JPH0356607A - Manufacture of tangsten ultra fine particles - Google Patents
Manufacture of tangsten ultra fine particlesInfo
- Publication number
- JPH0356607A JPH0356607A JP1189843A JP18984389A JPH0356607A JP H0356607 A JPH0356607 A JP H0356607A JP 1189843 A JP1189843 A JP 1189843A JP 18984389 A JP18984389 A JP 18984389A JP H0356607 A JPH0356607 A JP H0356607A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- fine particles
- ultra fine
- precipitation
- tungsten
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000011882 ultra-fine particle Substances 0.000 title abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 32
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000012452 mother liquor Substances 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 239000010937 tungsten Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000003658 tungsten compounds Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract 4
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229910020341 Na2WO4.2H2O Inorganic materials 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
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。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing ultrafine tungsten particles, and more particularly to a method for producing ultrafine tungsten particles without mechanical crushing.
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 for cemented carbide, which is mainly made 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 in demand as a raw material for drills for drilling holes in IC boards.
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, tungsten powder has been produced by reducing tungsten oxide powder by heating it to 700° C. or higher in a hydrogen stream.
また、微細なタングステン粉末の製造方浩として特開昭
６１−１２４５０８号には、バ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
．３〜０．６μｍの超微粒子を製造する方法が開示され
ている。Furthermore, as a method for producing fine tungsten powder, JP-A-61-124508 discloses that ammonium baratungstate crystals are dissolved in hydrogen peroxide solution, the resulting solution is dried to obtain a solidified product, and then The solidified product is reduced to 0
．． A method for producing ultrafine particles of 3 to 0.6 μm 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 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 of 0.3 μm or less, which has been difficult to produce in the past, without going through a mechanical crushing process.
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５Ｘ１０−’Ω−’３
−’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。The method for producing ultrafine tungsten particles of the present invention involves adjusting an aqueous solution of a tungsten compound to a pH of 3 or less to produce a gel-like precipitate, which has a specific conductivity of 5X10-'Ω-'3.
The above object is achieved by washing until the temperature is below -' and reducing the obtained plate-shaped 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。The method for producing ultrafine tungsten particles according to the present invention will be specifically described below.
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。Examples of the tungsten compound used as a starting material include tungstosilicic acid, tungstoboric acid, tungstophosphoric acid, and tungstate salts, particularly sodium tungstate, sodium metatungstate, potassium tungstate, calcium tungstate, magnesium tungstate, Tungstate salts such as lithium tungstate, ammonium metatungstate and ammonium paratungstate are good examples and are used in the present invention as an aqueous solution.
このタングステン化合物水溶液の濃度はＷＯ，として０
．５〜７重量％の範囲が望ましい。The concentration of this tungsten compound aqueous solution is 0 as WO,
．． A range of 5 to 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。A strong acid such as hydrochloric acid, nitric acid, or sulfuric acid is used to adjust the pH of the aqueous solution.
タングステン化合物水溶液が調整されるｐＨ値は特に重
要で与り、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 tungsten compound aqueous solution is adjusted is particularly important, and the desired gel-like precipitate is produced 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
Ｘ１０−’Ω一′３−１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。If the pH is higher than 3, the specific conductivity can be reduced to 5 by the washing procedure described below.
Even if it is washed to less than X10-'Ω-'3-1, the desired plate-shaped tungstic acid particles cannot be obtained, so this is not suitable.
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５Ｘ１０−ｓΩ一’ ａｍ− ’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-like precipitate produced by the above pH adjustment is washed with deionized water until the specific conductivity of the mother liquor becomes 5×10 −sΩ1′ am−′ or less to obtain plate-shaped tungstic acid particles. If the specific conductivity of the mother liquor exceeds the above value, desired plate-shaped tungstic acid particles cannot be obtained.
