JPH06321519A - Fine particulate compound carbide solid solution and its production - Google Patents
Fine particulate compound carbide solid solution and its productionInfo
- Publication number
- JPH06321519A JPH06321519A JP5135216A JP13521693A JPH06321519A JP H06321519 A JPH06321519 A JP H06321519A JP 5135216 A JP5135216 A JP 5135216A JP 13521693 A JP13521693 A JP 13521693A JP H06321519 A JPH06321519 A JP H06321519A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- solid solution
- composite carbide
- oxide powder
- temperature
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は炭化物固溶体の製造方法
に関し、特に、粒度の微細な炭化物固溶体の製造方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a carbide solid solution, and more particularly to a method for producing a carbide solid solution having a fine grain size.
【０００２】[0002]
【従来の技術】一般に、超硬合金、サーメット、及びセ
ラミックス等においては高硬度性及び高強度性が求めら
れており、このためには、均粒微細でかつ高純度の原料
粉末を得る必要がある。2. Description of the Related Art Generally, cemented carbides, cermets, ceramics, etc. are required to have high hardness and high strength. For this purpose, it is necessary to obtain raw material powders of uniform particle size and high purity. is there.
【０００３】従来、鋼切削用超硬合金の原料粉末として
（Ｗ・Ｔｉ・Ｔａ）Ｃ及び（Ｗ・Ｔｉ）Ｃ等のIVａ、Ｖ
ａ、VIａ族からなる所謂複合炭化物固溶体が用いられて
いる。これら複合炭化物固溶体を原料粉末として超硬合
金を製造すると、ＷＣ−Ｃｏ系超硬合金に比べて鋼に対
する溶着性に優れ、かつ高温強度を高くすることができ
る。Conventionally, as raw material powders of cemented carbide for steel cutting, (W.Ti.Ta) C and (W.Ti) C IVa, V, etc.
So-called composite carbide solid solutions of the groups a and VIa are used. When a cemented carbide is produced by using these composite carbide solid solutions as raw material powders, the weldability to steel is excellent and the high temperature strength can be increased as compared with the WC-Co based cemented carbide.
【０００４】上記のような複合炭化物固溶体を製造する
際には、一般に次の方法が知られている。The following methods are generally known for producing the above-mentioned composite carbide solid solution.
【０００５】IVａ族炭化物、Ｖａ族炭化物、及びVIａ
族炭化物の混合物を水素気流中において温度２０００℃
以上の高温域でプッシャータイプの連続炉又はバッチタ
イプの真空炉で固溶体処理を行う方法。プッシャータイ
プの連続炉で固溶体処理を行う際には、円筒状黒鉛の両
端に直流電流を供給して加熱し、その後、所定の温度と
なった炉に黒鉛製ボート内に被処理物を適当量充填して
プッシャーで順次炉内に送る。Group IVa carbides, Va group carbides, and VIa
A mixture of group carbides in a hydrogen stream at a temperature of 2000 ° C.
A method of performing solid solution treatment in a pusher type continuous furnace or a batch type vacuum furnace in the above high temperature range. When performing solid solution treatment in a pusher-type continuous furnace, a direct current is supplied to both ends of cylindrical graphite to heat it, and then a suitable amount of the object to be treated is placed in a graphite boat in a furnace that has reached a predetermined temperature. Fill and send to the furnace one by one with pusher.
【０００６】IVａ、Ｖａ、及びVIａ族の金属粉末と炭
素粉末とを混合して、この混合物を水素気流中において
温度２０００℃以上の高温域でプッシャータイプの連続
炉又はバッチタイプの真空炉で固溶体処理を行う方法。Metal powders of group IVa, Va, and VIa and carbon powder are mixed, and the mixture is mixed in a hydrogen stream in a high temperature range of 2000 ° C. or higher in a pusher type continuous furnace or a batch type vacuum furnace to form a solid solution. How to do the processing.
【０００７】IVａ、Ｖａ、及びVIａ族の酸化物とＷ粉
末と炭素粉末とを混合して、この混合物を水素気流中に
おいて温度２０００℃以上の高温域でプッシャータイプ
の連続炉又はバッチタイプの真空炉で固溶体処理を行う
方法。An oxide of group IVa, Va, and VIa, W powder and carbon powder are mixed, and the mixture is heated in a hydrogen stream at a high temperature range of 2000 ° C. or higher in a pusher type continuous furnace or a batch type vacuum. A method of performing solid solution treatment in a furnace.
【０００８】IVａ、Ｖａ、及びVIａ族の酸化物を窒素
気流中において１０００乃至１６００℃の温度域で回転
炉を用いて１次処理を行った後、水素気流中において１
６００℃以上の温度域で２次処理を行い、必要に応じて
真空中で１６００℃以上の温度域で３次処理を行う方法
（例えば、特公昭５１−２９５１９号公報、特公昭５４
−４２０００号公報）。回転炉は、その中心部に円柱型
ヒーターが配置され、このヒーターを包み込むように黒
鉛製の二重円筒が配置されており、これら二重円筒のう
ち外側の円筒は固定され、内側の円筒は回転される。The oxides of group IVa, Va, and VIa were subjected to primary treatment in a nitrogen stream in a temperature range of 1000 to 1600 ° C. using a rotary furnace, and then in a hydrogen stream.
A method of performing a secondary treatment in a temperature range of 600 ° C. or higher and, if necessary, a third treatment in a temperature range of 1600 ° C. or higher in vacuum (for example, JP-B-51-29519 and JP-B-54).
-42000). In the rotary furnace, a cylindrical heater is arranged at the center, and a double cylinder made of graphite is arranged so as to wrap this heater.The outer cylinder of these double cylinders is fixed, and the inner cylinder is Is rotated.
【０００９】IVａ、Ｖａ、及びVIａ族金属、IVａ、Ｖ
ａ、及びVIａ炭化物、及びIVａ、Ｖａ、及びVIａ酸化物
に固溶化促進剤（炭化物の拡散速度を増大させる）であ
るＣｏ及びＮｉを０．１乃至０．５％添加した後加熱し
て複合炭化物とする方法。IVa, Va, and VIa group metals, IVa, V
a and VIa carbides, and IVa, Va, and VIa oxides, 0.1 to 0.5% Co and Ni, which are solution solubilizers (which increase the diffusion rate of carbides), are added, and then heated to form a composite. Carbide method.
