JP6558897B2 - A manufacturing method for diamond structures with excellent thermal conductivity. - Google Patents
A manufacturing method for diamond structures with excellent thermal conductivity. Download PDFInfo
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- JP6558897B2 JP6558897B2 JP2014267205A JP2014267205A JP6558897B2 JP 6558897 B2 JP6558897 B2 JP 6558897B2 JP 2014267205 A JP2014267205 A JP 2014267205A JP 2014267205 A JP2014267205 A JP 2014267205A JP 6558897 B2 JP6558897 B2 JP 6558897B2
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- 239000010432 diamond Substances 0.000 title claims description 87
- 229910003460 diamond Inorganic materials 0.000 title claims description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000843 powder Substances 0.000 claims description 31
- 238000011282 treatment Methods 0.000 claims description 26
- 239000002113 nanodiamond Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
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- 239000011261 inert gas Substances 0.000 claims description 16
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
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- CBCIHIVRDWLAME-UHFFFAOYSA-N hexanitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O CBCIHIVRDWLAME-UHFFFAOYSA-N 0.000 description 2
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- Carbon And Carbon Compounds (AREA)
Description
本発明は、ダイヤモンド粉末を、高温、高圧下で固めて優れた熱伝導性を有するダイヤモンド構造体を、簡便に、効率よく、かつ高い生産性で製造する方法に関する。 The present invention relates to a method for easily and efficiently producing a diamond structure having excellent thermal conductivity by solidifying diamond powder at high temperature and high pressure with high productivity.
ダイヤモンドは、化学的安定性、生体適合性、半導体特性、硬度、熱伝導性等の物性の高さから、パワー半導体デバイス、電子放出源、電極、ＭＥＭＳ、バイオデバイス、切削工具、研磨工具、プローブ、ヒートシンク、触媒担体等への応用が期待されている。しかし、ダイヤモンド自体の正確な微細加工が困難であるという問題があり、これがデバイスの実用化を阻む原因の一つとなっている。ダイヤモンドの微細加工では、上記の困難さのために、まずは所定の構造を製造することが目的となっている。ダイヤモンド構造体の微細加工では、加工面の平坦性、形状を加工する方法等さまざまな技術開発が行われている。 Diamonds have high physical properties such as chemical stability, biocompatibility, semiconductor properties, hardness, and thermal conductivity, so power semiconductor devices, electron emission sources, electrodes, MEMS, biodevices, cutting tools, polishing tools, probes Application to heat sinks, catalyst carriers, etc. is expected. However, there is a problem that accurate microfabrication of diamond itself is difficult, and this is one of the causes that hinders practical use of devices. In the fine processing of diamond, first of all, the purpose is to manufacture a predetermined structure because of the above-mentioned difficulty. In the fine processing of a diamond structure, various technological developments such as a method for processing the flatness of the processed surface and the shape have been performed.
これらは所望の構造体を加工することによって得ることを目的とした技術開発であり、所望の構造体そのものを得る技術開発については検討されていない。 These are technical developments aimed at obtaining a desired structure, and technical development for obtaining the desired structure itself has not been studied.
従って、本発明の目的は、ダイヤモンド粉末を、高温、高圧下で固めて優れた熱伝導性を有するダイヤモンド構造体を、簡便に、効率よく、かつ高い生産性で製造する方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for easily and efficiently producing a diamond structure having excellent thermal conductivity by consolidating diamond powder at high temperature and high pressure with high productivity. is there.
上記目的に鑑み鋭意研究の結果、本発明者らは、不活性ガス雰囲気中で、ダイヤモンド粉末を高温、高圧下で成型して、熱伝導性に優れたダイヤモンド構造体を製造することができることを見出し、本発明に想到した。 As a result of diligent research in view of the above object, the present inventors have found that a diamond structure having excellent thermal conductivity can be produced by molding diamond powder at high temperature and high pressure in an inert gas atmosphere. The headline and the present invention were conceived.
すなわち、本発明のダイヤモンド構造体の製造法は、不活性ガス雰囲気中で、ダイヤモンド粉末を高温、高圧下で用途に応じた任意の形状に成型した熱伝導性に優れたことを特徴とするダイヤモンド構造体及びその製造法に関する。 That is, the method for producing a diamond structure according to the present invention is characterized in that the diamond powder is excellent in thermal conductivity by molding diamond powder into an arbitrary shape according to the application under high temperature and high pressure in an inert gas atmosphere. The present invention relates to a structure and a manufacturing method thereof.
