JP2834199B2 - Method for producing ultrafine tungsten particles - Google Patents
Method for producing ultrafine tungsten particlesInfo
- Publication number
- JP2834199B2 JP2834199B2 JP1189843A JP18984389A JP2834199B2 JP 2834199 B2 JP2834199 B2 JP 2834199B2 JP 1189843 A JP1189843 A JP 1189843A JP 18984389 A JP18984389 A JP 18984389A JP 2834199 B2 JP2834199 B2 JP 2834199B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- tungsten
- less
- plate
- ultrafine
- 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.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、タングステン超微粒子の製造方法に関し、
さらに詳しくは、機械的な粉砕操作なしにタングステン
超微粒子を製造する方法に関する。The present invention relates to a method for producing ultrafine tungsten particles,
More specifically, the present invention relates to a method for producing ultrafine tungsten particles without a mechanical pulverizing operation.
タングステン粉末は特殊鋼の成分として、また、タン
グステンカーバイトを主体とする超硬合金の原料として
用いられている。Tungsten powder is used as a component of special steel and as a raw material of cemented carbide mainly composed of tungsten carbide.
そして今日では、IC基板の穴あけ用ドリルの原料など
の用途として、微細なタングステン粉末が求められてい
る。Nowadays, fine tungsten powder is required as a raw material for a drill for drilling an IC substrate.
従来より、タングステン粉末の製造方法としては、酸
化タングステン粉末を水素気流中で700℃以上に加熱し
て還元する方法などが行われている。Conventionally, as a method for producing a tungsten powder, a method of reducing a tungsten oxide powder by heating it to 700 ° C. or more in a hydrogen stream has been used.
また、微細なタングステン粉末の製造方法として特開
昭61−124508号には、パラタングステン酸アンモニウム
の結晶を過酸化水素水に溶解せしめ、得られた溶液を乾
燥して固化物を得、ついで該固化物を還元して0.3〜0.6
μｍの超微粒子を製造する方法が開示されている。As a method for producing fine tungsten powder, JP-A-61-124508 discloses that a crystal of ammonium paratungstate is dissolved in aqueous hydrogen peroxide, and the obtained solution is dried to obtain a solidified product. 0.3-0.6 by reducing solidified material
A method for producing μm ultrafine particles is disclosed.
しかし、上記製造方法においては、得られるタングス
テン超微粒子の大きさは0.3μｍ程度が限度で、それ以
下の粒径のタングステン超微粒子の製造は困難であっ
た。However, in the above manufacturing method, the size of the obtained ultrafine tungsten particles is limited to about 0.3 μm, and it is difficult to manufacture the ultrafine tungsten particles having a particle size smaller than that.
本発明は、機械的粉砕工程を経ることなしに、従来製
造困難であった0.3μｍ以下のタングステン超微粒子の
製造方法を提供することを目的とする。An object of the present invention is to provide a method for producing ultrafine tungsten particles having a diameter of 0.3 μm or less, which has conventionally been difficult to produce, without going through a mechanical grinding step.
本発明のタングステン超微粒子の製造方法は、タング
ステン化合物の水溶液をpH3以下に調整して生成するゲ
ル状沈澱物を、母液の比電導度が５×10-5Ω-1cm-1以下
となるまで洗浄し、得られた板状のタングステン酸粒子
を温度700〜1200℃で還元することにより、上記目的を
達成するものである。In the method for producing ultrafine tungsten particles of the present invention, a gel precipitate produced by adjusting the aqueous solution of a tungsten compound to pH 3 or less has a specific conductivity of the mother liquor of 5 × 10 −5 Ω −1 cm −1 or less. The above object is achieved by reducing the obtained plate-like tungstic acid particles at a temperature of 700 to 1200 ° C.
以下に本発明に係るタングステン超微粒子の製造方法
について具体的に説明する。Hereinafter, the method for producing ultrafine tungsten particles according to the present invention will be specifically described.
