JP2004091843A - Manufacturing method of high purity high melting point metal powder - Google Patents
Manufacturing method of high purity high melting point metal powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 174
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 86
- 239000002184 metal Substances 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000002844 melting Methods 0.000 title abstract description 48
- 230000008018 melting Effects 0.000 title abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000003870 refractory metal Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000007670 refining Methods 0.000 abstract description 22
- 238000011084 recovery Methods 0.000 abstract description 18
- 239000012535 impurity Substances 0.000 abstract description 17
- 238000000746 purification Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 description 44
- 238000009826 distribution Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、粉末冶金の焼結用原料あるいは化学工業用触媒などに用いる、高純度高融点金属粉末の製造方法に関するものである。
【０００２】
【従来の技術】
近年、産業の急速な進展に伴って多くの技術分野で高純度高融点金属材料が求められている。例えば、スパッタリング用ターゲットの分野では、ターゲット材料は高融点金属を主成分とする高純度金属粉末の焼結による製造が最適であることが知られている。加えて、ターゲットの焼結による製造においてはニアネットシェップ製造のために、球状の粉末が求められている。
また、石油の分離精製の反応促進用触媒として、高純度Ｒｕなどの金属の利用が検討されている。その他、導電ペーストや人工臓器の製造などの用途で、高純度かつ球状の高融点金属粉末が求められている。
【０００３】
市販されている高融点金属粉末は、鉱石から化学湿式分離精製を繰り返して中間酸化物や化合物を製造し、得られた中間酸化物や化合物を分解、水素還元して製造される。
例えば、高融点金属であるＷ粉末の製造プロセスは、鉱石から溶媒抽出などの湿式方法によりＦｅ，Ａｌ，Ｓｉなどの物質を分離して、アンモニウム塩（ＡＰＴ）の結晶とし、これを熱分解してＷＯ３を得る。その酸化物を水素還元してＷ粉末を製造する。Ｍｏの精製もＷとほぼ同様のプロセスで製造され、Ｍｏアンモニウム塩結晶を熱分解してモリブデン酸化物（ＭｏＯ３）を製造する。その酸化物の還元により金属粉末を製造する。なお、Ｔａは化学湿式分離により、Ｔａ２Ｏ５を得た後、その酸化物の還元によりＴａ粉末を製造する。また、Ｒｕは分離精製したＲｕＯ２の還元によりＲｕ粉末を製造する。
【０００４】
上記の方法により得られる高融点金属粉末では純度が十分でないため、高純度高融点金属粉末を得る為には、市販されている高融点金属粉末を用いて、さらに高純度化のための精錬を行うことが必要である。従来行われている精錬方法として、市販の高融点金属粉末をＥＢ溶解などの真空冶金法により高純度化精錬し、そのインゴットを粉砕して高純度高融点金属粉末を製造する方法が知られている。しかしながらこの方法では、高融点金属粉末の高純度化は可能であるものの、インゴットの粉砕により粉末を製造する為、球状の粉末を得ることが出来ない。また、インゴットの粉砕時に不純物が混入しやすいという問題も包含している。
球状の高融点金属粉末を製造する方法としては、プラズマ回転電極法（ＰＲＥＰ法）による方法が、提案されているが（例えば、特許文献１参照。）、ＰＲＥＰ法では高純度化精錬の効果が認められない。
【０００５】
そこで、高融点金属粉末の高純度化と球状化を同時に実現する方法として、本発明者らは熱プラズマ液滴精錬法を提案した（特許文献２参照。）。この方法では、熱プラズマ炎に高融点金属粉末等を原料粉末として供給し、熱プラズマ炎を通過しながら、原料粉末の高純度化と球状化を同時に実現することが可能である。