【００１０】IVａ、Ｖａ、及びVIａ族金属、鉄族元素
又はアルミニューム、及び炭素粉末を溶融して（メンス
ラム法）、２０００℃以上の高温に加熱し、炭化物粉末
を析出させた後、金属を酸で溶解して複合炭化物を得る
方法。The IVa, Va, and VIa group metals, iron group elements or aluminum, and carbon powder are melted (Menslam method) and heated to a high temperature of 2000 ° C. or higher to precipitate a carbide powder, and then the metal is removed. A method of obtaining a composite carbide by dissolving with an acid.
【００１１】IVａ、Ｖａ、及びVIａ族金属ハロゲン化
物と炭化水素を高温中で反応させて複合炭化物を析出さ
せる方法。A method of reacting a group IVa, Va, and VIa metal halide with a hydrocarbon at a high temperature to precipitate a composite carbide.
【００１２】IVａ、Ｖａ、及びVIａ族金属のアルコキ
シドと炭素粉末とを分散させた後、加水分解して沈澱物
を生成し、この沈澱物を真空中又は不活性ガス中にて１
０００乃至１６００℃の温度域において反応させて複合
炭化物を得る方法（例えば、特公平１−１４１６７号公
報）。After dispersing the alkoxides of the IVa, Va and VIa metals and the carbon powder, they are hydrolyzed to form a precipitate, and the precipitate is formed in vacuum or in an inert gas.
A method of obtaining a composite carbide by reacting in a temperature range of 000 to 1600 ° C (for example, Japanese Patent Publication No. 1-14167).
【００１３】[0013]
【発明が解決しようとする課題】ところで、上記乃至
の方法では、固溶体化処理温度が２０００℃であるた
め、複合炭化物の粒成長が著しく、このため、微粒複合
炭化物を得るためには後工程において強力な粉砕を実行
する必要がある。加えて、プッシャータイプの連続炉又
はバッチタイプの真空炉によって固溶体化処理を行うた
め、混合物が均一に加熱されず、その結果、複合炭化物
において、炭素量及び固溶度等の品質にばらつきが大き
いという問題点がある。特に、の方法では、多量の反
応ガスによって熱伝達が不均一となって均一な固溶体が
得られない。By the way, in the above-mentioned methods, since the solid solution treatment temperature is 2000 ° C., the grain growth of the composite carbide is remarkable. Therefore, in order to obtain the fine grain composite carbide in the post-process. It is necessary to carry out a powerful crush. In addition, since the solid solution treatment is performed in a pusher type continuous furnace or a batch type vacuum furnace, the mixture is not uniformly heated, and as a result, the quality of the composite carbide, such as the amount of carbon and solid solubility, varies widely. There is a problem. In particular, in the method (1), heat transfer is non-uniform due to a large amount of reaction gas, and a uniform solid solution cannot be obtained.
【００１４】上記の方法では、２次処理において使用
する水素の影響によって脱酸素が十分に行われず、しか
も３次処理まで行う場合にはコスト高となってしまうと
いう問題点がある。In the above method, there is a problem that deoxidation is not sufficiently performed due to the influence of hydrogen used in the secondary treatment, and the cost becomes high when the tertiary treatment is performed.
【００１５】上記の方法では、固溶体化促進剤である
Ｃｏ、Ｎｉによって短時間で複合炭化物を得る関係上粉
末が焼結してしまい、強力な粉砕を実行しなければなら
ないという問題点がある。The above method has a problem that the powder is sintered by the solid solution accelerators Co and Ni in order to obtain the composite carbide in a short time, and strong pulverization must be performed.
【００１６】上記の方法では、Ｆｅ及びＮｉ等が完全
に除去できず、複合炭化物中に不純物として残ってしま
う。加えて、この方法によって得られた複合炭化物は粒
度が粗く、このため、強力な粉砕を行う必要がある。In the above method, Fe, Ni, etc. cannot be completely removed, and they remain as impurities in the composite carbide. In addition, the composite carbide obtained by this method has a coarse particle size, which requires strong grinding.
【００１７】上記の方法では、微粒かつ高純度の複合
炭化物を得ることができるが、収率が極めて悪く、量産
化が難しいという問題点がある。The above-mentioned method can obtain fine-grained and high-purity composite carbide, but has a problem that the yield is extremely low and mass production is difficult.
【００１８】上記の方法でも、の方法と同様に微粒
かつ高純度の複合炭化物を得ることができるが、収率が
極めて悪く、量産化が難しいという問題点がある。加え
て、薬品費の面を考慮すると、コスト面で不利になると
いう問題点がある。Similar to the above method, fine particles and high purity composite carbide can be obtained by the above method, but there is a problem that the yield is extremely poor and mass production is difficult. In addition, considering the cost of medicines, there is a problem in that it is disadvantageous in terms of cost.
【００１９】本発明の目的は粉砕した原料を使用するこ
とにより微粒かつ高純度の複合炭化物を得ることのでき
る製造方法を提供することにある。An object of the present invention is to provide a production method capable of obtaining a fine-grained and high-purity composite carbide by using a pulverized raw material.
【００２０】本発明の他の目的はコスト面で有利な微粒
複合炭化物固溶体の製造方法を提供することにある。Another object of the present invention is to provide a method for producing a fine-grain composite carbide solid solution which is advantageous in terms of cost.
【００２１】本発明のさらに他の目的は量産化を実現で
きる微粒複合炭化物固溶体の製造方法を提供することに
ある。Still another object of the present invention is to provide a method for producing a fine-grain composite carbide solid solution which can be mass-produced.
【００２２】[0022]
【課題を解決するための手段】本発明によれば、酸化タ
ングステン粉末、ＴｉＯ2 粉末、及び炭素粉末を混合し
てバインダーを用いてペレット状に成形する第１の工程
と、該ペレットを回転炉を用いて窒素気流中において温
度１４５０℃乃至１６００℃で処理して１次処理物を得
る第２の工程と、該１次処理物を真空中で温度１７５０
℃乃至１９００℃で処理して複合炭化物固溶体を得る第
３の工程とを有することを特徴とする微粒複合炭化物固
溶体の製造方法が得られる。According to the present invention, a first step of mixing a tungsten oxide powder, a TiO 2 powder, and a carbon powder into a pellet using a binder, and the pellet in a rotary furnace. In a nitrogen stream at a temperature of 1450 ° C. to 1600 ° C. to obtain a primary treated product, and the primary treated product in vacuum at a temperature of 1750 ° C.