出発原料となるタングステン化合物としては、タング
ストケイ酸、タングストホウ酸、タングストリン酸、タ
ングステン酸塩などが挙げられ、特に、タングステン酸
ナトリウム、メタタングステン酸ナトリウム、タングス
テン酸カリウム、タングステン酸カルシウム、タングス
テン酸マグネシウム、タングステン酸リチウム、メタタ
ングステン酸アンモニウム、パラタングステン酸アンモ
ニウムなどのタングステン酸塩は好例であり、本発明で
はこれらを水溶液として使用する。Tungsten silicic acid, tungstoboric acid, tungstophosphoric acid, tungstate, and the like may be mentioned as the tungsten compound serving as a starting material.In particular, sodium tungstate, sodium metatungstate, potassium tungstate, calcium tungstate, magnesium tungstate, Tungstates such as lithium tungstate, ammonium metatungstate and ammonium paratungstate are good examples, and these are used as aqueous solutions in the present invention.
このタングステン化合物水溶液の濃度はWO3として0.5
〜７重量％の範囲が望ましい。Concentration of the tungsten compound solution as WO 3 0.5
A range of about 7% by weight is desirable.
該水溶液のpH調整には、塩酸、硝酸、硫酸、などの強
酸が用いられる。For adjusting the pH of the aqueous solution, a strong acid such as hydrochloric acid, nitric acid, and sulfuric acid is used.
タングステン化合物水溶液が調整されるpH値は特に重
要であり、pH3以下好ましくは１〜２の範囲で目的とす
るゲル状沈澱物が生成される。The pH value at which the aqueous solution of the tungsten compound is adjusted is particularly important, and the desired gel precipitate is formed at a pH of 3 or less, preferably in the range of 1 to 2.
pH3より高い場合、後述する洗浄操作で比電導度を５
×10-5Ω-1cm-1以下に洗浄しても所望の板状タングステ
ン酸粒子が得られないので適当でない。When the pH is higher than 3, the specific conductivity is set to 5 by the washing operation described later.
Washing to 10-5 Ω -1 cm -1 or less is not suitable because desired plate-like tungstic acid particles cannot be obtained.
上記pH調整により生成したゲル状沈澱物を、母液の比
電導度が５×10-5Ω-1cm-1以下になるまで脱イオン水を
用いて洗浄し、板状のタングステン酸粒子を得る。母液
の比電導度が上記値以上では所望の板状タングステン酸
粒子が得られない。The gel precipitate formed by the above pH adjustment is washed with deionized water until the specific conductivity of the mother liquor becomes 5 × 10 −5 Ω −1 cm −1 or less, to obtain plate-like tungstic acid particles. . If the specific conductivity of the mother liquor is higher than the above value, desired plate-like tungstic acid particles cannot be obtained.
該板状タングステン酸粒子は、長さ約１〜６μｍ、幅
約0.5〜３μｍ、厚さ約400〜1000Åの範囲の大きさであ
ることが望ましく、特に、厚さが1500Å以上では、所望
の超微粒子が得られにくい。The plate-like tungstic acid particles preferably have a length of about 1 to 6 μm, a width of about 0.5 to 3 μm, and a thickness of about 400 to 1000 mm. Fine particles are difficult to obtain.
上記洗浄操作は、例えば限外濾過法などにより行われ
る。The washing operation is performed by, for example, an ultrafiltration method.
得られた板状タングステン酸粒子を温度700〜1200℃
で還元する。この温度範囲であれば、0.01〜0.2μｍの
タングステン超微粒子が得られるが、700℃より低い場
合は、還元速度が遅く、還元が不完全であったり、また
板状粒子が細かく破壊されないので好ましくない。一
方、1200℃以上での還元は、タングステン超微粒子が焼
結する傾向にあるので好ましくない。The obtained plate-like tungstic acid particles are heated at a temperature of 700 to 1200 ° C.
To reduce. Within this temperature range, 0.01 to 0.2 μm tungsten ultrafine particles can be obtained.However, if the temperature is lower than 700 ° C., the reduction rate is slow, reduction is incomplete, or the plate-like particles are not broken finely. Absent. On the other hand, reduction at 1200 ° C. or higher is not preferred because tungsten ultrafine particles tend to sinter.
還元剤としては、水素、炭素など通常、タングステン
粉末の製造に使用される還元剤が使用可能であり、１〜
５時間の還元時間が適当である。As the reducing agent, hydrogen, carbon and other reducing agents that are usually used in the production of tungsten powder can be used.
A reduction time of 5 hours is appropriate.