前記ダイヤモンド粉末を窒素、ヘリウム、アルゴン等の不活性ガス雰囲気下、高温、高圧下で焼結し、成型することが好ましい。 The diamond powder is preferably sintered and molded under an inert gas atmosphere such as nitrogen, helium or argon under high temperature and high pressure.
前記ダイヤモンド構造体において、高温が１３００〜３５００Ｋ、高圧が４〜１２ＧＰａの範囲の組合せで焼結し、成型することが好ましい。 The diamond structure is preferably sintered and molded in a combination of a high temperature of 1300 to 3500 K and a high pressure of 4 to 12 GPa.
前記ダイヤモンド構造体において、ダイヤモンドが爆轟法により得られたナノダイヤモンドであることが好ましい。 In the diamond structure, the diamond is preferably a nanodiamond obtained by a detonation method.
前記ダイヤモンド構造体において、ダイヤモンドの熱伝導率が５００Ｗ／ｍ・Ｋ以上であることが好ましい。 In the diamond structure, the thermal conductivity of diamond is preferably 500 W / m · K or more.
ここで言う熱伝導率は、ＪＩＳ Ｒ１６１１に準拠して測定した。
熱伝導率の単位は、Ｗ／ｍ・Ｋ で表される。ここで、
Ｗ；ワット
ｍ；メートル
Ｋ；絶対温度（ケルビン）
を表す。The heat conductivity said here was measured based on JISR1611.
The unit of thermal conductivity is expressed as W / m · K. here,
W; Watt m; Meter K; Absolute temperature (Kelvin)
Represents.
本発明は、不活性ガス雰囲気中で、ダイヤモンド粉末を高温、高圧下で焼結し、成型することによって、任意の形状の熱伝導性の良好な成型物とし、パワー半導体デバイス、電子放出源、電極、ＭＥＭＳ、バイオデバイス、切削工具、研磨工具、プローブ、ヒートシンク、触媒担体等への応用が期待できる。 The present invention sinters diamond powder at a high temperature and high pressure in an inert gas atmosphere and molds it to obtain a molded article having a good thermal conductivity in an arbitrary shape, a power semiconductor device, an electron emission source, Applications to electrodes, MEMS, biodevices, cutting tools, polishing tools, probes, heat sinks, catalyst carriers, etc. can be expected.
［１］ダイヤモンド構造体の製造方法
本発明のダイヤモンド構造体の製造方法の好ましい実施の形態について詳細に説明するが、本発明はこれらに限定されるものではない。[1] Method for Producing Diamond Structure A preferred embodiment of the method for producing a diamond structure of the present invention will be described in detail, but the present invention is not limited thereto.
（１）ダイヤモンド構造体の製造法
本発明のダイヤモンド構造体の製造方法は、高温、高圧圧縮機に金型をセットし、金型中にダイヤモンド粉末を窒素、ヘリウム、アルゴン、ネオン、クリプトン、キセノン等の不活性ガス雰囲気に満たし、高温、高圧下で圧縮、焼結し、構造体にすることを特徴とする。(1) Manufacturing method of diamond structure The manufacturing method of the diamond structure of the present invention is such that a mold is set in a high-temperature, high-pressure compressor, and diamond powder is put into nitrogen, helium, argon, neon, krypton, xenon in the mold. It is characterized in that it is filled with an inert gas atmosphere, and is compressed and sintered at a high temperature and high pressure to form a structure.
ダイヤモンド粉体には空気を含むので、高温に加熱するとダイヤモンドが酸化して燃焼するので、高温、高圧圧縮機にセットした金型にダイヤモンド粉末をセットした状態で、金型部分より吸引して、空気を予め除去しておくことが好ましい。真空で空気を除去するとダイヤモンド粉体が舞い上がるので、ダイヤモンド粉体が舞い上がらないように、徐々に真空度を上げて空気を除く事が好ましい。 Since diamond powder contains air, when heated to a high temperature, diamond oxidizes and burns, so in a state where diamond powder is set in a mold set in a high-temperature, high-pressure compressor, suction from the mold part, It is preferable to remove air in advance. When the air is removed in a vacuum, the diamond powder rises. Therefore, it is preferable to gradually increase the degree of vacuum to remove the air so that the diamond powder does not rise.
しかる後、金型部分にダイヤモンド粉末が舞い上がらないように、不活性ガスを徐々に注入することが好ましい。注入する不活性ガスとしては、窒素、ヘリウム、アルゴン、ネオン、クリプトン、キセノン等が挙げられるが、窒素、ヘリウム、アルゴンが特に好ましい。 After that, it is preferable to gradually inject an inert gas so that diamond powder does not rise in the mold part. Examples of the inert gas to be injected include nitrogen, helium, argon, neon, krypton, and xenon, and nitrogen, helium, and argon are particularly preferable.
