JP5500508B2 - 微粒多結晶ダイヤモンド焼結体の製造法 - Google Patents
微粒多結晶ダイヤモンド焼結体の製造法 Download PDFInfo
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- 229910003460 diamond Inorganic materials 0.000 title claims description 95
- 239000010432 diamond Substances 0.000 title claims description 95
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000000843 powder Substances 0.000 claims description 46
- 238000005245 sintering Methods 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
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- 239000003054 catalyst Substances 0.000 claims description 2
- 239000002775 capsule Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000007542 hardness measurement Methods 0.000 description 7
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 7
- 239000001095 magnesium carbonate Substances 0.000 description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 7
- 230000002939 deleterious effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
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- 239000011812 mixed powder Substances 0.000 description 2
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- 229920000915 polyvinyl chloride Polymers 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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Description
しかし、この製造方法においては、上記超臨界流体相を形成する有機物として、例えば、シュウ酸二水和物が用いられているが、シュウ酸二水和物は劇物であり、また、これを炭酸塩と事前に混合して焼結助剤を調製する必要があることから、その取り扱いは難しく実用化を図る上での障害となっている。
また、他の製造方法として、例えば、特許文献2に示されるように、天然ダイヤモンド粉末を脱珪酸塩処理する最終工程において該ダイヤモンド粉末を分散したpH3〜5の水溶液を容器に入れ振盪処理し、該容器中において該ダイヤモンド粉末を分散した水溶液を液体窒素を用いて凍結し、そのまま凍結乾燥して得られる該ダイヤモンド粉末を、有機物(シュウ酸二水和物)を混合した炭酸塩焼結助剤を用いて超高圧合成装置により1700℃以上の温度で焼結することも提案されている。
しかし、この製造方法では、焼結体原料であるダイヤモンド粉末の二次粒子形成が抑制され、比較的均質なダイヤモンド焼結体が得られるものの、凍結乾燥工程が必要とされ事前処理が煩雑であるばかりか、また、事前混合する焼結助剤として有機物(シュウ酸二水和物)を使用することによる問題も依然として残されていた。
「(1) 平均粒径4μm以下のダイヤモンド粉末の層間に、炭酸塩と、ダイヤモンド粉末に対して1/5000〜1/1000の重量比となる室温で固体のC−H系有機物からなる触媒を介在積層し、これを焼結圧力7.7GPa以上かつ焼結温度2000℃以上で焼結することを特徴とする微粒多結晶ダイヤモンド焼結体の製造法。
(2) 上記室温で固体のC−H系有機物は、ポリエチレン、ポリプロピレンおよびポリスチレンの内から選ばれた一種または二種以上である前記(1)に記載の微粒多結晶ダイヤモンド焼結体の製造法。」
に特徴を有するものである。
図1においては、Ta製カプセルの底部から上方へ順に、グラファイト円盤(厚さ:1mm)、ポリエチレン(0.2mg)、平均粒径4μm以下のダイヤモンド粉末(0.45g)、炭酸マグネシウム(0.2g)、ポリエチレン(0.2mg)、平均粒径4μm以下のダイヤモンド粉末(0.45g)、グラファイト円盤(厚さ:1mm)となるように積層した概略図を示しているが、本発明では、Taカプセル内に焼結用原料をこのように積層した状態で、ダイヤモンド安定領域である焼結圧力7.7GPa以上かつ焼結温度2000℃以上で焼結することによって微粒多結晶ダイヤモンド焼結体を製造する。
焼結体原料としてのダイヤモンド粉末としては、気相合成法に限らず、現在既によく知られている方法で製造されたダイヤモンド粉末を使用することができる。
本発明では、ダイヤモンド粉末のサイズについて、平均粒径4μm以下と定めているが、ダイヤモンド粉末の平均粒径が4μmを超える粗粒である場合には、焼結助剤としてシュウ酸二水和物を使用せず炭酸塩のみで焼結することが可能であることから、本発明では、焼結体原料としてのダイヤモンド粉末の平均粒径を4μm以下と定めた。