【０００６】
【特許文献１】
特開平３−１７３７０４号公報（第２頁）
【特許文献２】
特開２００１−２００６５号公報（第４−５頁、図１）
【０００７】
【発明が解決しようとする課題】
上述の熱プラズマ液滴精錬法では、高融点金属粉末の高純度化、球状化が可能であるものの、高純度化の効率を向上する課題が残されている。具体的には、熱プラズマ液滴精錬法では、原料粉末として用いる高融点金属粉末によって、高純度化後の金属粉末における不純物の低減の程度が異なるという課題を包含している。加えて、熱プラズマ炎に供給した原料粉末の重量に対する、高純度化後に回収できる金属粉末の重量、すなわち高純度化前後での金属粉末の回収率も用いる原料粉末によって異なるという課題を包含している。
【０００８】
本発明は、熱プラズマ液滴精錬法による高融点金属粉末の高純度化、球状化において、高純度化後の不純物をより低減すると共に不純物含有量のばらつきを低減し、高純度金属粉末の回収率を向上できる、高純度高融点金属粉末の製造方法を提供するものである。
【０００９】
【課題を解決するための手段】
本発明者は上記の課題を解決するために鋭意研究を行った。その結果、熱プラズマ液滴精錬法に原料粉末として使用する高融点金属粉末の粒径分布の制御により、高純度化効果を飛躍的に向上し、高純度高融点金属粉末の回収率を改善できることを見出し、本発明に至った。
【００１０】
すなわち本発明は、平均粒径がＤａの高融点金属粉末を熱プラズマ炎に導入する高純度高融点金属粉末の製造方法であって、質量分率で全体の９０％以上を占める前記高融点金属粉末の粒径が０．８Ｄａ〜１．２Ｄａである高純度高融点金属粉末の製造方法である。Ｄａは１０〜２６０μｍであることが好ましい。
また、高融点金属粉末はＷ、Ｔａ、ＲｕまたはＭｏの何れかであることが好ましい。
また、高純度高融点金属粉末の酸素含有量が１００ｐｐｍ以下、ガス成分を除いた純度が９９．９９９質量％以上であることが好ましい。
また、熱プラズマ炎に水素ガスを導入することが好ましい。
【００１１】
【発明の実施の形態】
本発明の最大の特徴は、原料粉末として熱プラズマ炎に導入する高融点金属粉末として、予め分級等により粒径分布を一定範囲に調整した高融点金属粉末を用いることである。
熱プラズマ液滴精錬法では、熱プラズマ炎中に導入された原料粉末は溶融した後、自身の表面張力により球状化して球状の液滴を形成し、この液滴が熱プラズマ炎の外で冷却、凝固し球状の金属粉末を形成する。この間に、原料粉末に含まれる不純物が、高温の熱プラズマ炎（５０００℃以上）により蒸発することにより、金属粉末の高純度化を実現する。
【００１２】
本発明者らは、この熱プラズマ液滴精錬法においては、原料粉末中の不純物の低減と金属粉末の回収率に対して、熱プラズマ炎中での原料粉末（液滴）の到達温度を、全ての原料粉末（液滴）について、できるだけ一定とすることが重要であることを想到した。そして、これを具体的に行う方法として、原料粉末である高融点金属粉末の粒径分布を一定範囲に調整することが有効であることを見出した。以下にこの知見について詳細に述べる。
【００１３】
先ず、熱プラズマ炎中に導入した原料粉末において、加熱不足の原料粉末が存在すると、原料粉末（液滴）が完全に溶融しなかったり、あるいは不純物を蒸発できる温度にまで到達できない等の理由により、十分な精錬効果が得られない場合を生じる。
一方、加熱が過剰な原料粉末が存在すると、不純物の蒸発のみならずマトリックスである高融点金属粉末の蒸発も多くなり、金属粉末の回収率が下がる。また、蒸発した金属は微粉末として凝固する為、金属球に微粉末が混入することになる。混入した微粉末は金属球の表面に付着するが、微粉末は粒径の大きい粉末と比べて活性である為酸化等を生じやすく、その結果、高純度高融点金属粉末の純度を低下させる場合がある。
従って、原料粉末の高純度化を達成し、金属粉末の回収率を向上するには熱プラズマ炎中での原料粉末（液滴）の到達温度を全ての原料粉末（液滴）について、できるだけ一定とすることが重要である。
【００１４】
一定の熱プラズマ処理条件において、粒径分布の広い原料粉末を熱プラズマ炎中に導入する場合、熱プラズマ炎中での単位体積あたりの受熱度合いが原料粉末（液滴）によって異なることになる。すなわち、大きい粒径の原料粉末では加熱不足となり、逆に小さい粒径の原料粉末では加熱過剰となる。
処理粒子の粒径分布を狭い範囲に制御し、それに整合した熱プラズマ処理条件を採用することで、原料粉末の加熱不足・過剰を減少できるため、液滴精錬の高純度化効果を飛躍的に向上することができる。同時に、マトリックスである高融点金属粉末の蒸発を抑制できるので、金属粉末の回収歩留まりも向上することができる。
【００１５】