And a third step of obtaining a composite carbide solid solution by treating at a temperature of from 1 ° C. to 1900 ° C., thereby obtaining a method for producing a fine-grain composite carbide solid solution.
【００２３】さらに、本発明によれば、酸化タングステ
ン粉末、ＴｉＯ2 粉末、及び炭素粉末とIVａ族酸化物粉
末、Ｖａ族酸化物粉末、及びVIａ族酸化物粉末の少なく
とも一種とを混合してバインダーを用いてペレット状に
成形する第１の工程と、該ペレットを回転炉を用いて窒
素気流中において温度１４５０℃乃至１６００℃で処理
して１次処理物を得る第２の工程と、該１次処理物を真
空中で温度１７５０℃乃至１９００℃で処理して複合炭
化物固溶体を得る第３の工程とを有することを特徴とす
る微粒複合炭化物固溶体の製造方法が得られる。Furthermore, according to the present invention, a binder is prepared by mixing tungsten oxide powder, TiO 2 powder, and carbon powder with at least one of group IVa oxide powder, group Va oxide and group VIa oxide powder. And a second step of forming the pellet-shaped product by using a rotating furnace, and treating the pellets in a nitrogen atmosphere in a rotary furnace at a temperature of 1450 ° C. to 1600 ° C. to obtain a primary treated product. And a third step of obtaining a composite carbide solid solution by treating the subsequent treated material in vacuum at a temperature of 1750 ° C to 1900 ° C.
【００２４】このようにして得られた複合炭化物固溶体
は粒径が１μｍ以下でしかも均粒であり、酸素の含有量
が０．２重量％以下、窒素の含有量が０．０３重量％以
下、鉄の含有量が０．０２重量％以下、コバルトの含有
量が０．０２重量％以下である。The composite carbide solid solution thus obtained has a particle size of 1 μm or less and is even, and has an oxygen content of 0.2% by weight or less and a nitrogen content of 0.03% by weight or less, The iron content is 0.02% by weight or less, and the cobalt content is 0.02% by weight or less.
【００２５】[0025]
【作用】本発明では、酸化タングステン粉末、ＴｉＯ2
粉末、及び炭素粉末又は酸化タングステン粉末、ＴｉＯ
2 粉末、及び炭素粉末とIVａ族酸化物粉末、Ｖａ族酸化
物粉末、及びVIａ族酸化物粉末の少なくとも一種とを混
合してバインダーを用いてペレット状に成形してペレッ
ト体を得る。そして、このペレット体を回転炉を用いて
窒素気流中において温度１４５０℃乃至１６００℃で処
理して１次処理物を得、１次処理物を真空中で温度１７
５０℃乃至１９００℃で処理する。このようにして、ペ
レット体を処理することによって、均粒微細でしかも高
純度で十分に固溶した優れた複合炭化物固溶体を得るこ
とができる。さらに、本発明の製造方法ではコスト面で
有利であるばかりでなく、量産化を実現することが可能
となる。In the present invention, tungsten oxide powder and TiO 2 are used.
Powder, carbon powder or tungsten oxide powder, TiO
2 powder, and carbon powder and at least one of group IVa oxide powder, group Va oxide powder, and group VIa oxide powder are mixed and molded into a pellet using a binder to obtain a pellet. Then, the pellets are treated at a temperature of 1450 ° C. to 1600 ° C. in a nitrogen stream using a rotary furnace to obtain a primary treated product, and the primary treated product is heated to a temperature of 17 ° C. in vacuum.
Process at 50 ° C to 1900 ° C. By treating the pellets in this manner, it is possible to obtain an excellent composite carbide solid solution which has a uniform grain size and is highly pure and sufficiently solid-dissolved. Furthermore, the manufacturing method of the present invention is not only advantageous in terms of cost, but can be mass-produced.
【００２６】[0026]
【実施例】以下本発明について実施例によって説明す
る。EXAMPLES The present invention will be described below with reference to examples.
【００２７】粉砕機によって粒度０．７５μｍに粉砕し
たＷＯ3 及び粒度０．２μｍに粉砕したＴｉＯ2 を炭素
粉末とヘンシルミキサーを用いて組成比がＴｉＣ：ＷＣ
＝３：７となるように混合して、混合粉末を得た。その
後、混合粉末に造粒バインダーに変性アルコールを用い
てペレット状に整粒した後、この造粒粉末を乾燥させて
原料粉末とした。そして、この原料粉末を回転炉を用い
て窒素気流中において温度１６００℃で反応させた。WO 3 crushed to a particle size of 0.75 μm and TiO 2 crushed to a particle size of 0.2 μm by a crusher were used in a composition ratio of TiC: WC using carbon powder and a Hensyl mixer.
= 3: 7 to obtain a mixed powder. Then, the mixed powder was sized into pellets using denatured alcohol as a granulating binder, and the granulated powder was dried to obtain a raw material powder. Then, this raw material powder was reacted at a temperature of 1600 ° C. in a nitrogen stream using a rotary furnace.
【００２８】ここで使用した回転炉は内径８５ｍｍで長
さ２４００ｍｍの黒鉛製円筒内に外形４０ｍｍで長さ２
６２０ｍｍの黒鉛製ヒーターが配置されており、外側円
筒を２ｒｐｍで回転させ、炉自体を水平面に対して約６
度傾けて使用した。回転炉内には窒素気流を１．２ｍ3
／ｈで供給し、ヒーターに通電することによって黒鉛製
円筒を加熱して温度１６００℃に維持した。そして、回
転炉上部から原料粉末を２０ｇ／ｍｉｎの割合で投入し
た（原料粉末の炉内滞在時間は１５分以内であった）。The rotary furnace used here is a graphite cylinder having an inner diameter of 85 mm and a length of 2400 mm, and an outer diameter of 40 mm and a length of 2 mm.