炭酸塩としては、従来から用いられている炭酸マグネシウム、炭酸カルシウム等を用いることができる。
従来は、例えば、炭酸塩と超臨界流体相を形成するシュウ酸二水和物を予め混合した焼結助剤をダイヤモンド層間に挿入介在することが必要とされていたが、本発明では、図1に示す積層状態となるように原料粉末をTaカプセル内に積層することから、炭酸塩(例えば、炭酸マグネシウム)と室温で固体のC−H系有機物(例えば、ポリエチレン)とを予め混合する必要はなく、それぞれの層を独立してダイヤモンド層間に介在積層すればよい。
本発明で用いる室温で固体のC−H系有機物としては、ポリエチレン、ポリプロピレン、ポリスチレンが好ましく、C−H系以外の有機物、例えば、ポリ塩化ビニルでは、Clによってダイヤ粒子同士の直接結合を妨げ、また、ポリテトラフルオロエチレンの場合も、Fによってダイヤ粒子同士の直接結合が妨げられることから、C−H系以外の有機物の使用は避けるべきである。
また、本発明で用いる室温で固体のC−H系有機物の使用量は、重量比で表わした場合、
(室温で固体のC−H系有機物の使用量)/(ダイヤモンド粉末の重量)
=1/5000〜1/1000
であることが必要であり、室温で固体のC−H系有機物が少なく、重量比がこの値より小さい(比の値が1/5000未満)場合には、ダイヤモンド層中において、ダイヤモンド粒子表面のクリーニング効果が小さく、また、ダイヤモンド層中への溶浸が不十分となり、二次粒子の分解効果も少なく、ダイヤモンド粒子相互の直接結合が不十分となる。一方、室温で固体のC−H系有機物の使用量が増加し、上記比の値が1/1000を超えるようになると、ダイヤモンド焼結体の強度、硬さが低下するばかりか耐熱性も低下するようになるから、ダイヤモンド粉末の重量に対する室温で固体のC−H系有機物の使用量(重量)の比の値は、1/5000〜1/1000とすることが必要である。
本発明では、図1に示す積層状態となるように原料粉末をTaカプセル内に積層した後、ダイヤモンドの安定領域である焼結圧力は、7.7GPa以上、焼結温度2000℃以上の条件で10〜30分間で処理すれば微粒多結晶ダイヤモンド焼結体を再現性良く合成することができる。
なお、圧力が7.7GPa未満では、ダイヤモンドの安定領域でないため焼結することができず、一方、圧力が8GPaを超えると、生産性が乏しく、装置も大型化することから、焼結圧力は7.7〜8GPaの範囲であることが望ましい。
また、焼結温度が2000℃未満では、ダイヤモンド層中に炭酸塩が十分に溶浸しないため焼結が困難であり、一方、焼結温度が2500℃を超えるとダイヤモンドがグラファイトに変換してしまうため、焼結温度は2000〜2500℃の範囲とすることが望ましい。
なお、天然ダイヤモンド粉末は珪酸塩を相当量含有しているため、予め、Zrルツボを用いて溶融NaOH中で天然ダイヤモンド粉末の脱シリケート処理したのち、さらに、ダイヤモンド粉末を熱王水中で処理することにより、ルツボから混入するZrを除去した。
次いで、それぞれが表1の本発明1〜6に示される割合となるようにダイヤモンド粉末、炭酸塩および室温で固体のC−H系有機物を準備し、図1に示される積層構造となるようにTaカプセル内に充填し、これを、通常のベルト型超高圧高温装置に装入し、同じく表2に示される圧力、温度で焼結を行うことにより本発明の微粒多結晶ダイヤモンド焼結体(以下、本発明1〜6という)を製造した。
なお、硬度測定は、ビッカース硬さ試験機を用いて測定し、また、耐熱性試験は、真空炉にて、温度1200℃で30分間保持する熱処理を施すことにより行った。
表2に、測定結果、試験結果を示す。
表2に、その測定結果、試験結果を示す。
表4に、その測定結果、試験結果を示す。
これに対して、比較例1、2では、室温で固体のC−H系有機物の使用量が、本発明で規定する範囲外であることから焼結体内部にクラックが発生し、さらに、硬さ測定時に、圧痕周辺が剥離し正確な硬さ測定を行うことができなかった。また、比較例3、4は、焼結条件が、本発明で規定する範囲外であることから、焼結体内部にクラックが発生するばかりかグラファイト化も生じ、比較例1、2と同様な理由で正確な硬さ測定を行うことができなかった。
また、参考例1、2では、C−H以外(Cl等)の元素がダイヤモンド粒子間に残留していて、ダイヤモンド粒子間の直接結合が妨げられ、硬度の高い焼結体が得られず、また熱処理するとすぐにクラックが発生し、比較例1〜4と同様に、硬さ測定時に、圧痕周辺が剥離し正確な硬さ測定を行うことができなかった。
Claims (2)
- 平均粒径4μm以下のダイヤモンド粉末の層間に、炭酸塩と、ダイヤモンド粉末に対して1/5000〜1/1000の重量比となる室温で固体のC−H系有機物からなる触媒を介在積層し、これを焼結圧力7.7GPa以上かつ焼結温度2000℃以上で焼結することを特徴とする微粒多結晶ダイヤモンド焼結体の製造法。
- 上記室温で固体のC−H系有機物は、ポリエチレン、ポリプロピレンおよびポリスチレンの内から選ばれた一種または二種以上である請求項1に記載の微粒多結晶ダイヤモンド焼結体の製造法。
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US10350734B1 (en) | 2015-04-21 | 2019-07-16 | Us Synthetic Corporation | Methods of forming a liquid metal embrittlement resistant superabrasive compact, and superabrasive compacts and apparatuses using the same |
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