理想的には、全ての粒子の粒径が一定である原料粉末を採用する場合、高純度化効果、金属粉末の回収率は最も高く、粒径分布の範囲が広がることにより、高純度化効果は次第に低減する。
実際には、原料粉末の粒径分布において、平均粒径をＤａとした場合に、粒径が０．８Ｄａ〜１．２Ｄａ範囲である粒子が質量分率で９０％以上を占める場合には、それに合わせて熱プラズマ炎等の処理条件を設定することにより、高い精錬効果と回収歩留まりを得ることができる。この範囲を超えて原料粉末の粒径分布が広くなると、精錬効果、回収歩留まりともに急激に低下する。
【００１６】
従って、本発明では原料粉末である高融点金属粉末の粒径分布を、質量分率で全体の９０％以上を占める高融点金属粉末の粒径が０．８Ｄａ〜１．２Ｄａとする。
望ましくは、質量分率で全体の９８％以上を占める高融点金属粉末の粒径が０．８Ｄａ〜１．２Ｄａである。
本発明の製造方法に用いる高融点金属粉末は、市販されている高融点金属粉末をふるい等により分級して得ることが出来る。
【００１７】
本発明では原料粉末には、平均粒径Ｄａが１０〜２６０μｍである高融点金属粉末を用いることが好ましい。
原料粉末である高融点金属粉末が細かくなると、熱プラズマ炎に導入する前の高融点金属粉末が凝集しやすくなる。一旦、高融点金属粉末が凝集すると、熱プラズマ炎中では分散し難く、実質的に粒径が平均粒径から大きくはずれた金属粉末を用いるのと同じになってしまう。また、平均粒径が小さいほど、熱プラズマ炎の発生条件等の処理条件についての最適化が困難となるので、高融点金属粉末の平均粒径が小さすぎると、精錬効果、回収歩留まりとも低下し易い。
Ｄａが１０μｍ以上であれば、上記の問題を生じ難く好ましい。より望ましくは１５μｍ以上である。
【００１８】
一方、平均粒径Ｄａの増大に伴って、熱プラズマ炎中に飛行期間での完全加熱が困難になり、精錬効果が低減する。本発明者らの検討によれば、Ｄａは２６０μｍ以下の場合、熱プラズマ炎中で十分な高純度化の効果を達成することができる。よって、Ｄａは２６０μｍ以下とすることが好ましい。望ましくは２００μｍ以下である。
【００１９】
本発明では、高融点金属粉末はＷ、Ｔａ、ＲｕまたはＭｏの何れかであることが好ましい。
既に述べたように、熱プラズマ液滴精錬では熱プラズマ炎中での低融点不純物の蒸発を通じて高純度化精錬を実現する。従って、マトリックスである高融点金属粉末の融点が高いほど、精錬温度でのマトリックス元素と不純物元素の蒸気圧差を大きくすることが可能であり、高純度化効果が大きくなる。本発者らの検討では、融点がＦｅの融点（１５３８℃）以上の高融点金属元素に対して有効であるが、特にＷ、Ｔａ、Ｍｏ、Ｒｕに有効である。
【００２０】
このような方法で、製造した高融点金属粉末は、酸素含有量が１００ｐｐｍ以下、高純度高融点金属粉末の純度がガス分を除いた純度で９９．９９９質量％以上を実現できる。このように、高純度化を達成し、さらに球状化された高純度高融点金属粉末は、ターゲット材に用いる粉末材料として好ましい。
【００２１】
本発明では、熱プラズマ炎に水素ガスを導入することが好ましい。既に述べたように熱プラズマ炎を用いた場合、不純物元素の蒸発により高融点金属粉末の高純度化を達成することが出来るが、さらに水素ガスを導入することで、酸素等の不純物をより低減できることができる。加えて、水素ガスにより熱プラズマ炎の状態を制御することができる。さらにプラズマの熱伝導率も制御できるため、平均粒径Ｄａに合わせて、液滴精錬の最適状態に制御することが可能となる。
【００２２】
本発明に適用することができる、熱プラズマ炎には代表的なものとしてＤＣプラズマ、ＲＦプラズマがあるが、本発明にはＲＦプラズマを用いることが好ましい。ＲＦプラズマは、ＤＣプラズマと異なり、電極が不要で、電極材料等に起因する不純物の混入の少ない為である。
【００２３】
本願発明の製造方法は例えば図５に示す装置により実施することが出来る。
図５において、水冷管１０により冷却されているＲＦプラズマトーチ８は、プラズマ動作ガス供給装置１１によりプラズマ動作ガス供給位置６から供給されるプラズマ動作ガスと、コイル７から発生する高周波エネルギにより熱プラズマ炎３を発生する。
原料供給装置１（例えば電磁振動原料供給装置）に投入された高融点金属粉末は、キャリアガスと共に原料供給位置２より熱プラズマ炎３内部の高温部（５０００〜１００００℃）に投入される。熱プラズマ炎中に投入された原料粉末は瞬時に溶融し、表面張力により球状となる。
【００２４】
熱プラズマ炎の上流側に位置する原料供給位置２から供給された原料粉末は、十分に加熱、溶融された状態で水素ガスを含有する精錬効果の高いプラズマ部分を通過し、不純物元素が低減される。
熱プラズマ炎内で処理された金属粉末はチャンバ４中を落下しながら不活性ガス雰囲気中で凝固し、高純度高融点金属粉末９として下部の金属粉末回収部５に集められ、回収される。
以上のようにして、球状の高純度高融点金属粉末を効率的に製造することができる。