A 620 mm graphite heater is placed, the outer cylinder is rotated at 2 rpm, and the furnace itself is about 6
I used it at an angle. 1.2m 3 of nitrogen gas flow in the rotary furnace
/ H and the heater was energized to heat the graphite cylinder to maintain the temperature at 1600 ° C. Then, the raw material powder was charged from the upper part of the rotary furnace at a rate of 20 g / min (the stay time of the raw material powder in the furnace was within 15 minutes).
【００２９】上述のようにして、１次処理粉末を得た
後、１次処理粉末を真空炭化炉を用いて真空中１８００
℃で２次処理した。そして、このようにして処理された
粉末（複合炭化物）を試験番号１とした。After the primary treatment powder is obtained as described above, the primary treatment powder is processed in a vacuum carbonization furnace in vacuum at 1800.
Secondary treatment was performed at ° C. The powder (composite carbide) thus treated was designated as test number 1.
【００３０】また、１次処理温度を１５３０℃、２次処
理温度を１９００℃とし、他の条件は試験番号１の複合
炭化物と同様にして複合炭化物を得て、これを試験番号
２とした。さらに、１次処理温度を１４７０℃、２次処
理温度を１９００℃とし、他の条件は試験番号１の複合
炭化物と同様にして複合炭化物を得て、これを試験番号
３とした。The primary treatment temperature was 1530 ° C., the secondary treatment temperature was 1900 ° C., and the other conditions were the same as those of the test number 1 to obtain a composite carbide, which was designated as test number 2. Furthermore, the primary treatment temperature was 1470 ° C., the secondary treatment temperature was 1900 ° C., and the other conditions were the same as the composite carbide of Test No. 1 to obtain a composite carbide, which was designated as Test No. 3.
【００３１】以下同様にして、１次処理温度を１４００
℃、２次処理温度を１８００℃として複合炭化物を得
て、これを試験番号４とし、１次処理温度を１７００
℃、２次処理温度を１８００℃として複合炭化物を得
て、これを試験番号５とし、１次処理温度を１６００
℃、２次処理温度を１６５０℃として複合炭化物を得
て、これを試験番号６とし、１次処理温度を１６００
℃、２次処理温度を２０００℃として複合炭化物を得
て、これを試験番号７とした。Similarly, the primary treatment temperature is set to 1400.
C., the secondary treatment temperature was 1800.degree. C. to obtain a composite carbide, which was designated as test number 4, and the primary treatment temperature was 1700.
C., the secondary treatment temperature was 1800.degree. C. to obtain a composite carbide, which was designated as test number 5, and the primary treatment temperature was 1600.
C., the secondary treatment temperature was 1650.degree. C. to obtain a composite carbide, which was designated as test number 6, and the primary treatment temperature was 1600.
C. and the secondary treatment temperature was 2000.degree. C. to obtain a composite carbide, which was designated as test number 7.
【００３２】また、比較のため、粉砕機によって粒度
０．２μｍに粉砕したＴｉＯ2 及び粒度０．９μｍのＷ
を炭素粉末とヘンシルミキサーを用いて組成比がＴｉ
Ｃ：ＷＣ＝３：７となるように混合して、混合粉末を得
た。この混合粉末から前述のようにペレット体を整粒し
た後、このペレット体をプッシャータイプの連続炉（炉
長：１６００ｍｍ）を用いて処理した。ここでは、連続
炉は温度２０００℃に保って水素ガスを１．２ｍ3 ／ｈ
で炉内に流入させた。そして、長さ３００ｍｍの黒鉛製
ボートに上記のペレット体を乗せて、このボートを１５
分間隔で炉に挿入した。このようにして得られた複合炭
化物を試験番号８とした。さらに、この試験番号８の複
合炭化物を超硬ボールを用いて粉砕して粉末を得て、こ
の粉末を試験番号９とした。For comparison, TiO 2 ground to a particle size of 0.2 μm and W having a particle size of 0.9 μm were used for comparison.
The composition ratio is Ti using carbon powder and a Hencil mixer.
The mixture was mixed so that C: WC = 3: 7 to obtain a mixed powder. After the pellets were sized from the mixed powder as described above, the pellets were processed using a pusher type continuous furnace (furnace length: 1600 mm). Here, the continuous furnace is kept at a temperature of 2000 ° C. and hydrogen gas is 1.2 m 3 / h.
It was made to flow into the furnace. Then, the above pellet was placed on a graphite boat having a length of 300 mm, and the boat was
It was inserted into the furnace at minute intervals. The composite carbide thus obtained was designated as test number 8. Further, the composite carbide of Test No. 8 was crushed using a cemented carbide ball to obtain a powder, and this powder was designated as Test No. 9.
【００３３】これら試験番号１乃至９の複合炭化物の製
造条件及び分析値を図１に示す。図１から明らかなよう
に試験番号１乃至３の複合炭化物においてはＦＳＳＳが
１．０μｍ以下である。また、試験番号１乃至３の複合
炭化物においては残留酸素の量及び残留窒素の量が極め
て少ない。The manufacturing conditions and analytical values of the composite carbides of these test numbers 1 to 9 are shown in FIG. As is clear from FIG. 1, the FSSS of the composite carbides of Test Nos. 1 to 3 is 1.0 μm or less. Further, in the composite carbides of test numbers 1 to 3, the amount of residual oxygen and the amount of residual nitrogen are extremely small.
【００３４】試験番号４の複合炭化物ではＦＳＳＳが
１．０μｍ以下であるが、残留酸素の量及び残留窒素の
量が多くなってしまう。さらに、試験番号５の複合炭化
物ではＦＳＳＳが１．０μｍ以下であるが、残留窒素の
量が多くなってしまう。試験番号６の複合炭化物ではＦ
ＳＳＳが１．０μｍ以下であるが、Ｘ線回折の結果、未
固溶体であることがわかった。試験番号７の複合炭化物
ではＦＳＳＳが２．０μｍとなってしまい、試験番号８
の複合炭化物ではＦＳＳＳが３．０μｍとなってしま
う。試験番号９の複合炭化物においてもＦＳＳＳは１．
４μｍである。The composite carbide of Test No. 4 has an FSSS of 1.0 μm or less, but the amount of residual oxygen and the amount of residual nitrogen increase. Further, although the composite carbide of Test No. 5 has an FSSS of 1.0 μm or less, the amount of residual nitrogen increases. F in the composite carbide of test number 6
Although the SSS was 1.0 μm or less, the result of X-ray diffraction revealed that it was a non-solid solution. With the composite carbide of test number 7, FSSS was 2.0 μm, and test number 8
FSSS becomes 3.0 μm in the composite carbide of. In the composite carbide of test number 9, FSSS was 1.
