quantities of diamond particles. The purpose is to provide a method.
請求項1記載のダイヤモンド粒子の製造方法は、ダイヤ
モンド発生の核となる物質を蒸着した固体を、ダイヤモ
ンド合成用原料ガスがプラズマ又は火炎或いはホットフ
ィラメントによって分解反応を起こす反応場中に配し、
固体表面にダイヤモンド結晶層を析出させるものである
。The method for producing diamond particles according to claim 1 includes placing a solid material on which a substance that is a nucleus for diamond generation is deposited in a reaction field where a raw material gas for diamond synthesis undergoes a decomposition reaction by plasma, flame, or hot filament;
This method deposits a diamond crystal layer on the solid surface.
請求項2記載のダイヤモンド粒子の製造方法は、ダイヤ
モンド発生の核となる物質を蒸着した多孔質炭素粒子を
、プラズマ又は火炎或いはホットフィラメントによって
ダイヤモンド合成用原料ガスが分解反応を起こす流動層
又は回転炉中で流動化乃至転動して、多孔質炭素粒子内
に多量のダイヤモンド粒子を析出させるものである。The method for producing diamond particles according to claim 2 is characterized in that porous carbon particles on which a material that becomes the core of diamond generation is vapor-deposited are subjected to a decomposition reaction with raw material gas for diamond synthesis using plasma, flame, or hot filament in a fluidized bed or a rotary furnace. The porous carbon particles are fluidized or rolled in the carbon particles to precipitate a large amount of diamond particles within the porous carbon particles.
請求項3記載のダイヤモンド粒子の製造方法は、請求項
2に於て、ダイヤモンド粒子を析出後に、多孔質炭素粒
子を500〜800℃で焼却除去するものである。The method for producing diamond particles according to claim 3 is the method according to claim 2, wherein after the diamond particles are precipitated, the porous carbon particles are removed by incineration at 500 to 800°C.
請求項1に係るダイヤモンド結晶層を析出させるダイヤ
モンド粒子の製造方法に於ては、先ず、例えば、グラフ
ァイト及び不定形炭素質物質、酸化物・窒化物・炭化物
系セラミック等の1000℃程度の高温に耐えられる固
体の表面に、例えば、Mo。In the method for producing diamond particles to precipitate a diamond crystal layer according to claim 1, first, for example, graphite, amorphous carbonaceous materials, oxide/nitride/carbide ceramics, etc. are heated to a high temperature of about 1000°C. For example, Mo on a resistant solid surface.
Co、 W、 Si等のダイヤモンド発生の核となる物
質を、気相蒸着法(化学的蒸着(CVD法)、物理的蒸
着(PVD法)(真空蒸着法、スパッタリング法等)を
含む)に従って蒸着して、ダイヤモンド発生の核となる
物質を蒸着した固体を造る。次に、水素(ヘリウム又は
アルゴン等のキャリアガスを含むこともある)と気体状
の炭化水素(例えば、C)14゜C’2H6,C3H5
,エチルアルコール、メチルアルコール等)等から成る
ダイヤモンド合成用原料ガスが、プラズマ銃(DCプラ
ズマ、 RFプラズマ、マイクロ波プラズマ等)による
プラズマ又は燃焼バーナによる火炎或いはホットフィラ
メント等によって、化学的に反応性に冨む励起状態の水
素原子と炭素分子とに活性化されて、ダイヤモンドを析
出する反応を起こす600〜1100℃程度の温度の反
応場(例えば、固定層、移動層1回転炉、流動層、気流
層、気相等)を形成し、この中に上記固体を配する。こ
れによって、固体表面に蒸着されたダイヤモンド発生の
核となる物質が、活性化されて、固体表面に、ダイヤモ
ンド結晶層を析出させることができる。Co, W, Si, etc., which are the core of diamond generation, are deposited using a vapor phase deposition method (including chemical vapor deposition (CVD method), physical vapor deposition (PVD method) (vacuum evaporation method, sputtering method, etc.)) Then, a solid material is created on which the material that forms the core of diamond formation is deposited. Next, hydrogen (which may include a carrier gas such as helium or argon) and a gaseous hydrocarbon (e.g. C)14°C'2H6,C3H5
, ethyl alcohol, methyl alcohol, etc.) is made chemically reactive by using plasma from a plasma gun (DC plasma, RF plasma, microwave plasma, etc.), flame from a combustion burner, hot filament, etc. A reaction field with a temperature of about 600 to 1100 °C (e.g., fixed bed, moving bed single rotary furnace, fluidized bed, (air flow layer, gas phase, etc.), and the above-mentioned solid is placed in this. As a result, the substance that is deposited on the solid surface and becomes the nucleus for diamond generation is activated, and a diamond crystal layer can be deposited on the solid surface.