ダイヤモンド粉末は、使用用途に応じて作製された金型にコンパクトに充填され次工程で高温に加熱され、高圧がかけられる。高温加熱、加圧に先だって、金型中のダイヤモンド粉末より空気を完全に除くために、空気を除く真空操作と不活性ガスを注入する操作を数回繰り返し行う事が好ましい。 The diamond powder is compactly filled in a mold produced according to the intended use, heated to a high temperature in the next step, and subjected to high pressure. Prior to high temperature heating and pressurization, in order to completely remove air from the diamond powder in the mold, it is preferable to repeat the vacuum operation for removing air and the operation for injecting an inert gas several times.
不活性ガスで置換されたダイヤモンド粉末を金型に充填した状態で、不活性ガスを温度７００〜１２００Ｋで１分から３０分かけて予熱して、しかる後、高温、高圧をかけてダイヤモンド構造体を作製する。かける温度としては、７００〜４０００Ｋ、好ましくは１３００〜３３００Ｋであることが良い。このときの圧力は、１Ｇｐａ〜１５Ｇｐａ、好ましくは４〜１２Ｇｐａであることが良い。温度、圧力は、これら両者の組合せの範囲内で有れば良い。加熱する温度、圧力が７００Ｋ以下、１Ｇｐａ以下であると構造体としての形状の保持が難しく、力を加えると容易に崩れる。また熱伝導率が目的とする５００Ｗ／ｍ・Ｋ以上を達成できない。その理由は良く分からないが、不活性ガス等がダイヤモンド間に介在し、ダイヤモンドの密着が十分でない事が理由であるかもしれない。加熱する温度、圧力の上限は特に限定されないが、生産技術上４０００Ｋ、１５Ｇｐａ程度が限界である。また４０００Ｋ以上では加熱による劣化が大きく好ましくない。加熱、加圧する時間は、数秒から５分の間で有れば良く、好ましくは１５秒から３分程度かければ良い。高温で加圧圧縮終了後、冷却スピードが遅いとナノダイヤモンドは酸化劣化するので、冷却は速いほうが良く、冷却するスピードは、５００〜６０００Ｋ／分であることが良い。 In a state where the diamond powder substituted with the inert gas is filled in the mold, the inert gas is preheated at a temperature of 700 to 1200 K for 1 to 30 minutes, and then the diamond structure is formed by applying high temperature and high pressure. Make it. The applied temperature is 700 to 4000K, preferably 1300 to 3300K. The pressure at this time is 1 Gpa to 15 Gpa, preferably 4 to 12 Gpa. The temperature and pressure may be within the range of the combination of both. When the heating temperature and pressure are 700 K or less and 1 Gpa or less, it is difficult to maintain the shape as a structure, and when a force is applied, it easily collapses. Moreover, the thermal conductivity of 500 W / m · K or more cannot be achieved. The reason is not well understood, but it may be because an inert gas or the like is interposed between the diamonds and the diamond is not sufficiently adhered. The upper limit of the heating temperature and pressure is not particularly limited, but is limited to about 4000 K and 15 Gpa in terms of production technology. Further, when the temperature is 4000K or more, deterioration due to heating is large and not preferable. The heating and pressurizing time may be between several seconds and 5 minutes, preferably 15 seconds to 3 minutes. After completion of pressurization and compression at a high temperature, if the cooling speed is slow, the nanodiamond is oxidized and deteriorated. Therefore, the cooling is preferably fast, and the cooling speed is preferably 500 to 6000 K / min.