It is 4 μm.
【００３５】ここで、試験番号１、８、及び９の複合炭
化物の電子顕微鏡写真（拡大率５０００倍）をそれぞれ
図２乃至図４に示す。図２乃至図４に示すように試験番
号１の複合炭化物はその粒径が極めて小さいことがわか
る。2 to 4 are electron micrographs (magnification of 5000 times) of the composite carbides of Test Nos. 1, 8 and 9, respectively. As shown in FIGS. 2 to 4, it is understood that the composite carbide of test number 1 has an extremely small particle size.
【００３６】次に衝撃粉砕機を用いて粒度０．７５μｍ
に粉砕したＷＯ3 、粒度０．５μｍに粉砕したＴａ2 Ｏ
5 、及び粒度０．２μｍのＴｉＯ2 を炭素粉末とヘンシ
ルミキサーを用いて組成比がＷＣ：ＴａＣ：ＴｉＣ＝
５：２：３となるように混合して、混合粉末を得た。そ
の後、混合粉末に造粒バインダーに変性アルコールを用
いてペレット状に整粒した後、この造粒粉末を乾燥させ
て原料粉末とした。そして、この原料粉末を回転炉を用
いて窒素気流中において温度１６００℃で反応させた。Then, using an impact crusher, the particle size is 0.75 μm.
Ground WO 3 and Ta 2 O ground to a particle size of 0.5 μm
5 , and a composition ratio of TiO 2 having a particle size of 0.2 μm using carbon powder and a Hensyl mixer, WC: TaC: TiC =
The mixture was mixed in a ratio of 5: 2: 3 to obtain a mixed powder. Then, the mixed powder was sized into pellets using denatured alcohol as a granulating binder, and the granulated powder was dried to obtain a raw material powder. Then, this raw material powder was reacted at a temperature of 1600 ° C. in a nitrogen stream using a rotary furnace.
【００３７】ここで使用した回転炉は内径８５ｍｍで長
さ２４００ｍｍの黒鉛製円筒内に外形４０ｍｍで長さ２
６２０ｍｍの黒鉛製ヒーターが配置されており、外側円
筒を２ｒｐｍで回転させ、炉自体を水平面に対して約６
度傾けて使用した。回転炉内には窒素気流を１．２ｍ3
／ｈで供給し、ヒーターに通電することによって黒鉛製
円筒を加熱して温度１６００℃に維持した。そして、回
転炉上部から原料粉末を２０ｇ／ｍｉｎの割合で投入し
た（原料粉末の炉内滞在時間は１５分以内であった）。The rotary furnace used here is a graphite cylinder having an inner diameter of 85 mm and a length of 2400 mm and an outer diameter of 40 mm and a length of 2 mm.
A 620 mm graphite heater is placed, the outer cylinder is rotated at 2 rpm, and the furnace itself is about 6
I used it at an angle. 1.2m 3 of nitrogen gas flow in the rotary furnace
/ H and the heater was energized to heat the graphite cylinder to maintain the temperature at 1600 ° C. Then, the raw material powder was charged from the upper part of the rotary furnace at a rate of 20 g / min (the stay time of the raw material powder in the furnace was within 15 minutes).
【００３８】上述のようにして、１次処理粉末を得た
後、１次処理粉末を真空炭化炉を用いて真空中１８５０
℃で２次処理した。そして、このようにして処理された
粉末（複合炭化物）を試験番号１０とした。After the primary treated powder is obtained as described above, the primary treated powder is placed in a vacuum carbonization furnace at 1850 in vacuum.
Secondary treatment was performed at ° C. The powder (composite carbide) thus treated was designated as test number 10.
【００３９】比較のため、粒度０．９μｍのＷ、粒度
０．５μｍに粉砕したＴａ2 Ｏ5 、及び粒度０．２μｍ
に粉砕したＴｉＯ2 を炭素粉末とヘンシルミキサーを用
いて組成比がＷＣ：ＴａＣ：ＴｉＣ＝５：２：３となる
ように混合して、混合粉末を得た。この混合粉末をプッ
シャータイプの連続炉（炉長：１６００ｍｍ）を用いて
処理した。ここでは、連続炉は温度２１００℃に保って
水素ガスを１．２ｍ3 ／ｈで炉内に流入させた。そし
て、長さ３００ｍｍの黒鉛製ボートに上記の混合粉末
（造粒粉末）を乗せて、このボートを１５分間隔で炉に
挿入した。このようにして得られた複合炭化物を試験番
号１１とした。For comparison, W having a particle size of 0.9 μm, Ta 2 O 5 ground to a particle size of 0.5 μm, and particle size of 0.2 μm
The TiO 2 pulverized in the above manner was mixed with carbon powder using a Hensyl mixer so that the composition ratio became WC: TaC: TiC = 5: 2: 3 to obtain a mixed powder. This mixed powder was processed using a pusher type continuous furnace (furnace length: 1600 mm). Here, the temperature of the continuous furnace was maintained at 2100 ° C., and hydrogen gas was introduced into the furnace at 1.2 m 3 / h. Then, the above-mentioned mixed powder (granulated powder) was put on a graphite boat having a length of 300 mm, and the boat was inserted into the furnace at intervals of 15 minutes. The composite carbide thus obtained was designated as test number 11.
【００４０】ここで、試験番号１０及び１１の複合炭化
物の製造条件及び分析値を図５に示す。図５に示すよう
に、試験番号１０の複合炭化物においてはＦＳＳＳが
１．０μｍ以下であるが、試験番号１１の複合炭化物で
はＦＳＳＳが２．２μｍとなってしまう。Here, the manufacturing conditions and analytical values of the composite carbides of test numbers 10 and 11 are shown in FIG. As shown in FIG. 5, the FSSS of the composite carbide of test number 10 is 1.0 μm or less, but the FSSS of the composite carbide of test number 11 is 2.2 μm.