なお、還元に先立ち、300〜600℃で１〜５時間加熱処
理することが望ましい。この加熱処理により、板状タン
グステン酸粒子は板状の形状を保持した状態で酸化タン
グステンとなる。Prior to the reduction, it is desirable to perform a heat treatment at 300 to 600 ° C. for 1 to 5 hours. By this heat treatment, the plate-like tungstic acid particles become tungsten oxide while maintaining the plate-like shape.
試薬特級のタングステン酸ナトリウム（Na2WO4・2H
2O）384gを11の脱イオン水に溶解して、濃度約3.1重
量％のタングステン酸ナトリウム水溶液を調製した。こ
の水溶液を撹拌しながら、35重量％塩酸を添加して、pH
1.20に調整した後、４時間静置してレモン色のゲル状沈
澱物を得た。得られた沈澱物の上澄液を除去し、次い
で、該沈澱物を脱イオン水を用いて限外濾過膜（旭化
成、マイクローザPW−103）により母液の比電導度が２
×10-5Ω-1cm-1となるまで洗浄して、板状タングステン
酸粒子が分散した分散液１を得た。該分散液を電子顕
微鏡（TEM）で観察すると、長さ１〜４μｍ、幅0.5〜２
μｍ、厚さ600〜700Åの板状粒子が認められた。Special grade of sodium tungstate (Na 2 WO 4 · 2H
The 2 O) 384 g was dissolved in deionized water 11 to prepare a concentration of about 3.1 wt% of sodium tungstate aqueous solution. While stirring this aqueous solution, 35% by weight hydrochloric acid was added to adjust the pH.
After adjusting to 1.20, the mixture was allowed to stand for 4 hours to obtain a lemon gel precipitate. The supernatant of the obtained precipitate was removed, and then the precipitate was filtered using an ultrafiltration membrane (Asahi Kasei, Microza PW-103) using deionized water so that the specific conductivity of the mother liquor was 2%.
The dispersion was washed until it became × 10 −5 Ω −1 cm −1 to obtain a dispersion liquid 1 in which plate-like tungstic acid particles were dispersed. When the dispersion was observed with an electron microscope (TEM), the length was 1-4 μm and the width was 0.5-2.
Plate-like particles having a thickness of 600 μm and a thickness of 600 to 700 ° were observed.
次いで、ロータリーエバポレーターを用いて前記分散
液の水分を蒸発して粉末を得た。この粉末を600℃で２
時間焼成した後、水素雰囲気下に800℃で２時間還元処
理して黒色のタングステン超微粒子を得た。このタング
ステン超微粒子の粒子径を電子顕微鏡法で測定すると、
0.1〜0.2μｍの範囲にあった。Next, water was evaporated from the dispersion using a rotary evaporator to obtain a powder. This powder is heated at 600 ° C for 2
After calcination for a period of time, reduction treatment was performed at 800 ° C. for 2 hours in a hydrogen atmosphere to obtain black tungsten ultrafine particles. When the particle size of the tungsten ultrafine particles is measured by electron microscopy,
It was in the range of 0.1-0.2 μm.
試薬特級タングステン酸ナトリウムNa2WO4・2H2O）38
4gを11の脱イオン水に溶解し、この溶液を撹拌しなが
ら、試薬特級の35％塩酸を添加し、液のpHを5.1とし
た。４時間静置後、白青色の沈澱が生じたところで、上
澄液を除去し、沈澱を限外濾過膜（旭化成、マイクロー
ザPW−103）により脱イオン水を用いて母液の比電導度
が２×10-4Ω-1cm-1となるまで洗浄すると共に液量が１
になるまで濃縮した。Sodium reagent grade tungstate Na 2 WO 4 · 2H 2 O ) 38
4 g was dissolved in 11 deionized water, and while stirring the solution, reagent-grade 35% hydrochloric acid was added to adjust the pH of the solution to 5.1. After standing for 4 hours, when a white-blue precipitate was formed, the supernatant was removed, and the precipitate was subjected to ultrafiltration (Asahi Kasei, Microza PW-103) using deionized water to reduce the specific conductivity of the mother liquor. Wash until 2 × 10 -4 Ω -1 cm -1 and liquid volume is 1
And concentrated to.