（２）ダイヤモンドの製造法
ダイヤモンド粉末としては、市販のナチュラルダイヤモンドを用いることが好ましい。０〜０．１μから３０〜４０μ大きさのナチュラルダイヤモンドは多数あるが、細かく粉砕したメジアン径で１００ｎｍ程度のダイヤモンド粉末を用いることが好ましい。本発明に於いて用いるダイヤモンドは、爆轟法ナノダイヤモンドが更に好ましい。爆轟法ナノダイヤモンドは、コアがＳＰ３ダイヤモンドで、その表面のシェルはＳＰ２グラファイトからなるコア・シェル構造から成っている。シェルのＳＰ２グラファイト表面に多数の官能基、すなわち、水酸基（−ＯＨ）、カルボキシル基（−ＣＯＯＨ）等が存在している。高温・高圧を加えることで固い構造体になる理由は明らかでないが、−ＯＨと−ＣＯＯＨが、又は−ＯＨ同士が反応して、エーテル結合を作製するためと考えられている。いずれにしろ、しっかりと結合したダイヤモンド構造体が得られる。(2) Diamond production method It is preferable to use commercially available natural diamond as the diamond powder. There are many natural diamonds having a size of 0 to 0.1 μ to 30 to 40 μm, but it is preferable to use diamond powder having a median diameter of about 100 nm and finely ground. The diamond used in the present invention is more preferably detonated nanodiamond. The detonation nanodiamond has a core-shell structure in which the core is SP3 diamond and the surface shell is SP2 graphite. Many functional groups, that is, hydroxyl groups (—OH), carboxyl groups (—COOH), and the like are present on the surface of the SP2 graphite of the shell. Although the reason why a hard structure is formed by applying high temperature and high pressure is not clear, it is considered that —OH and —COOH or —OH react with each other to form an ether bond. In any case, a tightly bonded diamond structure is obtained.
爆轟法によるナノダイヤモンドの合成は、例えば、水と多量の氷を満たした純チタン製の耐圧容器に、電気雷管を装着した爆薬［例えば、ＴＮＴ（トリニトロトルエン）／ＨＭＸ（シクロテトラメチレンテトラニトラミン）＝５０／５０］を胴内に収納させ、片面プラグ付き鋼鉄製パイプを水平に沈め、この鋼鉄製パイプに鋼鉄製のヘルメット状カバーを被覆して、前記爆薬を爆裂させることにより行うことができる。反応生成物としてのナノダイヤモンドは容器中の水中から回収する。 Nano-diamond synthesis by the detonation method is, for example, an explosive in which an electric detonator is mounted on a pressure vessel made of pure titanium filled with water and a large amount of ice [for example, TNT (trinitrotoluene) / HMX (cyclotetramethylenetetranitra). Min) = 50/50] is stored in the body, a steel pipe with a single-sided plug is sunk horizontally, a steel helmet-like cover is covered on the steel pipe, and the explosive is exploded. Can do. Nanodiamond as a reaction product is recovered from the water in the container.
爆薬としては、トロメチルアニリン（テトリル）、トリアミノトリニトロベンゼン（ＴＡＴＢ）、ジアミノトリニトロベンゼン（ＤＡＴＢ）、ヘキサニトロスチルベン（ＨＮＳ）、ヘキサニトロアゾベンゼン（ＨＮＡＢ）、ヘキサニトロジフェニルアミン（ＨＮＤＰ）、ピクリン酸、ピクリン酸アンモニウム、ベンゾトリアゾール（ＴＡＣＯＴ）、エチレンジニトラミン（ＥＤＮＡ）、ニトログアニジン（ＮＱ）、ペンタエリスリトールテトラナイトレート（ペンスリット）、ベンゾトリフルオキサン（ＢＴＦ）等が挙げられ、これらを単独又は混合して使用する。特に、ＲＤＸ（６０％）とＴＮＴ（４０％）との混合爆薬であるコンポジションＢ、ＨＭＸ（７５％）とＴＮＴ（２５％）との混合爆薬であるオクトール等を使用するのが好ましい。 Explosives include tromethylaniline (tetril), triaminotrinitrobenzene (TATB), diaminotrinitrobenzene (DATB), hexanitrostilbene (HNS), hexanitroazobenzene (HNAB), hexanitrodiphenylamine (HNDP), picric acid, Examples include ammonium picrate, benzotriazole (TACOT), ethylenedinitramine (EDNA), nitroguanidine (NQ), pentaerythritol tetranitrate (pen slit), benzotrifluoroxane (BTF), etc. And use it. In particular, it is preferable to use Composition B which is a mixed explosive of RDX (60%) and TNT (40%), octol which is a mixed explosive of HMX (75%) and TNT (25%), and the like.
これらの有機系爆薬は、炭素原子含有率が１５質量％以上、好ましくは２０〜３５質量％、密度が１．５ｇ／ｃｃ以上、好ましくは１．６ｇ／ｃｃ以上、爆速は７０００ｍ／ｓ以上、好ましくは７５００ｍ／ｓ以上であり、酸素バランスが負、好ましくは−０．２〜−０．６であり、爆轟圧が１８ＧＰａ以上、好ましくは２０〜３０ＧＰａ、爆轟温度が３０００Ｋ以上、好ましくは３０００〜４０００Ｋである。そのため、爆薬中の炭素原子を効率よくダイヤモンドに転換することができる。 These organic explosives have a carbon atom content of 15% by mass or more, preferably 20 to 35% by mass, a density of 1.5 g / cc or more, preferably 1.6 g / cc or more, an explosion speed of 7000 m / s or more, Preferably it is 7500 m / s or more, oxygen balance is negative, preferably -0.2 to -0.6, detonation pressure is 18 GPa or more, preferably 20 to 30 GPa, detonation temperature is 3000 K or more, preferably It is 3000-4000K. Therefore, carbon atoms in the explosive can be efficiently converted to diamond.
回収した爆発生成物は、ナノオーダーサイズのダイヤモンドの表面をグラファイト系炭素が覆ったコア／シェル構造を有しており、黒く着色している。この未精製のナノダイヤモンドは、２．４〜２．６ｇ／ｃｍ３程度の密度を有し、メジアン径（動的光散乱法）は５０〜５００ｎｍ程度である。未精製ナノダイヤモンドの精製の程度によっては目的とする熱伝導性に差異が出るので、高熱伝導性を求める場合は、ＳＰ２グラファイトを除去して構造体に供することが好ましい。この未精製のダイヤモンドを後述の方法で酸化処理することにより、グラファイト系炭素のシェル層を除去し、ナノダイヤモンドの粒子を得ることができる。酸化処理により精製したダイヤモンド粒子は、２〜１０ｎｍ程度の一次粒子からなるメジアン径５０〜２５０ｎｍ程度の二次粒子である。The recovered explosion product has a core / shell structure in which the surface of a nano-order diamond is covered with graphite-based carbon, and is colored black. This unpurified nanodiamond has a density of about 2.4 to 2.6 g / cm 3 and a median diameter (dynamic light scattering method) of about 50 to 500 nm. Depending on the degree of purification of the unpurified nanodiamond, the desired thermal conductivity differs. Therefore, when high thermal conductivity is desired, it is preferable to remove SP2 graphite and use it for the structure. By oxidizing this unpurified diamond by the method described later, the graphite carbon shell layer can be removed to obtain nanodiamond particles. The diamond particles purified by the oxidation treatment are secondary particles having a median diameter of about 50 to 250 nm composed of primary particles of about 2 to 10 nm.
未精製のナノダイヤモンド（粗ダイヤモンド）の酸化処理方法としては、（ａ）硝酸等の共存下で高温高圧処理する方法（酸化処理Ａ）、（ｂ）水及び／又はアルコールからなる超臨界流体中で処理する方法（酸化処理Ｂ）、（ｃ）水及び／又はアルコールからなる溶媒に酸素を共存させて、前記溶媒の標準沸点以上の温度及び０．１ＭＰａ（ゲージ圧）以上の圧力で処理する方法（酸化処理Ｃ）、又は（ｄ）３８０〜４５０℃で酸素を含む気体により処理する方法（酸化処理Ｄ）が挙げられる。これらの酸化処理は、単独で行ってもよいし、組合せて行っても良い。酸化処理を組合せる場合は、爆轟法で得られた未精製のナノダイヤモンドにまず酸化処理Ａを施し、さらに酸化処理Ｂ〜Ｃのいずれかを施すのが好ましい。 As an oxidation treatment method of unpurified nanodiamond (crude diamond), (a) a method of high-temperature and high-pressure treatment in the presence of nitric acid (oxidation treatment A), (b) in a supercritical fluid composed of water and / or alcohol (C) Treatment is carried out at a temperature not lower than the normal boiling point of the solvent and a pressure not lower than 0.1 MPa (gauge pressure) in the presence of oxygen in a solvent comprising water and / or alcohol. Examples thereof include a method (oxidation treatment C) and (d) a method of treatment with a gas containing oxygen at 380 to 450 ° C. (oxidation treatment D). These oxidation treatments may be performed alone or in combination. When combining the oxidation treatment, it is preferable to first subject the unpurified nanodiamond obtained by the detonation method to oxidation treatment A and then to any of oxidation treatments B to C.
爆轟法で得られた未精製のダイヤモンドに酸化処理Ａを施すことによりグラファイト層の一部が除去されたダイヤモンド粒子（グラファイト−ダイヤモンド粒子）が得られ、このグラファイト−ダイヤモンド粒子に酸化処理Ｂ〜Ｃのいずれかの処理を施すことにより前記グラファイト層をさらに除去することができる。 Oxidation treatment A is applied to unpurified diamond obtained by the detonation method to obtain diamond particles from which a part of the graphite layer has been removed (graphite-diamond particles). The graphite layer can be further removed by performing any of the treatments of C.