【００４１】上述の実施例では、酸化タングステンとし
て粒度０．７５μｍに粉砕したものを用いたが、化学処
理を施した粒度０．３μｍの酸化タングステンを用いて
も試験番号１及び１０と同様な特性を有する複合炭化物
が得られる。このような化学処理を施した酸化タングス
テンを得るには、例えば、タングステン酸アンモニウム
溶液を塩酸分解してタングステン酸を得、このタングス
テン酸を焙焼して酸化物を得ている。In the above embodiment, the tungsten oxide pulverized to a particle size of 0.75 μm was used, but the same characteristics as those of Test Nos. 1 and 10 can be obtained even if a chemically treated tungsten oxide having a particle size of 0.3 μm is used. A composite carbide having is obtained. To obtain tungsten oxide that has been subjected to such a chemical treatment, for example, an ammonium tungstate solution is decomposed with hydrochloric acid to obtain tungstic acid, and the tungstic acid is roasted to obtain an oxide.
【００４２】加えて、１次処理温度を１４５０℃乃至１
６００℃、２次処理温度を１７５０℃乃至１９００℃と
すれば、同様な特性を有する複合炭化物が得られること
がわかった。In addition, the primary treatment temperature is 1450 ° C. to 1
It has been found that when the secondary treatment temperature is 600 ° C. and 1750 ° C. to 1900 ° C., a composite carbide having similar characteristics can be obtained.
【００４３】上述の実施例において、造粒ペレットに整
粒して処理した理由は、回転炉内で転がり易くするため
であり、また、回転炉を使用することによって、反応ガ
ス（ＣＯガス）の除去が迅速になされ、炭素量及び窒素
量のばらつきが少なく、しかも酸素量の少ない複合炭窒
化物を得ることができる。In the above-mentioned embodiment, the reason why the granulated pellets are sized and treated is to make them easily rolled in the rotary furnace, and by using the rotary furnace, the reaction gas (CO gas) It is possible to obtain a composite carbonitride that is rapidly removed, has a small variation in carbon content and nitrogen content, and has a small oxygen content.
【００４４】１次処理を窒素気流中で行うことによっ
て、微粒のＴｉＣＮとＷＣとを製造してこれら粒子の固
溶拡散距離を小さくすることができる。アルゴンガスを
使用しても同様に微粒のＴｉＣＮとＷＣとを製造するこ
とができるが、コスト面を考慮すると望ましくない。ま
た、水素気流中ではＷＯ3 がＨ2 と反応する結果、Ｈ2
Ｏが生成され、炉内の異常摩耗及び炭素量の変動が発生
してしまい好ましくない。By carrying out the primary treatment in a nitrogen stream, fine particles of TiCN and WC can be produced and the solid solution diffusion distance of these particles can be shortened. Similarly, fine particles of TiCN and WC can be produced by using argon gas, but this is not desirable in terms of cost. Moreover, as a result of the reaction of WO 3 with H 2 in a hydrogen stream, H 2
O is generated, which causes abnormal wear in the furnace and variation in the carbon content, which is not preferable.
【００４５】１次処理温度が１４５０℃未満では１次処
理後における酸素含有量が２．０重量％以上となってし
まい、２次処理において脱酸素を行うためには２０００
℃以上の温度で処理しなければならず、このような温度
で２次処理を行うと複合炭化物において粒成長が発生し
てしまう。また、１次処理温度が１６００℃を越える
と、（Ｔｉ・Ｗ）ＣＮの固溶体が生成され、２次処理に
おいて脱窒素することが困難となってしまう。If the primary treatment temperature is less than 1450 ° C., the oxygen content after the primary treatment will be 2.0% by weight or more, and 2000 will be necessary for deoxidation in the secondary treatment.
The treatment must be performed at a temperature of not less than 0 ° C., and if the secondary treatment is performed at such a temperature, grain growth will occur in the composite carbide. Further, when the primary treatment temperature exceeds 1600 ° C., a solid solution of (Ti · W) CN is formed, and it becomes difficult to denitrify in the secondary treatment.
【００４６】２次処理を真空中で行う理由は脱窒素及び
脱酸素処理のためである。水素気流中で処理を行うと、
脱窒素は行われるが、脱酸素を十分に行うことができな
い。アルゴンガス中で処理を行ってもよいが、コスト面
で不利である。The reason why the secondary treatment is carried out in vacuum is for denitrification and deoxidation treatment. When processed in a hydrogen stream,
Although denitrification is performed, deoxidation cannot be sufficiently performed. Although the treatment may be performed in argon gas, it is disadvantageous in terms of cost.
【００４７】２次処理温度が１７５０℃未満では脱窒素
処理及び固溶体化が十分ではなく、また、２次処理温度
が１９００℃を越えると、粒成長が急速に進行して好ま
しくない。If the secondary treatment temperature is lower than 1750 ° C., denitrification treatment and solid solution treatment are not sufficient, and if the secondary treatment temperature exceeds 1900 ° C., grain growth proceeds rapidly, which is not preferable.
【００４８】なお、複合炭化物中に窒素が０．１重量％
以上含まれると、真空焼結においては合金表面に軟化相
（１０乃至１００μｍ程度）が生成され、耐摩耗性が低
下してしまう。このため、複合炭化物中の窒素量は０．
１重量％未満とする必要がある。It should be noted that the composite carbide contains 0.1% by weight of nitrogen.
If included, a softening phase (about 10 to 100 μm) is generated on the alloy surface in vacuum sintering, and wear resistance is reduced. Therefore, the amount of nitrogen in the composite carbide is 0.
It should be less than 1% by weight.