このようにして得られたタングステン酸の沈澱を電子
顕微鏡（TEM）で観察すると実施例で認められた板状粒
子は観測されず、粒径約100Åの粒子よりなるゲル状物
であった。このゲル状沈澱をロータリーエバボレーター
で水分を蒸発させると容器壁に白青色の固形物が付着し
た。When the tungstic acid precipitate thus obtained was observed with an electron microscope (TEM), the plate-like particles observed in Examples were not observed, and the gel was a gel having particles of about 100 mm in diameter. When this gel precipitate was evaporated by a rotary evaporator, a white-blue solid substance adhered to the vessel wall.
この固形物を取り出し粉砕後、温度600℃で２時間焼
成し酸化タングステンの粉末とし、さらにこの粉末を実
施例と同様に、水素雰囲気下で温度800℃で２時間還元
処理した。得られた黒色のタングステン粉末を電子顕微
鏡（TEM）で観察すると、１〜２μｍの粒子であること
が認められた。The solid was taken out and pulverized, and calcined at a temperature of 600 ° C. for 2 hours to obtain a tungsten oxide powder. This powder was subjected to a reduction treatment at a temperature of 800 ° C. for 2 hours in a hydrogen atmosphere in the same manner as in the example. Observation of the obtained black tungsten powder with an electron microscope (TEM) confirmed that the particles were particles having a size of 1 to 2 μm.
本発明によれば、機械的粉砕工程を経ることなく、簡
便な方法により従来製造困難であった0.3μｍ以下のタ
ングステン超微粒子を製造することができる。According to the present invention, ultrafine tungsten particles of 0.3 μm or less can be produced by a simple method without a mechanical pulverization step.
従って、微細なタングステン粉末が求められる、超硬
合金材料、構造材料、耐熱材料用のタングステン粉末と
して利用可能である。Therefore, it can be used as a tungsten powder for a cemented carbide material, a structural material, and a heat-resistant material, for which a fine tungsten powder is required.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) B22F 9/22 C22B 34/36 C01G 41/00──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) B22F 9/22 C22B 34/36 C01G 41/00
Claims (1)
調整して生成するゲル状沈澱物を、母液の比電導度が５
×10-5Ω-1cm-1以下となるまで洗浄し、得られた板状の
タングステン酸粒子を温度700〜1200℃で還元すること
を特徴とするタングステン超微粒子の製造方法1. A gel-like precipitate formed by adjusting the pH of an aqueous solution of a tungsten compound to 3 or less, and having a specific conductivity of a mother liquor of 5 or less.
× 10 −5 Ω −1 cm −1 or less, and the resulting plate-like tungstic acid particles are reduced at a temperature of 700 to 1200 ° C. to produce tungsten ultrafine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1189843A JP2834199B2 (en) | 1989-07-21 | 1989-07-21 | Method for producing ultrafine tungsten particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1189843A JP2834199B2 (en) | 1989-07-21 | 1989-07-21 | Method for producing ultrafine tungsten particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0356607A JPH0356607A (en) | 1991-03-12 |
| JP2834199B2 true JP2834199B2 (en) | 1998-12-09 |
Family
ID=16248135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1189843A Expired - Lifetime JP2834199B2 (en) | 1989-07-21 | 1989-07-21 | Method for producing ultrafine tungsten particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2834199B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3411497B2 (en) * | 1998-03-25 | 2003-06-03 | 科学技術振興事業団 | W ultrafine particles, method for producing the same, and W nanocrystal thin film |
| JP4817486B2 (en) * | 2000-09-29 | 2011-11-16 | 株式会社東芝 | Tungsten powder, manufacturing method thereof, sputter target and cutting tool |
| CN1796029B (en) | 2001-07-30 | 2010-05-26 | 三菱麻铁里亚尔株式会社 | Fine tungsten carbide powder |
| DE102004023068B4 (en) * | 2004-05-11 | 2008-06-19 | H.C. Starck Gmbh | Tungstic acid and process for its preparation |
| CN116119719B (en) * | 2023-04-18 | 2023-06-27 | 崇义章源钨业股份有限公司 | Superfine platy tungsten oxide and preparation method thereof |
-
1989
- 1989-07-21 JP JP1189843A patent/JP2834199B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0356607A (en) | 1991-03-12 |
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