【００２５】
【実施例】
（実施例１）
網目サイズの異なるふるいを用いて分級を行った二種類の粒径分布のＴａ金属粉末（平均粒径Ｄａが７５μｍ）をＴａ原料粉末として、図５に示す装置を用い、高純度高融点金属粉末であるＴａ粉末を製造した。また、比較の為、分級を行っていない市販されているままのＴａ原料粉末を用いて同様に高純度高融点金属粉末の製造を行った。
Ｔａ原料粉末の粒径分布を表１に、粒径分布以外の製造条件を表２に示す。なお、本発明例において、粒径分布の測定は日機装（株）製のレーザ光粒度分布測定装置であるマイクロトラックＭＴ３０００を用いて行った。
【００２６】
【表１】
【表２】
製造終了後に装置の金属粉末回収部に回収することが出来たＴａ粉末の重量を、熱プラズマ炎中に導入したＴａ原料粉末の重量と比較し、Ｔａ粉末の回収歩留まりを算出した。また、回収したＴａ粉末について、グロー放電質量分析法（ＧＤ−ＭＳ）によりＴａ、及び代表的な不純物の含有量を測定した。加えて、走査電子顕微鏡（ＳＥＭ）により回収したＴａ粉末の形状の比較を行った。
Ｔａ粉末の回収歩留まり、及びＧＤ−ＭＳによる測定の結果を表３に、Ｔａ粉末の形状を図１〜３に示す。
【００２９】
【表３】
表３に示すように平均粒径が７５μｍのＴａ粉末において、質量分率で全体の９０％以上を占めるＴａ粉末の粒径が６０〜９０μｍを達成している本発明例１、２では、Ｔａ原料粉末の純度が３Ｎであるのに対し、回収されたＴａ粉末の純度において何れも５Ｎを達成している。本発明例１、２のＴａ粉末の純度は、分級を行っていない比較例と比べても一桁高い値となっている。
【００３１】
また図１〜３に示すＴａ粉末の形状においても、比較例である図３では、殆ど溶融していないＴａ粉末が多く見られるのに対して、本発明例１、２である図１、２では何れのＴａ粉末もほぼ球形をしており、熱プラズマ炎中において十分溶融していることが分かる。特に分級が十分に行われている本発明例１では、球状化の程度が高い。図１、２に示す形状、及び表３に示す純度、回収歩留まりのデータと併せ、本発明の製造方法によれば、Ｔａ粉末は熱プラズマ炎中において均一、かつ十分に溶融していることが分かる。
【００３２】
（実施例２）
ふるいを用いた分級により、平均粒径Ｄａを８１μｍ、粒径６５〜９７μｍ（０．８Ｄａ〜１．２Ｄａ）粉末の質量分率を９６％に調整したＲｕ金属粉末をＲｕ原料粉末として、図５に示す装置を用い、表４に示す製造条件により高純度高融点金属粉末であるＲｕ粉末を製造した。なお、粒径分布の測定は実施例１と同様の方法で行った。
【００３３】
【表４】
製造終了後に装置の金属粉末回収部に回収することが出来たＲｕ粉末について、実施例１と同様の評価を行った。Ｒｕ粉末の回収歩留まり、及びＧＤ−ＭＳによる測定の結果を表５に、Ｒｕ粉末の形状を図４に示す。
【００３５】
【表５】
表５示すようにＲｕ粉末においても、平均粒径が８１μｍ、質量分率で全体の９０％以上を占めるＲｕ粉末の粒径が６５〜９７μｍを達成している本発明例３では、Ｒｕ原料粉末の純度が３Ｎであるのに対し、回収されたＲｕ粉末の純度において５Ｎとなっており、高純度化が十分に達成されている。
【００３７】
また図４に示す球状化後のＲｕ粉末の形状においても、未溶融のＲｕ粉末は見られず、何れのＲｕ粉末も、ほぼ球形をしており、熱プラズマ炎中において十分溶融していることが分かる。
【００３８】
【発明の効果】
本発明によれば、熱プラズマ液滴精錬法による高融点金属粉末の高純度化、球状化において、高純度化後の不純物をより低減すると共に不純物含有量のばらつきを低減し、高純度金属粉末の回収率を向上できる。したがって本発明の高純度高融点金属粉末の製造方法は、スパッタリング用ターゲット等に用いられる高純度高融点金属材料を工業的に製造するにおいて非常に有用である。
【図面の簡単な説明】
【図１】本発明例によるＴａ粉末の形状を示す模式図である。
【図２】本発明例によるＴａ粉末の形状を示す模式図である。
【図３】比較例によるＴａ粉末の形状を示す模式図である。
【図４】本発明例によるＲｕ粉末の形状を示す模式図である。
【図５】本発明の製造方法を実施する製造装置の一例を示す模式図である。
【符号の説明】
１．原料供給装置、２．原料供給位置、３．熱プラズマ炎、４．チャンバ、５．金属粉末回収部、６．プラズマ動作ガス供給位置、７．コイル、８．ＲＦプラズマトーチ、９．高純度高融点金属粉末、１０．水冷管、１１．プラズマ動作ガス供給装置[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a high-purity high-melting-point metal powder used as a raw material for sintering in powder metallurgy or a catalyst for the chemical industry.