【００４９】また、上述の実施例では（Ｔｉ・Ｗ）Ｃの
複合炭化物について説明したが、（Ｔｉ・Ｔａ）Ｃ、
（Ｔｉ・Ｔａ・Ｗ）Ｃ、（Ｔｉ・Ｔａ・Ｎｂ・Ｗ）Ｃ等
の複合炭化物についても同様に本発明を適用することが
できる。つまり、IVａ族（例えば、Ｚｒ、Ｈｆ）、Ｖａ
族（例えば、Ｖ、Ｎｂ、Ｔａ）、及びVIａ族（例えば、
Ｃｒ、Ｍｏ）の酸化物粉末の少なくとも一種を加えても
同様の特性を有する複合炭化物が得られることがわかっ
た。In the above-mentioned embodiment, the composite carbide of (Ti.W) C is explained, but (Ti.Ta) C,
The present invention can be similarly applied to composite carbides such as (Ti.Ta.W) C and (Ti.Ta.Nb.W) C. That is, IVa group (eg, Zr, Hf), Va
Group (eg, V, Nb, Ta), and Group VIa (eg,
It has been found that a composite carbide having similar properties can be obtained even if at least one of oxide powders of Cr and Mo) is added.
【００５０】加えて、ＷＯ3 としてはその粒径が０．３
μｍ乃至１．５μｍであることが望ましく、ＴｉＯ2 粉
末はその粒径が０．１μｍ乃至１．０μｍであることが
望ましい。In addition, WO 3 has a particle size of 0.3.
The particle size of the TiO 2 powder is preferably 0.1 μm to 1.0 μm.
【００５１】ところで、粉砕機によって原料を粉砕する
際、不可避的に鉄分及びコバルトが混入するが、上述の
実施例で製造された複合炭化物固溶体は不純物として含
まれる鉄及びコバルトがともに０．０２重量％以下であ
り、しかも酸素及び窒素の含有量がそれぞれ０．２重量
％以下及び０．０３重量％以下であって、粒径が１μｍ
以下の均粒である。そして、このような複合炭化物固溶
体は焼結性がよく、例えば、切削性能の優れた鋼切削用
超硬合金を得ることができる。By the way, when the raw material is pulverized by a pulverizer, iron and cobalt are inevitably mixed in. However, in the composite carbide solid solution produced in the above-mentioned embodiment, both iron and cobalt contained as impurities are 0.02 wt. % Or less, the oxygen and nitrogen contents are 0.2 wt% or less and 0.03 wt% or less, respectively, and the particle size is 1 μm.
The following is the average particle size. Then, such a composite carbide solid solution has good sinterability, and for example, a cemented carbide for steel cutting having excellent cutting performance can be obtained.
【００５２】[0052]
【発明の効果】以上説明したように本発明によれば、均
粒微細でしかも高純度で固溶化の優れた複合炭化物固溶
体を得ることができるばかりでなく、低コストでしかも
量産化を実現できるという効果がある。そして、本発明
による複合炭化物粉末は焼結性がよく、その結果、例え
ば、切削性能の優れた鋼切削用超硬合金を得ることが可
能となる。As described above, according to the present invention, not only a composite carbide solid solution having a uniform grain size, high purity and excellent solid solution can be obtained, but also low cost and mass production can be realized. There is an effect. The composite carbide powder according to the present invention has good sinterability, and as a result, for example, it becomes possible to obtain a cemented carbide for steel cutting having excellent cutting performance.
【図１】本発明の製造方法による複合炭化物を他の製造
条件で製造された複合炭化物とともにその分析値を示す
図である。FIG. 1 is a diagram showing an analysis value of a composite carbide produced by a production method of the present invention together with a composite carbide produced under other production conditions.
【図２】図１に示す試験番号１の複合炭化物の粒子構造
を示す電子顕微鏡写真（拡大率５０００倍）である。FIG. 2 is an electron micrograph (magnification: 5000 times) showing the particle structure of the composite carbide of test number 1 shown in FIG.
【図３】図１に示す試験番号８の複合炭化物の粒子構造
を示す電子顕微鏡写真（拡大率５０００倍）である。FIG. 3 is an electron micrograph (magnification: 5000 times) showing the particle structure of the composite carbide of test number 8 shown in FIG.
【図４】図１に示す試験番号９の複合炭化物の粒子構造
を示す電子顕微鏡写真（拡大率５０００倍）である。FIG. 4 is an electron micrograph (magnification: 5000 times) showing the particle structure of the composite carbide of test number 9 shown in FIG.
【図５】本発明の製造方法による複合炭化物を他の製造
条件で製造された複合炭化物とともにその分析値を示す
図である。FIG. 5 is a diagram showing the analysis values of the composite carbide produced by the production method of the present invention together with the composite carbide produced under other production conditions.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年６月２２日[Submission date] June 22, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図１[Name of item to be corrected] Figure 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図１】 [Figure 1]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図５[Name of item to be corrected] Figure 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図５】 [Figure 5]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 湊 嘉洋 兵庫県伊丹市昆陽北１丁目１番１号 住友 電気工業株式会社伊丹製作所内 (72)発明者 森 茂芳 兵庫県伊丹市昆陽北１丁目１番１号 住友 電気工業株式会社伊丹製作所内 (72)発明者 山本 英司 兵庫県伊丹市昆陽北１丁目１番１号 住友 電気工業株式会社伊丹製作所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kayo Minato 1-1-1 Kunyokita, Itami City, Hyogo Prefecture Sumitomo Electric Industries, Ltd. Itami Works (72) Inventor Shigeyoshi Mori 1-1 Kunyo Kita, Itami City, Hyogo Prefecture No. 1 Sumitomo Electric Industries, Ltd. Itami Works (72) Inventor Eiji Yamamoto 1-1-1 Kunyokita, Itami City, Hyogo Prefecture Sumitomo Electric Industries Itami Works
Claims (6)
及び炭素粉末を混合してバインダーを用いてペレット状
に成形する第１の工程と、該ペレットを回転炉を用いて
窒素気流中において温度１４５０℃乃至１６００℃で処
理して１次処理物を得る第２の工程と、該１次処理物を
真空中で温度１７５０℃乃至１９００℃で処理して複合
炭化物固溶体を得る第３の工程とを有することを特徴と
する微粒複合炭化物固溶体の製造方法。1. A tungsten oxide powder, a TiO 2 powder,
And a first step of mixing carbon powder and forming a pellet using a binder, and treating the pellet at a temperature of 1450 ° C to 1600 ° C in a nitrogen stream using a rotary furnace to obtain a primary treated product. A method for producing a fine-grain composite carbide solid solution, which comprises a second step and a third step of treating the primary treated product in vacuum at a temperature of 1750 ° C to 1900 ° C to obtain a complex carbide solid solution.