該板状タングステン酸粒子は、長さ約１〜６μｍ１幅約
０ ． ５ 〜３ μｍ ｓ厚さ約４００ 〜１００
０人の範囲の大きさであることが望ましく、特に、厚さ
が１５００人以上では、所望の超微粒子が得られにくい
。The plate-shaped tungstic acid particles have a length of about 1 to 6 μm and a width of about 0.5 μm. 5 ~ 3 μm s Thickness approx. 400 ~ 100
It is desirable that the size is in the range of 0.0 mm, and in particular, if the thickness is 1500 mm or more, it will be difficult to obtain the desired ultrafine particles.
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 above-mentioned washing operation is performed, for example, by ultrafiltration.
得られた板状タングステン酸粒子を温度７００〜１２０
０℃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、７
００℃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-shaped tungstic acid particles were heated to a temperature of 700 to 120°C.
Reduce at 0°C. In this temperature range, 0.01 to 0
．． Ultrafine tungsten particles of 2 μm are obtained, but 7
If the temperature is lower than 00°C, the reduction rate is slow, the reduction may be incomplete, and the plate-like particles may not be finely broken, which is not preferable. On the other hand, reduction at a temperature of 1200° C. or higher is not preferable because the ultrafine tungsten 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、ｌ〜５
時間の還元時間が適当である。As the reducing agent, reducing agents normally used in the production of tungsten powder such as hydrogen and carbon can be used.
Time reduction time is appropriate.
なお、還元に先立ち、３００〜６００℃で１〜５時間加
熱処理を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。Note that, prior to reduction, it is desirable to perform a heat treatment at 300 to 600°C for 1 to 5 hours. Through this heat treatment, the plate-shaped tungstic acid particles turn into tungsten oxide while maintaining their plate-like shape.
試薬特級のタングステン酸ナトリウム（ＮａｇＷ Ｏ
ａ ・２Ｈ！ ０）３８４ｇをｌｌｌ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。この水溶液を攪拌しながら
、３５重量％塩酸を添加して、ＤＨ１．２０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ｐ
ｗ− ｉ ｏ３）により母液の比電導度が２Ｘ１０−’
Ω一’ １１３ − ’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ＩＮ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０．５〜２μｍ１厚さ６００〜７００人の板状粒子
が認められた。Reagent grade sodium tungstate (NagWO
a ・2H! 0) Dissolve 384g in lll of deionized water to give a concentration of approximately 3.0g. A 1% by weight aqueous sodium tungstate solution was prepared. While stirring this aqueous solution, 35% by weight hydrochloric acid was added to adjust the DH to 1.20, and the mixture was allowed to stand for 4 hours to obtain a lemon-colored gel precipitate. The supernatant liquid of the obtained precipitate was removed, and then the precipitate was filtered using an ultrafiltration membrane (Asahi Kasei, Microza P) using deionized water.
w-io3) makes the specific conductivity of the mother liquor 2X10-'
The dispersion liquid IN in which plate-shaped tungstic acid particles were dispersed was obtained by washing until Ω1'113-'. When the dispersion was observed with an electron microscope (TEM), the length was 1 to 4 μm.
, plate-like particles with a width of 0.5 to 2 μm and a thickness of 600 to 700 were observed.
次いで、ロータリーエバボ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 in the dispersion was evaporated using a rotary evaporator to obtain a powder. This powder was heated at 600℃ for 2
After firing for an hour, reduction treatment was performed at 800° C. for 2 hours in a hydrogen atmosphere to obtain black ultrafine tungsten particles. When the particle diameter of these ultrafine tungsten particles was measured by electron microscopy, it was found to be 0. It was in the range of 1 to 0.2 μm.
試薬特級タングステン酸ナトリウム（ＮａｚＷＯ１ ●
２Ｈ２ ０） ３ ８ ４ ｇをＩｆＩ！の脱イオン水
に溶解し、この溶液を攪拌しながら、試薬特級の３５％
塩酸を添加し、液のｐＨを５．１とした。Reagent grade sodium tungstate (NazWO1
2H2 0) 3 8 4 g IfI! of 35% reagent grade, while stirring the solution.
Hydrochloric acid was added to adjust the pH of the solution to 5.1.