[0002]
[Prior art]
In recent years, with the rapid progress of industry, high-purity high-melting point metal materials are required in many technical fields. For example, in the field of sputtering targets, it is known that the target material is optimally produced by sintering a high-purity metal powder containing a high-melting-point metal as a main component. In addition, in the production of a target by sintering, a spherical powder is required for the production of a near net shep.
Also, the use of metals such as high-purity Ru as a catalyst for accelerating the reaction of separating and refining petroleum has been studied. In addition, high-purity and spherical high-melting-point metal powders are required for applications such as production of conductive pastes and artificial organs.
[0003]
Commercially available high melting point metal powder is produced by repeating chemical wet separation and purification from ore to produce intermediate oxides and compounds, and decomposing and hydrogen reducing the obtained intermediate oxides and compounds.
For example, in the manufacturing process of W powder, which is a high melting point metal, a substance such as Fe, Al, or Si is separated from an ore by a wet method such as solvent extraction to form a crystal of ammonium salt (APT), which is thermally decomposed. obtain WO 3 Te. The oxide is hydrogen reduced to produce W powder. Mo is also purified by a process similar to that of W, and Mo ammonium salt crystals are thermally decomposed to produce molybdenum oxide (MoO 3 ). A metal powder is produced by reduction of the oxide. Note that Ta is obtained by obtaining Ta 2 O 5 by chemical wet separation and then reducing the oxide to produce Ta powder. Ru produces Ru powder by reduction of RuO 2 separated and purified.
[0004]
Since the high melting point metal powder obtained by the above method is not sufficiently pure, in order to obtain a high purity high melting point metal powder, use a commercially available high melting point metal powder and further refine it for further purification. It is necessary to do. As a conventional refining method, a method is known in which a commercially available refractory metal powder is refined and refined by vacuum metallurgy such as EB melting, and the ingot is pulverized to produce a high-purity refractory metal powder. I have. However, in this method, although the high melting point metal powder can be highly purified, a spherical powder cannot be obtained because the powder is produced by crushing the ingot. It also includes a problem that impurities are likely to be mixed in the pulverization of the ingot.
As a method for producing a spherical high melting point metal powder, a method using a plasma rotating electrode method (PREP method) has been proposed (for example, see Patent Document 1). unacceptable.
[0005]
Therefore, the present inventors have proposed a thermal plasma droplet refining method as a method for simultaneously realizing high purity and spheroidization of a high melting point metal powder (see Patent Document 2). According to this method, a high melting point metal powder or the like is supplied as a raw material powder to the thermal plasma flame, and the raw material powder can be simultaneously purified and spheroidized while passing through the thermal plasma flame.
[0006]
[Patent Document 1]
JP-A-3-173704 (page 2)
[Patent Document 2]
JP 2001-20065 A (page 4-5, FIG. 1)
[0007]
[Problems to be solved by the invention]
In the above-described thermal plasma droplet refining method, although the high melting point metal powder can be purified and spheroidized, there remains a problem of improving the efficiency of the purification. Specifically, the thermal plasma droplet refining method involves a problem that the degree of impurity reduction in the highly purified metal powder differs depending on the high melting point metal powder used as the raw material powder. In addition, with respect to the weight of the raw material powder supplied to the thermal plasma flame, the weight of the metal powder that can be recovered after the high purification, that is, the problem that the recovery rate of the metal powder before and after the high purification also varies depending on the raw material powder used. I have.
[0008]
In the present invention, the high-purity metal powder is refined and spheroidized by a thermal plasma droplet refining method, and the impurities after the purification are further reduced, and the dispersion of the impurity content is reduced. An object of the present invention is to provide a method for producing a high-purity high-melting point metal powder capable of improving the rate.
[0009]
[Means for Solving the Problems]
The present inventor has conducted intensive studies in order to solve the above problems. As a result, by controlling the particle size distribution of the high melting point metal powder used as the raw material powder in the thermal plasma droplet refining method, the effect of high purification can be dramatically improved, and the recovery rate of the high purity high melting point metal powder can be improved. And found the present invention.
[0010]
That is, the present invention relates to an average particle diameter of a method for producing high purity refractory metal powder introducing a refractory metal powder D a thermal plasma flame, the refractory which occupy the entire 90% by mass fraction the particle size of the metal powder is process for producing a high-purity refractory metal powder that is a 0.8D a ~1.2D a. D a is preferably 10～260Myuemu.
Further, the high melting point metal powder is preferably any of W, Ta, Ru and Mo.
Further, it is preferable that the oxygen content of the high-purity high-melting-point metal powder is 100 ppm or less, and the purity excluding gas components is 99.999% by mass or more.
Further, it is preferable to introduce hydrogen gas into the thermal plasma flame.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The greatest feature of the present invention is that a high melting point metal powder whose particle size distribution has been adjusted to a certain range in advance by classification or the like is used as a high melting point metal powder to be introduced into a thermal plasma flame as a raw material powder.
In the thermal plasma droplet refining method, the raw material powder introduced into the thermal plasma flame is melted and then sphericalized by its own surface tension to form spherical droplets, which are cooled outside the thermal plasma flame Solidifies to form a spherical metal powder. During this time, the impurities contained in the raw material powder are evaporated by the high-temperature thermal plasma flame (5000 ° C. or higher), so that the metal powder is highly purified.
[0012]
In the thermal plasma droplet refining method, the present inventors set the ultimate temperature of the raw material powder (droplets) in the thermal plasma flame to the reduction of impurities in the raw material powder and the recovery rate of the metal powder. It has been conceived that it is important for all the raw material powders (droplets) to be as constant as possible. As a method for specifically performing this, it has been found that it is effective to adjust the particle size distribution of the high melting point metal powder as the raw material powder to a certain range. Hereinafter, this finding will be described in detail.
[0013]
First, if the raw material powder introduced into the thermal plasma flame contains insufficiently heated raw material powder, the raw material powder (droplets) may not be completely melted or may not reach a temperature at which impurities can be evaporated. In some cases, a sufficient refining effect cannot be obtained.
On the other hand, if there is a raw material powder that is overheated, not only evaporation of impurities but also evaporation of the high melting point metal powder as a matrix increases, and the recovery rate of the metal powder decreases. Further, since the evaporated metal solidifies as fine powder, the fine powder is mixed into the metal sphere. The mixed fine powder adheres to the surface of the metal sphere, but the fine powder is more active than the powder having a large particle diameter, so it tends to oxidize.As a result, the purity of the high-purity high-melting metal powder is reduced. There is.
Therefore, in order to achieve high purity of the raw material powder and improve the recovery rate of the metal powder, the ultimate temperature of the raw material powder (droplets) in the thermal plasma flame is kept as constant as possible for all the raw material powders (droplets). It is important that
[0014]
When a raw material powder having a wide particle size distribution is introduced into a thermal plasma flame under certain thermal plasma processing conditions, the degree of heat reception per unit volume in the thermal plasma flame varies depending on the raw material powder (droplets). That is, the raw material powder having a large particle diameter is insufficiently heated, while the raw material powder having a small particle diameter is excessively heated.
By controlling the particle size distribution of the treated particles to a narrow range and adopting thermal plasma processing conditions matched to that, it is possible to reduce insufficient heating and excessive heating of the raw material powder, dramatically improving the high purification effect of droplet refining. Can be improved. At the same time, since the evaporation of the high melting point metal powder as the matrix can be suppressed, the recovery yield of the metal powder can be improved.
[0015]
Ideally, when using a raw material powder in which all particles have a uniform particle size, the purifying effect is the highest, the recovery rate of metal powder is the highest, and the range of particle size distribution is widened, resulting in a high purifying effect. Gradually decreases.
In practice, the particle size distribution of the raw material powder, when the average particle diameter is D a, if the particle diameter is 0.8D a ~1.2D a range grains account for more than 90% by mass fraction By setting processing conditions such as thermal plasma flame in accordance with the above, a high refining effect and a recovery yield can be obtained. If the particle size distribution of the raw material powder is widened beyond this range, both the refining effect and the recovery yield sharply decrease.