請求項2に係るダイヤモンド粒子の製造方法に於ては、
先ず、予め流動し易い40μm以上の粒径に揃えた多孔
質炭素粒子に、例えば、Mo、 Co、 WSi等のダ
イヤモンド発生の核となる物質を、気相蒸着法(化学的
蒸着(CVD法)、物理的蒸着(PVD法)(真空蒸着
法、スパッタリング法等)を含む)に従って蒸着して、
ダイヤモンド発生の核となる物質を表面及び細孔に蒸着
した多孔質炭素粒子を造る。次に、この多孔質炭素粒子
を、常圧又は減圧状態の気泡流動層、循環流動層又は回
転炉内に導入し、水素(ヘリウム又はアルゴン等のキャ
リアガスを含むこともある)と気体状の炭化水素(例え
ば、CH,、C2Hb、 C31’18+エチルアルコ
ール メチルアルコール等)等から成るダイヤモンド合
成用原料ガスにより流動化乃至転動させる。その後、そ
の流動層又は回転炉中にプラズマ銃(DCプラズマ、
RFプラズマ、マイクロ波プラズマ等)によるプラズマ
又は燃焼バーナによる火炎或いはホットフィラメント等
を起こし、これによって、ダイヤモンド合成用原料ガス
が、化学的に反応性に冨む励起状態の水素原子と炭素分
子とに活性化されて、ダイヤモンドを析出する反応を起
こす600〜1100℃程度の温度となり、多孔質炭素
粒子の表面及び細孔内に蒸着されたダイヤモンド発生の
核となる物質上で、活性化されて、多孔質炭素粒子の外
表面のみならず、その内部細孔表面上に、多数のダイヤ
モンドを析出させることができる。In the method for producing diamond particles according to claim 2,
First, a substance that will become the nucleus of diamond generation, such as Mo, Co, WSi, etc., is applied to porous carbon particles whose particle size has been adjusted to a particle size of 40 μm or more that is easy to flow, using a vapor phase deposition method (chemical vapor deposition (CVD method)). , physical vapor deposition (PVD method) (including vacuum evaporation method, sputtering method, etc.),
Porous carbon particles are made by depositing a substance that becomes the nucleus for diamond generation on the surface and in the pores. The porous carbon particles are then introduced into a bubbling fluidized bed, circulating fluidized bed, or rotary furnace at normal or reduced pressure, and hydrogen (which may also include a carrier gas such as helium or argon) and gaseous Fluidization or rolling is performed using a raw material gas for diamond synthesis consisting of hydrocarbons (for example, CH, C2Hb, C31'18+ ethyl alcohol, methyl alcohol, etc.). Then, a plasma gun (DC plasma,
RF plasma, microwave plasma, etc.) or a combustion burner generates a flame or hot filament, which converts the raw material gas for diamond synthesis into chemically reactive excited hydrogen atoms and carbon molecules. It is activated to a temperature of about 600 to 1100°C that causes a reaction to precipitate diamond, and is activated on the material that is the nucleus of diamond generation deposited on the surface of the porous carbon particles and in the pores. A large number of diamonds can be deposited not only on the outer surface of the porous carbon particles but also on the inner pore surfaces thereof.
請求項3に係るダイヤモンド粒子の製造方法に於ては、
請求項2に係るダイヤモンド粒子の製造方法によって表
面、細孔内にダイヤモンドが生成したマトリックスに相
当する多孔質炭素粒子を、流動層法で500〜800℃
程度の低温で燃焼して、多孔質炭素粒子を焼却除去する
ことによって、ダイヤモンド微粒子を回収することがで
きる。In the method for producing diamond particles according to claim 3,
Porous carbon particles corresponding to a matrix in which diamonds are formed on the surface and in the pores by the method for producing diamond particles according to claim 2 are heated at 500 to 800°C by a fluidized bed method.