酸化処理したダイヤモンドの密度は、ダイヤモンド粒子中のダイヤモンドとグラファイトとの量によって決まる。すなわち、未精製のナノダイヤモンドに施す酸化処理の程度によって、ダイヤモンド粒子中のダイヤモンドとグラファイトとの量を変え、ダイヤモンド粒子の密度を調節することができる。グラファイト系炭素（グラファイトの密度：２．２５ｇ／ｃｍ３）の残存量が少なくなればなるほどダイヤモンドの密度（３．５０ｇ／ｃｍ３）に近づく。従って、精製度が高くグラファイト系炭素の残存量が少ないほど密度が高くなる。The density of the oxidized diamond is determined by the amount of diamond and graphite in the diamond particles. That is, the density of diamond particles can be adjusted by changing the amount of diamond and graphite in the diamond particles according to the degree of oxidation treatment performed on the unpurified nanodiamond. (Density of Graphite: 2.25g / cm 3) graphitic carbon approaches the density of the remaining amount is small, the more an Diamond (3.50g / cm 3). Therefore, the higher the degree of purification and the smaller the residual amount of graphite carbon, the higher the density.
本発明を実施例によりさらに詳細に説明するが、本発明はそれらに限定されるものではない。 The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
実施例１〜５、比較例１〜２
（１）爆薬の準備
図４（ａ）に示すように、ＴＮＴ（トリニトロトルエン）とＲＤＸ（シクロトリメチレントリニトロアミン）を６０／４０の比で含む０．６５ｋｇの爆薬３を、円筒状のＰＥＴ製の容器２０ａに充填し、同じくＰＥＴ製の蓋２０ｂをして容器２０ａを密閉した。前記蓋２０ｂに設けられたノズル２１から容器２０ａ内の空気を吸引し、代わりに窒素ガスを充填する操作を５回繰り返した後、ノズルを閉めて容器２０ａを密閉した。このような操作により、容器２０ａ内は窒素ガスで満たされ、このときの酸素濃度は０．５容量％であった。なお爆薬３には、起爆用爆薬及び電気雷管を取り付けた。Examples 1-5, Comparative Examples 1-2
(1) Preparation of explosive As shown in FIG. 4 (a), 0.65 kg of explosive 3 containing TNT (trinitrotoluene) and RDX (cyclotrimethylenetrinitroamine) in a ratio of 60/40 is formed into a cylindrical shape. The
（２）爆薬の設置
この爆薬３を充填した容器２０ａを、図１に示すように、５ｍ３の大きさの耐圧性容器１内のほぼ中央部分に吊材４で吊り下げ、耐圧性容器１内の空気を窒素と置換した。前記吊材４として銅線を使用し、爆薬３を起爆するための電気雷管への電流はこの銅線を通して供給した。このときの耐圧性容器１内は１気圧であり、酸素濃度は４容量％であった。(2) Installation of explosive The
（３）爆発
耐圧性容器１の外壁に、送風機で風を当てながら窒素ガスで満たした容器２０ａに充填した爆薬３を爆発させた。(3)
（４）爆発生成物の回収
爆発後５分間静置し、耐圧性容器１の上蓋７を開け、水で耐圧性容器の内壁面を洗浄しながら黒色液状の爆発生成物（未精製のダイヤモンド）を回収した。この未精製のダイヤモンドの収率は使用した爆薬量に対して７．５質量％であり、密度は２．４４ｇ／ｃｍ３、メジアン径（動的光散乱法）は１００ｎｍであった。この未精製のダイヤモンドは、密度から計算して、８５体積％のグラファイト系炭素と１５体積％のダイヤモンドからなっていると推定された。(4) Recovery of explosive products Leave for 5 minutes after the explosion, open the top lid 7 of the pressure-resistant container 1 and clean the inner wall surface of the pressure-resistant container with water (black liquid explosive product (unrefined diamond)) Was recovered. The yield of the unpurified diamond was 7.5% by mass with respect to the amount of explosive used, the density was 2.44 g / cm 3 , and the median diameter (dynamic light scattering method) was 100 nm. This unrefined diamond was estimated from the density to be composed of 85% by volume of graphite-based carbon and 15% by volume of diamond.