[0016]
Accordingly, the present invention the particle size distribution of the refractory metal powder as the starting material powder, the particle diameter of the high melting point metal powder occupying the entire 90% by mass fraction and 0.8D a ~1.2D a.
Desirably, the particle diameter of the high melting point metal powder, which accounts for 98% of the total mass fraction of 0.8D a ~1.2D a.
The high melting point metal powder used in the production method of the present invention can be obtained by classifying a commercially available high melting point metal powder using a sieve or the like.
[0017]
The raw material powder in the present invention, it is preferable that an average particle diameter D a is used a high melting point metal powder is 10～260Myuemu.
When the high melting point metal powder as the raw material powder is fine, the high melting point metal powder before being introduced into the thermal plasma flame is easily aggregated. Once the high-melting-point metal powder is agglomerated, it is difficult to disperse in a hot plasma flame, which is substantially the same as using metal powder whose particle size deviates greatly from the average particle size. Further, the smaller the average particle size, the more difficult it is to optimize processing conditions such as the generation condition of the thermal plasma flame, so if the average particle size of the high melting point metal powder is too small, the refining effect and the recovery yield also decrease. easy.
When the value of Da is 10 μm or more, the above-described problem hardly occurs, which is preferable. More preferably, it is 15 μm or more.
[0018]
On the other hand, with increasing average particle diameter D a, full heating of flight time in the thermal plasma flame becomes difficult and refining effect is reduced. According to the studies of the present inventors, D a in the following cases 260 .mu.m, it is possible to achieve a sufficient effect of high purification in the thermal plasma flame. Therefore, D a is preferably less 260 .mu.m. Desirably, it is 200 μm or less.
[0019]
In the present invention, the high melting point metal powder is preferably any of W, Ta, Ru and Mo.
As described above, in the thermal plasma droplet refining, high-purity refining is realized by evaporating low-melting-point impurities in a thermal plasma flame. Therefore, as the melting point of the high melting point metal powder as the matrix is higher, the vapor pressure difference between the matrix element and the impurity element at the refining temperature can be increased, and the high purification effect is increased. According to the study by the present inventors, it is effective for refractory metal elements whose melting point is equal to or higher than the melting point of Fe (1538 ° C.), but is particularly effective for W, Ta, Mo, and Ru.
[0020]
The high melting point metal powder produced by such a method can realize an oxygen content of 100 ppm or less, and a high purity high melting point metal powder having a purity of 99.999 mass% or more excluding gas. As described above, the high-purity, high-purity, high-melting-point metal powder that has been made more highly purified and spherical is preferable as the powder material used for the target material.
[0021]
In the present invention, it is preferable to introduce hydrogen gas into the thermal plasma flame. As described above, when a thermal plasma flame is used, high-purification of the refractory metal powder can be achieved by evaporation of impurity elements, but impurities such as oxygen are further reduced by further introducing hydrogen gas. You can do it. In addition, the state of the thermal plasma flame can be controlled by the hydrogen gas. Since more control the thermal conductivity of the plasma, in accordance with the average particle diameter D a, it is possible to control the optimal condition of the droplet refining.
[0022]
DC plasma and RF plasma are typical thermal plasma flames applicable to the present invention, but it is preferable to use RF plasma in the present invention. RF plasma is different from DC plasma in that an electrode is not required and impurities are less mixed due to an electrode material and the like.
[0023]
The manufacturing method of the present invention can be implemented by, for example, an apparatus shown in FIG.
In FIG. 5, an RF plasma torch 8 cooled by a
The high melting point metal powder supplied to the raw material supply device 1 (for example, an electromagnetic vibration raw material supply device) is supplied to the high temperature part (5000 to 10000 ° C.) inside the thermal plasma flame 3 from the raw material supply position 2 together with the carrier gas. The raw material powder charged in the thermal plasma flame is instantaneously melted and becomes spherical due to surface tension.
[0024]
The raw material powder supplied from the raw material supply position 2 located on the upstream side of the thermal plasma flame passes through a plasma portion having a high refining effect containing hydrogen gas in a sufficiently heated and molten state, and impurity elements are reduced. You.
The metal powder treated in the thermal plasma flame is solidified in an inert gas atmosphere while falling in the chamber 4 and is collected as a high-purity high-melting-point metal powder 9 in the lower metal powder collecting section 5 and collected.
As described above, a spherical high-purity high-melting metal powder can be efficiently produced.
[0025]
【Example】
(Example 1)
As Ta raw material powders of two kinds of Ta metal powder of the particle size distribution (75 [mu] m average particle diameter D a is) subjected to classifying using different sieve of mesh size, using the apparatus shown in FIG. 5, the high-purity refractory metal A Ta powder as a powder was produced. For comparison, a high-purity high-melting-point metal powder was similarly produced using a commercially available Ta raw material powder that had not been classified.
Table 1 shows the particle size distribution of the Ta raw material powder, and Table 2 shows production conditions other than the particle size distribution. In the examples of the present invention, the particle size distribution was measured using Microtrac MT3000, a laser light particle size distribution measuring device manufactured by Nikkiso Co., Ltd.
[0026]
[Table 1]
[Table 2]
After the production was completed, the weight of the Ta powder that could be recovered in the metal powder recovery section of the apparatus was compared with the weight of the Ta raw material powder introduced into the thermal plasma flame, and the recovery yield of the Ta powder was calculated. Further, for the recovered Ta powder, the contents of Ta and typical impurities were measured by glow discharge mass spectrometry (GD-MS). In addition, the shape of the recovered Ta powder was compared by a scanning electron microscope (SEM).
Table 3 shows the recovery yield of the Ta powder and the result of measurement by GD-MS, and FIGS. 1 to 3 show the shape of the Ta powder.
[0029]
[Table 3]
As shown in Table 3, in Ta powders having an average particle diameter of 75 μm, the Ta powders occupying 90% or more of the whole by mass fraction have a particle diameter of 60 to 90 μm. The purity of the raw material powder is 3N, whereas the purity of the recovered Ta powder achieves 5N in all cases. The purity of the Ta powders of Inventive Examples 1 and 2 is an order of magnitude higher than that of the comparative example in which classification is not performed.
[0031]
Also in the shape of the Ta powder shown in FIGS. 1 to 3, in FIG. 3 which is a comparative example, there are many Ta powders which are hardly melted, whereas in FIGS. It can be seen that each of the Ta powders has a substantially spherical shape and is sufficiently melted in the thermal plasma flame. In particular, in Example 1 of the present invention in which the classification was sufficiently performed, the degree of spheroidization was high. According to the manufacturing method of the present invention, together with the shape shown in FIGS. 1 and 2 and the data of the purity and the recovery yield shown in Table 3, the Ta powder is uniformly and sufficiently melted in the thermal plasma flame. I understand.
[0032]
(Example 2)
By classification using a sieve, the average particle diameter D a 81μm, the Ru metal powder by adjusting the particle size 65~97μm (0.8D a ~1.2D a) the mass fraction of powder 96% as Ru material powder Using the apparatus shown in FIG. 5, Ru powder as a high-purity high-melting-point metal powder was manufactured under the manufacturing conditions shown in Table 4. The measurement of the particle size distribution was performed in the same manner as in Example 1.
[0033]
[Table 4]
The same evaluation as in Example 1 was performed on the Ru powder that could be recovered in the metal powder recovery section of the device after the production was completed. Table 5 shows the recovery yield of Ru powder and the result of measurement by GD-MS, and FIG. 4 shows the shape of Ru powder.
[0035]
[Table 5]
As shown in Table 5, also in the Ru powder, the average particle diameter is 81 μm, and the Ru powder occupying 90% or more of the whole by mass fraction has a particle diameter of 65 to 97 μm. Has a purity of 3N, whereas the purity of the recovered Ru powder is 5N, and high purification has been sufficiently achieved.
[0037]
Also, in the shape of the Ru powder after spheroidization shown in FIG. 4, no unmelted Ru powder was observed, and all of the Ru powders were substantially spherical and were sufficiently melted in the thermal plasma flame. I understand.
[0038]
【The invention's effect】
According to the present invention, the high-purity metal powder is refined and refined by the thermal plasma droplet refining method. Recovery rate can be improved. Therefore, the method for producing a high-purity high-melting-point metal powder of the present invention is very useful in industrially producing a high-purity high-melting-point metal material used for a sputtering target or the like.
[Brief description of the drawings]
FIG. 1 is a schematic view showing the shape of a Ta powder according to an example of the present invention.
FIG. 2 is a schematic view showing a shape of a Ta powder according to an example of the present invention.
FIG. 3 is a schematic diagram showing the shape of a Ta powder according to a comparative example.
FIG. 4 is a schematic view showing a shape of a Ru powder according to an example of the present invention.
FIG. 5 is a schematic view showing an example of a manufacturing apparatus for performing the manufacturing method of the present invention.
[Explanation of symbols]
1. Raw material supply device, 2. 2. Raw material supply position; 3. thermal plasma flame; 4. chamber; Metal powder collection unit, 6. 6. Plasma operation gas supply position; Coil, 8. 8. RF plasma torch, 10. High purity high melting point metal powder; 10. water-cooled tube; Plasma operation gas supply device
Claims (5)
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Cited By (17)
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