The diamond fine particles can be recovered by incinerating and removing the porous carbon particles by burning at a relatively low temperature.
以下、本発明の実施例を具体的に説明する。 Examples of the present invention will be specifically described below.
実施例1
本実施例は、請求項1記載のダイヤモンド結晶層を析出
させるダイヤモンド粒子の製造方法に関するものであり
、その方法に用いられる装置の概要が第1図及び第2図
に示されている。Example 1 This example relates to a method for producing diamond particles to precipitate a diamond crystal layer according to claim 1, and an outline of an apparatus used in the method is shown in FIGS. 1 and 2. .
先ず、炭素多孔質板に、CVD法によってモリブデン微
粒子を蒸着させ、モリブデン蒸着処理済の炭素多孔質板
1を作成する。First, molybdenum fine particles are deposited on a carbon porous plate by the CVD method to create a molybdenum vapor-deposited carbon porous plate 1.
このモリブデン蒸着処理済の炭素多孔質板1は、冷却管
2と共に、中央に孔4を設けたモリブデン箔のベルト3
に掛けられている。このベルト3は、バネ5で保持され
ている。又、冷却管2には、水が通しである。This molybdenum vapor-deposited carbon porous plate 1, together with a cooling pipe 2, is made up of a molybdenum foil belt 3 having a hole 4 in the center.
It is hung on. This belt 3 is held by a spring 5. Further, water is passed through the cooling pipe 2.
一方、これらの下方には、DCプラズマ装置6が設けら
れている。このDCプラズマ装置6は、アノード7と、
このアノード7に設けた孔8の下方に所定の間隔を隔て
てカソード9が配され、両者の隙間からダイヤモンド合
成用原料ガス10が供給されるようになっている。On the other hand, below these, a DC plasma device 6 is provided. This DC plasma device 6 includes an anode 7,
A cathode 9 is arranged below the hole 8 provided in the anode 7 at a predetermined interval, and a raw material gas 10 for diamond synthesis is supplied from the gap between the two.
斯くして、モリブデン蒸着処理済の炭素多孔質板1を配
置した後、ダイヤモンド合成用原料ガス10として、ア
ルゴン<5.21 (20℃)/分)、水素(2,61
20℃)/分)、メタン(0,0651(20℃)/分
)を用い、アーク放電は電流約35A、電圧約20V、
圧力は300Torrとし、反応時間は30〜60分と
して、プラズマジェット11をモリブデン箔のベルト3
で固定したモリブデン蒸着処理済の炭素多孔質板1に向
かって放射した。After disposing the carbon porous plate 1 subjected to molybdenum vapor deposition treatment, argon <5.21 (20° C./min) and hydrogen (2,61
20℃/min), methane (0,0651 (20℃)/min), arc discharge at a current of about 35A, voltage of about 20V,
The pressure was 300 Torr, the reaction time was 30 to 60 minutes, and the plasma jet 11 was connected to the molybdenum foil belt 3.
The beam was radiated toward a carbon porous plate 1 fixed with molybdenum vapor deposition.
その結果、プラズマジェット11によってモリブデン蒸
着処理済の炭素多孔質板1の内表面のモリブデンが核と
なってそこから、ダイヤモンドを析出する反応を起こし
、その表面に数十μmのダイヤモンドを析出させること
ができた。As a result, the plasma jet 11 causes the molybdenum on the inner surface of the carbon porous plate 1, which has been subjected to the molybdenum vapor deposition process, to become a nucleus, which causes a reaction to precipitate diamond, and several tens of micrometers of diamond are precipitated on the surface. was completed.
比較例1
モリブデンを蒸着しない炭素多孔質板を上記と同様の処
理を施したものと比較した処、粒子密度が飛躍的に増加
し、更に粒子径も大幅に増大していることが確認できた
。又、モリブデンを蒸着しない場合には、核生成に時間
が掛り、同一反応時間内での粒子成長時間が短くなって
成長粒子径が小さくなったものと考えられる。Comparative Example 1 When a porous carbon plate without molybdenum vapor deposited was compared with one treated in the same manner as above, it was confirmed that the particle density increased dramatically and the particle size also increased significantly. . Moreover, it is thought that when molybdenum was not vapor-deposited, it took time for nucleation to occur, and the particle growth time within the same reaction time became shorter, resulting in a smaller grown particle size.
実施例2
本実施例は請求項2記載のダイヤモンド粒子の製造方法
に関するものである。Example 2 This example relates to the method for producing diamond particles according to claim 2.
多孔質炭素粒子として、見掛は密度0.28〜0.36
g/ctl、比表面積900〜1100n(/g、平均
気孔径20〜40μm、気孔率0.78〜0.84のも
のを用いた。As porous carbon particles, the apparent density is 0.28-0.36
g/ctl, specific surface area of 900 to 1100 n(/g, average pore diameter of 20 to 40 μm, and porosity of 0.78 to 0.84).
先ず、多孔質炭素粒子に、CVD法によりモリブデン微
粒子を蒸着した後、流動化し易い粒度に揃えたモリブデ
ン蒸着処理済みの多孔質炭素粒子12を用意する。First, molybdenum fine particles are deposited on porous carbon particles by the CVD method, and then porous carbon particles 12 which have been subjected to molybdenum vapor deposition treatment and whose particle size is adjusted to be easily fluidized are prepared.
次に、このモリブデン蒸着処理済みの多孔質炭素粒子1
2を、第3図に示す装置を用いてダイヤモンド粒子を生
成させた。Next, the porous carbon particles 1 subjected to molybdenum vapor deposition treatment are
2, diamond particles were produced using the apparatus shown in FIG.
先ず、モリブデン蒸着処理済の多孔質炭素粒子12を、
流動層装置反応容器13内に入れ、流動層装置反応容器
13の下部から、夫々の容器10a、10b、10cに
圧填されているダイヤモンド合成用原料ガス(本例では
、アルゴン、水素。First, porous carbon particles 12 that have been subjected to molybdenum vapor deposition are
The raw material gas for diamond synthesis (in this example, argon, hydrogen) is put into the fluidized bed reactor 13 and is pressurized into each of the containers 10a, 10b, 10c from the lower part of the fluidized bed reactor 13.
メタン)10を供給し、このダイヤモンド合成用原料ガ
ス10により、モリブデン蒸着処理済の多孔質炭素粒子
12を流動化させ、流動層装置反応容器13内で流動懸
垂された多孔質炭素粒子部14を形成する。次に、流動
層装置反応容器13の下部に設けたDCプラズマ装置1
5によってプラズマ16を起こし、上記流動層中のダイ
ヤモンド合成用原料ガス10を高温で分解し、600〜
1100’C程度の温度でダイヤモンドを析出する反応
を起こさせ、モリブデン蒸着処理済の多孔質炭素粒子I
2に、ダイヤモンドを析出させた。methane) 10 is supplied, and with this raw material gas 10 for diamond synthesis, the porous carbon particles 12 that have been subjected to molybdenum vapor deposition are fluidized, and the porous carbon particles 14 suspended in fluidization in the reaction vessel 13 of the fluidized bed apparatus are Form. Next, the DC plasma device 1 installed at the bottom of the fluidized bed device reaction vessel 13
5 generates plasma 16 and decomposes the raw material gas 10 for diamond synthesis in the fluidized bed at high temperature.
Porous carbon particles I subjected to molybdenum vapor deposition by causing a reaction to precipitate diamond at a temperature of about 1100'C.
2, diamond was deposited.
尚、流動層装置反応容器13の上部には、フィルタ22
を内蔵した排気管21が設けられている。Note that a filter 22 is installed in the upper part of the fluidized bed apparatus reaction vessel 13.
An exhaust pipe 21 containing a built-in exhaust pipe is provided.