（５）ダイヤモンドの精製
この未精製のダイヤモンドを６０質量％硝酸水溶液と混合し、１６０℃、１４気圧、２０分の条件で酸化性分解処理を行った後、１３０℃、１３気圧、１時間で酸化性エッチング処理を行った。酸化性エッチング処理により、グラファイトが一部除去された粒子が得られた。この粒子を、アンモニアを用いて、２１０℃、２０気圧、２０分還流し中和処理した後、自然沈降させデカンテーションにより３５質量％硝酸での洗浄を行い、さらにデカンテーションにより３回水洗し、遠心分離により脱水し、１２０℃で加熱乾燥し、ダイヤモンドの粉末を得た。このダイヤモンド粉末の収率は使用した爆薬量に対して４．１質量％であり、密度は３．３６ｇ／ｃｍ３、メジアン径は３５ｎｍ（動的光散乱法）であった。密度から計算して、８９体積％のダイヤモンドと１１体積％のグラファイト系炭素からなっていると推定された。(5) Purification of diamond This unpurified diamond is mixed with a 60% by mass nitric acid aqueous solution and subjected to oxidative decomposition under conditions of 160 ° C, 14 atm and 20 minutes, and then at 130 ° C, 13 atm and 1 hour. Oxidative etching treatment was performed. Particles from which graphite was partially removed were obtained by the oxidative etching treatment. The particles were refluxed with ammonia at 210 ° C., 20 atm for 20 minutes, neutralized, then naturally settled, washed with 35 mass% nitric acid by decantation, and further washed with water three times by decantation. It was dehydrated by centrifugation and dried by heating at 120 ° C. to obtain a diamond powder. The yield of this diamond powder was 4.1% by mass with respect to the amount of explosive used, the density was 3.36 g / cm 3 , and the median diameter was 35 nm (dynamic light scattering method). Calculated from the density, it was estimated to be composed of 89% by volume of diamond and 11% by volume of graphite-based carbon.
実施例１〜５、比較例１〜２の項で得られたナノダイヤモンド粉末を、金型に入れ、ナノダイヤモンド粉末が飛ばないように空気を抜き、同様にナノダイヤモンドが飛ばないように、徐々に不活性ガスアルゴン注入をする。これを５回繰り返し、アルゴン雰囲気のナノダイヤモンドを１０００Ｋで２分間、予め加熱して、表１に記載の温度、圧力で圧縮機にかけて１０ｍｍ径の厚み３ｍｍのナノダイヤモンド構造体を作製した。この試料の熱伝導率を測定した結果を表１に示す。 The nanodiamond powders obtained in the sections of Examples 1 to 5 and Comparative Examples 1 and 2 are put into a mold, air is evacuated so that the nanodiamond powder does not fly, and gradually, so that the nanodiamond does not fly. Inject an inert gas with argon. This was repeated 5 times, and nanodiamond in an argon atmosphere was preliminarily heated at 1000 K for 2 minutes, and a nanodiamond structure having a diameter of 3 mm and a diameter of 3 mm was produced by applying a compressor at the temperature and pressure shown in Table 1. The results of measuring the thermal conductivity of this sample are shown in Table 1.
実施例２
実施例１と同様にして、（１）爆薬の準備、（２）爆薬の設置、及び（３）爆発の操作を行った後、さらに、（１）爆薬の準備、（２）爆薬の設置、及び（３）爆発の操作を４回繰り返し、続けて合計で５回の爆発を行った。ただし、２回目以降の爆発においては、爆薬を設置した後に容器内のガスを窒素で置換する操作は省略した。５回目の爆発後、実施例１と同様にして、（４）爆発生成物の回収作業、及び（５）ダイヤモンドの精製を行った。この未精製のダイヤモンドを６０質量％硝酸水溶液と混合し、１３０℃、１０気圧、１０分の条件で酸化性分解処理を行った後、１１０℃、１０気圧、３０分で酸化性エッチング処理を行った。酸化性エッチング処理により、グラファイトが一部除去された粒子が得られた。この粒子を、アンモニアを用いて、１８０℃、１５気圧、２０分還流し中和処理した後、自然沈降させデカンテーションにより３５質量％硝酸での洗浄を行い、さらにデカンテーションにより３回水洗し、遠心分離により脱水し、１２０℃で加熱乾燥し、ダイヤモンドの粉末を得た。このダイヤモンド粉末の収率は使用した爆薬量に対して４．３質量％であり、密度は３．１３ｇ／ｃｍ３、メジアン径は３０ｎｍ（動的光散乱法）であった。密度から計算して、７０体積％のダイヤモンドと３０体積％のグラファイト系炭素からなっていると推定された。Example 2
In the same manner as in Example 1, (1) Preparation of explosives, (2) Installation of explosives, and (3) Explosive operation, (1) Preparation of explosives, (2) Installation of explosives, And (3) The explosion operation was repeated four times, followed by a total of five explosions. However, in the second and subsequent explosions, the operation of replacing the gas in the container with nitrogen after installing the explosive was omitted. After the fifth explosion, (4) explosive product recovery work and (5) diamond purification were performed in the same manner as in Example 1. This unpurified diamond is mixed with a 60% by mass nitric acid aqueous solution, subjected to oxidative decomposition treatment at 130 ° C., 10 atm and 10 minutes, and then subjected to oxidative etching treatment at 110 ° C., 10 atm and 30 minutes. It was. Particles from which graphite was partially removed were obtained by the oxidative etching treatment. The particles were refluxed with ammonia at 180 ° C., 15 atm for 20 minutes, neutralized, then naturally settled, washed with 35 mass% nitric acid by decantation, and further washed with water three times by decantation. It was dehydrated by centrifugation and dried by heating at 120 ° C. to obtain a diamond powder. The yield of this diamond powder was 4.3% by mass with respect to the amount of explosive used, the density was 3.13 g / cm 3 , and the median diameter was 30 nm (dynamic light scattering method). Calculated from the density, it was estimated to be composed of 70% by volume of diamond and 30% by volume of graphite-based carbon.
実施例６〜１０、比較例３〜４の項で得られたナノダイヤモンド粉末を、金型に入れ、ナノダイヤモンド粉末が飛ばないように空気を抜き、同様にナノダイヤモンドが飛ばないように、徐々に不活性ガスアルゴン注入をする。これを５回繰り返し、アルゴン雰囲気のナノダイヤモンドを１０００Ｋで２分間、予め加熱して、表２に記載の温度、圧力で圧縮機にかけて１０ｍｍ径の厚み６００μのナノダイヤモンド構造体を作製した。この試料の熱伝導率を測定した結果を表２に示す。 The nanodiamond powder obtained in Examples 6 to 10 and Comparative Examples 3 to 4 is put into a mold, and air is evacuated so that the nanodiamond powder does not fly, and gradually, so that the nanodiamond does not fly. Inject an inert gas with argon. This was repeated 5 times, and nanodiamond in an argon atmosphere was preliminarily heated at 1000 K for 2 minutes, and a nanodiamond structure having a diameter of 600 mm and a diameter of 600 mm was applied to the compressor at the temperature and pressure shown in Table 2. The results of measuring the thermal conductivity of this sample are shown in Table 2.
表１、表２の結果から明らかなように、熱伝導率が５００Ｗ／ｍ・Ｋを満足するダイヤモンド構造体を作製するには、高温、高圧圧縮機にセットした金型中に、ダイヤモンド粉末をセットし、空気を除き、不活性ガスを充填を数回繰り返し、予め余熱を加えてしかる後、処理温度は、７００〜４０００Ｋ、処理圧力が１〜１５ＧＰａの組み合わせが好ましく、処理温度が１３００〜３３００Ｋ、処理圧力が４〜１２ＧＰａである事が最も好ましい事が理解される。 As is apparent from the results of Tables 1 and 2, in order to produce a diamond structure having a thermal conductivity of 500 W / m · K, diamond powder is placed in a mold set in a high-temperature, high-pressure compressor. After setting and removing air and filling with inert gas several times and adding preheat in advance, the processing temperature is preferably 700-4000K, the processing pressure is 1-15GPa, the processing temperature is 1300-3300K It is understood that the treatment pressure is most preferably 4 to 12 GPa.
１・・・耐圧性容器
２・・・容器
３・・・爆薬
４・・・吊材
５・・・リーク弁
６・・・耐圧性の密閉容器
７・・・上蓋
２０ａ・・・容器
２０ｂ・・・蓋
２１・・・ノズル
２２ａ，２２ｂ・・・氷の容器DESCRIPTION OF SYMBOLS 1 ... Pressure-resistant container 2 ...
Claims (5)
前記高温が７００〜４０００Ｋ、前記高圧が１〜１５ＧＰａであり、
前記ダイヤモンド粉末は、曝轟法によって得られたナノダイヤモンドを硝酸の共存下で高温高圧処理することによりグラファイト層の一部を除去したナノダイヤモンドである、熱伝導性に優れたダイヤモンド構造体の製造方法。 Only diamond powder is put in a mold, and the diamond powder is sintered at a high temperature and high pressure in an inert gas atmosphere, and includes a step of molding.
The high temperature is 700 to 4000 K, the high pressure is 1 to 15 GPa,
The diamond powder is a nanodiamond obtained by removing a part of the graphite layer by subjecting the nanodiamond obtained by the exposure method to high-temperature and high-pressure treatment in the presence of nitric acid, and producing a diamond structure having excellent thermal conductivity. Method.
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