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Ｐ
Ｗ−１０３）により脱イオン水を用いて母液の比電導度
が２Ｘ１０−’Ω−’ａｍ〜１となるまで洗浄すると共
に液量がｌｌになるまで濃縮した。After standing for 4 hours, when a white-blue precipitate was formed, the supernatant was removed and the precipitate was filtered through an ultrafiltration membrane (Asahi Kasei, Microza P).
W-103) using deionized water until the specific conductivity of the mother liquor became 2×10-'Ω-'am~1 and concentrated until the liquid volume became 1 liter.
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１００人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 using an electron microscope (TEM), the plate-like particles observed in the examples were not observed, and it was found to be a gel-like substance consisting of particles of approximately 100 particles in diameter. When the water content of this gel-like precipitate was evaporated using a rotary evaporator, a whitish-blue solid substance adhered to the wall of the container.
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、Ｉ〜２μｍの粒子である
ことが認められた。This solid material was taken out, pulverized, and then calcined at a temperature of 600° C. for 2 hours to obtain a tungsten oxide powder, and this powder was further 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. When the obtained black tungsten powder was observed with an electron microscope (TEM), it was found to be particles of I 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, which have been difficult to produce in the past, can be produced by a simple method without going through a mechanical crushing process.
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 tungsten powder for cemented carbide materials, structural materials, and heat-resistant materials, which require fine tungsten powder.
Claims (1)
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７００〜１２０
０℃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A gel-like precipitate produced by adjusting an aqueous solution of a tungsten compound to a pH of 3 or lower is prepared when the specific conductivity of the mother liquor is 5 × 10^-
The plate-shaped tungstic acid particles obtained were washed until the resistance became ^5 Ω^-^1 cm^-^1 or less at a temperature of 700 to 120 Ω.
Method for producing ultrafine tungsten particles characterized by reduction at 0°C
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 true JPH0356607A (en) | 1991-03-12 |
| JP2834199B2 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) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999049099A1 (en) * | 1998-03-25 | 1999-09-30 | Japan Science And Technology Corporation | Tungsten super fine particle and method for producing the same |
| JP2002105632A (en) * | 2000-09-29 | 2002-04-10 | Toshiba Corp | Tungsten powder and its manufacturing method, and sputtering target and cutting tool |
| US6852304B2 (en) | 2001-07-30 | 2005-02-08 | Mitsubishi Materials Corporation | Fine tungsten carbide powder and process for producing the same |
| JP2007537121A (en) * | 2004-05-11 | 2007-12-20 | ハー ツェー シュタルク ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンデイトゲゼルシヤフト | Tungstic acid and method for producing the same |
| CN116119719A (en) * | 2023-04-18 | 2023-05-16 | 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
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999049099A1 (en) * | 1998-03-25 | 1999-09-30 | Japan Science And Technology Corporation | Tungsten super fine particle and method for producing the same |
| US6440562B1 (en) | 1998-03-25 | 2002-08-27 | Kabushiki Kaisha Toshiba | Tungsten super fine particle and method for producing the same |
| JP2002105632A (en) * | 2000-09-29 | 2002-04-10 | Toshiba Corp | Tungsten powder and its manufacturing method, and sputtering target and cutting tool |
| US6852304B2 (en) | 2001-07-30 | 2005-02-08 | Mitsubishi Materials Corporation | Fine tungsten carbide powder and process for producing the same |
| US7465432B2 (en) | 2001-07-30 | 2008-12-16 | Mitsubishi Materials Corp. | Fine tungsten carbide powder and process for producing the same |
| JP2007537121A (en) * | 2004-05-11 | 2007-12-20 | ハー ツェー シュタルク ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンデイトゲゼルシヤフト | Tungstic acid and method for producing the same |
| CN116119719A (en) * | 2023-04-18 | 2023-05-16 | 崇义章源钨业股份有限公司 | Superfine platy tungsten oxide and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2834199B2 (en) | 1998-12-09 |
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