斯くして得られたダイヤモンドを析出させた多孔質炭素
粒子は、表面だけではなく内部にもダイヤモンドが析出
していることが確認できた。又、モリブデンを蒸着しな
かった多孔質炭素粒子を同様に処理したものと比較して
、粒子密度が増加し、粒子径も増大していることが確認
された。更に、析出した粒子の大半は、その形状が、ボ
ール状であった。これは多孔体の場合、析出面温度が平
面に比して高くなるからと考えられる。It was confirmed that diamond was precipitated not only on the surface but also inside the porous carbon particles obtained in this manner. Furthermore, it was confirmed that the particle density and particle size were increased compared to porous carbon particles on which molybdenum was not vapor-deposited and similarly treated. Furthermore, most of the precipitated particles were ball-shaped. This is thought to be because in the case of a porous body, the precipitation surface temperature is higher than that in a flat body.
尚、請求項2記載のダイヤモンド粒子の製造方法は、第
3図に示す装置に限らず、例えば、第4図乃至第7図に
示す流動層装置を用いた場合にも同様の効果を得ること
ができた。Note that the method for manufacturing diamond particles according to claim 2 is not limited to the apparatus shown in FIG. 3, and similar effects can be obtained when using, for example, fluidized bed apparatuses shown in FIGS. 4 to 7. was completed.
第4図では、循環流動層サイクロン17を設けて多孔質
炭素粒子が循環流動できるようにしたものである。循環
流動層サイクロン17の上部には、フィルタ22を内蔵
した排気管21が設けられでいる。尚、第4図に示す流
動層装置の流動層装置反応容器13の外側部には、高周
波コイルを巻回して使用する場合もある。又、第5図は
大量に反応を起こさせるために多数のプラズマ銃18を
平面的に並べ、広面積で流動層部を形成し、ダイヤモン
ド生成を行なえるようにしたものである。更に、第6図
は第5図と同様に大量に反応を起こさせるために多数の
バーナ燃焼器19を平面的に並べ、広面積で流動層部を
形成し、火炎20によってダイヤモンド生成を行なえる
ようにしたものである。更に又、図示しないが、第5図
と第6図の装置には、第4図と同様に循環流動層サイク
ロンを設けることによって、多孔質炭素粒子が循環流動
できるようにした装置でも同様の効果があった。In FIG. 4, a circulating fluidized bed cyclone 17 is provided to allow porous carbon particles to circulate and flow. At the top of the circulating fluidized bed cyclone 17, an exhaust pipe 21 containing a filter 22 is provided. Incidentally, a high frequency coil may be wound around the outer side of the fluidized bed apparatus reaction vessel 13 of the fluidized bed apparatus shown in FIG. 4 in some cases. Further, in FIG. 5, a large number of plasma guns 18 are arranged in a plane to cause a large amount of reaction, and a fluidized bed portion is formed over a wide area so that diamond can be generated. Furthermore, as in FIG. 5, in FIG. 6, a large number of burner combustors 19 are arranged in a plane to cause a large amount of reaction, a fluidized bed is formed over a wide area, and diamond can be generated by flame 20. This is how it was done. Furthermore, although not shown in the drawings, similar effects can be obtained by providing the apparatuses shown in FIGS. 5 and 6 with a circulating fluidized bed cyclone similar to that shown in FIG. was there.
更に、第7図に示す装置は、モリブデン蒸着処理済の炭
素多孔質粒子を、流動層装置に連続的に供給するための
供給部23から導入し、ダイヤモンド粒子含有の炭素多
孔質粒子を排出部24から排出するように構成されてお
り、下部には、第6図と同様に、火炎20を起こす多数
のバーナ燃焼器19が設けられている。尚、第7図の装
置では、第5図に示す装置と同様に、バーナ燃焼器19
に代えてDCプラズマ装置15を使用しても同様の効果
が奏される。Furthermore, the apparatus shown in FIG. 7 introduces carbon porous particles that have been subjected to molybdenum vapor deposition from a supply section 23 for continuously supplying them to the fluidized bed apparatus, and sends carbon porous particles containing diamond particles to a discharge section. 24, and a number of burner combustors 19 for generating flames 20 are provided at the bottom, similar to FIG. 6. Note that in the device shown in FIG. 7, the burner combustor 19 is similar to the device shown in FIG.
Similar effects can be obtained even if the DC plasma device 15 is used instead.
実施例3
本実施例は請求項3記載のダイヤモンド粒子の製造方法
に関するものである。Example 3 This example relates to the method for producing diamond particles according to claim 3.
実施例2で得られた表面及び細孔にダイヤモンドが析出
した多孔質炭素粒子を、流動法によって500〜800
℃の温度でマトリックスに相当する多孔質炭素粒子を焼
却し、析出したダイヤモンド微粒子を回収した。The porous carbon particles obtained in Example 2 with diamond precipitated on the surface and pores were heated to 500 to 800 particles by a flow method.
The porous carbon particles corresponding to the matrix were incinerated at a temperature of °C, and the precipitated diamond fine particles were collected.
以上の如く、請求項1に係るダイヤモンド粒子の製造方
法によれば、ダイヤモンドを析出させる固体の表面に、
ダイヤモンド発生の核となる物質を蒸着することによっ
て、ダイヤモンド発生反応を行なうものであるから、粒
子密度が増加し、粒子径も増大したダイヤモンド粒子を
得ることができる。而も、ダイヤモンド発生反応温度で
ある600〜1100℃程度の温度に耐えられる物質で
あれば、如何なるものであっても使用できるので、従来
の低圧法の如く析出する固体の制約がなくなる。又、微
小粒子の析出が可能となる。更に、ダイヤモンド析出層
の粒子密度は高いので、装飾用としても適用できる。As described above, according to the method for producing diamond particles according to claim 1, on the surface of the solid on which diamond is precipitated,
Since the diamond generation reaction is carried out by vapor depositing a substance that becomes the core of diamond generation, diamond particles with increased particle density and particle size can be obtained. However, any substance can be used as long as it can withstand the diamond generation reaction temperature of about 600 to 1100°C, so there is no restriction on solids precipitated as in the conventional low-pressure method. Furthermore, precipitation of fine particles becomes possible. Furthermore, since the diamond precipitated layer has a high particle density, it can also be used for decoration.
請求項2記載のダイヤモンド粒子の製造方法によれば、
ダイヤモンド発生の核となる物質を蒸着した多孔質炭素
粒子を使用することにより、表面及び細孔内部にダイヤ
モンドを析出させることが可能となり、従来の平面上或
いは粒子表面のみの析出に比ベダイヤモンド析出の効率
が高くなる。According to the method for producing diamond particles according to claim 2,
By using porous carbon particles on which a substance that forms the nucleus of diamond generation is deposited, it is possible to deposit diamonds on the surface and inside the pores. becomes more efficient.
又、ダイヤモンドを多孔質炭素粒子に析出させるに当た
り、予めダイヤモンド発生の核となり得る物質を蒸着に
よりコーティングして置くことにより、ダイヤモンドの
析出密度を飛躍的に高めることができる。更に、流動化
し易い粒径に揃えた多孔質炭素粒子を用いて、流動層に
よりプラズマ又は火炎或いはホットフィラメントにより
ダイヤモンド合成用原料ガスを分解1反応させることに
より多量にダイヤモンドを析出させることが可能となる
。特に、回分式流動層で行えば、数μmオーダの粒度の
揃ったダイヤモンド微粉が製造でき、研磨剤、粉末冶金
原料等として極めて有用である。Furthermore, when diamond is precipitated onto porous carbon particles, by coating the porous carbon particles with a substance that can become a nucleus for diamond generation by vapor deposition, the density of diamond precipitation can be dramatically increased. Furthermore, it is possible to precipitate a large amount of diamond by decomposing and reacting raw material gas for diamond synthesis with plasma, flame, or hot filament in a fluidized bed using porous carbon particles whose particle size is adjusted to facilitate fluidization. Become. In particular, if the process is carried out in a batch-type fluidized bed, fine diamond powder with a uniform particle size on the order of several μm can be produced, which is extremely useful as an abrasive, a raw material for powder metallurgy, etc.
而も、多孔質炭素粒子の中にダイヤモンド粒子を保持し
ているため、ダイヤモンド粒子による装置の摩耗も抑え
られる。Furthermore, since the diamond particles are held within the porous carbon particles, wear of the device due to the diamond particles can be suppressed.
請求項3記載のダイヤモンド粒子の製造方法によれば、
ダイヤモンド析出後に、マトリックスに相当する多孔質
炭素粒子を500〜800℃の温度で焼却除去するため
、ダイヤモンドを担持していた多孔質炭素粒子がなくな
り、ダイヤモンド微粒子を直接容易に回収することがで
きる。According to the method for producing diamond particles according to claim 3,
After the diamond is precipitated, the porous carbon particles corresponding to the matrix are removed by incineration at a temperature of 500 to 800°C, so the porous carbon particles supporting the diamond disappear, and the diamond fine particles can be directly and easily recovered.
第1図は請求項1に係る実施例に用いた装置の一部を切
り欠いて示す正面図である。
第2図は請求項1に係る実施例に用いた装置の一部を切
り欠いて示す側面図である。
第3図は請求項2に係る実施例に用いた装置を示す概要
説明図である。
第4図乃至第7図は請求項2に係る実施例に用いた装置
の変形例を示す概要説明図である。
〔主要な部分の符号の説明〕
1・・・モリブデン蒸着処理済の炭素多孔質板6.15
・・・DCプラズマ装置
10・・・ダイヤモンド合成用原料ガス11・・・プラ
ズマジェット
12・・・モリブデン蒸着処理済の多孔質炭素粒子13
・・・流動層装置反応器
14・・・多孔質炭素粒子部
16・・・プラズマ
19・・・バーナ燃焼器
20・・・火炎。
第5図FIG. 1 is a partially cutaway front view of a device used in an embodiment according to claim 1. FIG. 2 is a partially cutaway side view of the apparatus used in the embodiment according to claim 1. FIG. 3 is a schematic explanatory diagram showing an apparatus used in an embodiment according to claim 2. 4 to 7 are schematic explanatory diagrams showing modifications of the apparatus used in the embodiment according to claim 2. [Explanation of symbols of main parts] 1... Carbon porous plate treated with molybdenum vapor deposition 6.15
. . . DC plasma device 10 . . . Raw material gas for diamond synthesis 11 . . . Plasma jet 12 . . . Molybdenum vapor-deposited porous carbon particles 13
... Fluidized bed reactor 14 ... Porous carbon particle section 16 ... Plasma 19 ... Burner combustor 20 ... Flame. Figure 5
Claims (3)
を、ダイヤモンド合成用原料ガスがプラズマ又は火炎或
いはホットフィラメントによって分解反応を起こす反応
場中に配し、固体表面にダイヤモンド結晶層を析出させ
ることを特徴とするダイヤモンド粒子の製造方法。(1) Placing a solid material on which a substance that becomes the core of diamond generation is deposited in a reaction field where raw material gas for diamond synthesis undergoes a decomposition reaction by plasma, flame, or hot filament, and depositing a diamond crystal layer on the solid surface. A method for producing diamond particles characterized by:
質炭素粒子を、プラズマ又は火炎或いはホットフィラメ
ントによってダイヤモンド合成用原料ガスが分解反応を
起こす流動層又は回転炉中で流動化乃至転動して、多孔
質炭素粒子内に多量のダイヤモンド粒子を析出させるこ
とを特徴とするダイヤモンド粒子の製造方法。(2) Porous carbon particles on which the material that forms the core of diamond generation is vapor-deposited are fluidized or rolled in a fluidized bed or rotary furnace where raw material gas for diamond synthesis undergoes a decomposition reaction using plasma, flame, or hot filament. , a method for producing diamond particles, characterized by precipitating a large amount of diamond particles within porous carbon particles.
多孔質炭素粒子を500〜800℃で焼却除去すること
を特徴とするダイモヤンド粒子の製造方法。(3) In claim 2, after precipitating the diamond particles,
A method for producing dymoyand particles, which comprises removing porous carbon particles by incineration at 500 to 800°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP02190012A JP3128807B2 (en) | 1990-07-17 | 1990-07-17 | Method for producing diamond particles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP02190012A JP3128807B2 (en) | 1990-07-17 | 1990-07-17 | Method for producing diamond particles |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5748595A (en) * | 1995-03-30 | 1998-05-05 | Ricoh Company, Ltd. | Cartridge loading mechanism with a door closing assembly |
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-
1990
- 1990-07-17 JP JP02190012A patent/JP3128807B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5748595A (en) * | 1995-03-30 | 1998-05-05 | Ricoh Company, Ltd. | Cartridge loading mechanism with a door closing assembly |
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