及び炭素粉末とIVａ族酸化物粉末、Ｖａ族酸化物粉末、
及びVIａ族酸化物粉末の少なくとも一種とを混合してバ
インダーを用いてペレット状に成形する第１の工程と、
該ペレットを回転炉を用いて窒素気流中において温度１
４５０℃乃至１６００℃で処理して１次処理物を得る第
２の工程と、該１次処理物を真空中で温度１７５０℃乃
至１９００℃で処理して複合炭化物固溶体を得る第３の
工程とを有することを特徴とする微粒複合炭化物固溶体
の製造方法。2. A tungsten oxide powder, a TiO 2 powder,
And carbon powder and IVa group oxide powder, Va group oxide powder,
And a first step of mixing at least one of Group VIa oxide powders and forming into pellets using a binder,
The pellets were heated at a temperature of 1 in a nitrogen stream using a rotary furnace.
A second step of treating at 450 ° C. to 1600 ° C. to obtain a primary treated material, and a third step of treating the primary treated material in vacuum at a temperature of 1750 ° C. to 1900 ° C. to obtain a composite carbide solid solution. A method for producing a fine-grained composite carbide solid solution, which comprises:
よって製造された複合炭化物固溶体であって、粒径が１
μｍ以下でしかも均粒であり、酸素の含有量が０．２重
量％以下、窒素の含有量が０．０３重量％以下、鉄の含
有量が０．０２重量％以下、コバルトの含有量が０．０
２重量％以下であることを特徴とする微粒複合炭化物固
溶体。3. A composite carbide solid solution produced by the production method according to claim 1 or 2, having a particle size of 1
The content of oxygen is 0.2 μ% or less, the content of nitrogen is 0.03 wt% or less, the content of iron is 0.02 wt% or less, and the content of cobalt is 0.0
A fine-grained composite carbide solid solution, which is 2% by weight or less.
化物固溶体の製造方法において、前記酸化タングステン
粉末はその粒径が０．３μｍ乃至１．５μｍであり、前
記ＴｉＯ2 粉末はその粒径が０．１μｍ乃至１．０μｍ
であることを特徴とする微粒複合炭化物固溶体の製造方
法。4. The method for producing a fine-grain composite carbide solid solution according to claim 1, wherein the tungsten oxide powder has a particle size of 0.3 μm to 1.5 μm, and the TiO 2 powder has a particle size. Is 0.1 μm to 1.0 μm
And a method for producing a fine-grained composite solid solution of carbide.
溶体の製造方法において、前記酸化タングステン粉末は
粉砕機を用いて微粉末化されていることを特徴とする微
粒複合炭化物固溶体の製造方法。5. The method for producing a fine grain composite carbide solid solution according to claim 4, wherein the tungsten oxide powder is pulverized using a pulverizer.
溶体の製造方法において、前記酸化タングステン粉末は
化学処理によって微粉末化されていることを特徴とする
微粒複合炭化物固溶体の製造方法。6. The method for producing a fine-grain composite carbide solid solution according to claim 4, wherein the tungsten oxide powder is finely divided by a chemical treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5135216A JP2700988B2 (en) | 1993-05-14 | 1993-05-14 | Fine-grained composite carbide solid solution and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5135216A JP2700988B2 (en) | 1993-05-14 | 1993-05-14 | Fine-grained composite carbide solid solution and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06321519A true JPH06321519A (en) | 1994-11-22 |
| JP2700988B2 JP2700988B2 (en) | 1998-01-21 |
Family
ID=15146552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5135216A Expired - Fee Related JP2700988B2 (en) | 1993-05-14 | 1993-05-14 | Fine-grained composite carbide solid solution and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2700988B2 (en) |
-
1993
- 1993-05-14 JP JP5135216A patent/JP2700988B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2700988B2 (en) | 1998-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4097275A (en) | Cemented carbide metal alloy containing auxiliary metal, and process for its manufacture | |
| CN1254339C (en) | Sinter-active metal and alloy powders for powder metallurgy applications and methods for their production and their use | |
| EP2098482A1 (en) | Silicon alloy and its powder, production apparatus, production process, and sinter | |
| EP1144147B2 (en) | METHOD FOR PRODUCING METAL POWDERS BY REDUCTION OF THE OXIDES, Nb AND Nb-Ta POWDERS AND CAPACITOR ANODE OBTAINED THEREWITH | |
| EP2055412A2 (en) | Metal powders produced by the reduction of the oxides with gaseous magnesium | |
| CN110102752B (en) | Solid solution alloy powder for metal ceramic and preparation method thereof | |
| CN109336612B (en) | Preparation method of superfine titanium carbonitride powder | |
| JP6802180B2 (en) | Composite carbonitride powder and its manufacturing method | |
| KR101691410B1 (en) | Method for Preparing Titanium Carbonitride Powder | |
| JP2617140B2 (en) | Ultrafine WC powder and method for producing the same | |
| JP6912238B2 (en) | Manufacturing method of fine tungsten carbide powder | |
| JPS6289803A (en) | Powdery particle for fine granular hard alloy and its production | |
| CN113493191B (en) | Method for preparing high-purity alpha-silicon nitride powder and high-purity alpha-silicon nitride powder | |
| Asada et al. | Particle size of fine grain WC by the ‘continuous direct carburizing process’ | |
| EP3712109B1 (en) | Powder containing tungsten carbide | |
| CN1485450A (en) | Method for producing WC-Fe composite powder of ultra fine grain by tungsten alloy scrap | |
| JP3413625B2 (en) | Method for producing titanium carbonitride powder | |
| CN101663237B (en) | Method for producing carbide and/or conposite carbide of transition metal | |
| JP2008031016A (en) | Tantalum carbide powder, tantalum carbide-niobium composite powder and their production method | |
| JP6953157B2 (en) | Fine Tungsten Carbide Powder | |
| JP2700988B2 (en) | Fine-grained composite carbide solid solution and method for producing the same | |
| CN106573775A (en) | Novel process and product | |
| JP2958851B2 (en) | Method for producing fine chromium carbide | |
| JP2007045670A (en) | Manufacturing method of metal carbide | |
| JP2593112B2 (en) | Method for producing composite carbonitride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19970826 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |