JP2000204404A - Production of regenerated tungsten - cobalt raw powder from cemented carbide scrap, and production of tangsten base sintered heavy alloy obtained by this production - Google Patents
Production of regenerated tungsten - cobalt raw powder from cemented carbide scrap, and production of tangsten base sintered heavy alloy obtained by this productionInfo
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- JP2000204404A JP2000204404A JP795099A JP795099A JP2000204404A JP 2000204404 A JP2000204404 A JP 2000204404A JP 795099 A JP795099 A JP 795099A JP 795099 A JP795099 A JP 795099A JP 2000204404 A JP2000204404 A JP 2000204404A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- production
- cemented carbide
- raw powder
- scrap
- 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.)
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Classifications
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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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＷＣ−Ｃｏ系超硬
スクラップからの再生Ｗ−Ｃｏ原料粉末の製造方法、お
よびそれを用いたタングステン基焼結重合金の製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a recycled W-Co raw material powder from a WC-Co-based superhard scrap and a method for producing a tungsten-based sintered heavy metal using the same.
【０００２】[0002]
【従来の技術】超硬合金の主原料となるＷ、Ｔａ、Ｃｏ
等は高価な工業材料であって、世界的にも稀少資源とさ
れている。2. Description of the Related Art W, Ta, Co, which are the main raw materials of cemented carbide,
Are expensive industrial materials, and are regarded as rare resources worldwide.
【０００３】近年の省資源化傾向の中で、これらレアメ
タルの有効利用を目的とした超硬合金スクラップの回収
およびその再利用方法（リサイクル）が検討されてお
り、従来より、ＷＣ−Ｃｏ系超硬スクラップの再利用に
関しては、亜鉛処理法、化学処理法、コールドストリー
ム法、高熱処理法、アルカリ溶解法等、種々の方法が提
案されている。[0003] With the recent trend toward resource saving, collection and reuse of hard metal scrap for the purpose of effective use of these rare metals has been studied. Regarding the reuse of hard scrap, various methods such as a zinc treatment method, a chemical treatment method, a cold stream method, a high heat treatment method, and an alkali dissolution method have been proposed.
【０００４】これらの再利用処理方法の概要を説明すれ
ば、亜鉛処理法は、溶融亜鉛が超硬合金Ｃｏ結合相と容
易に合金を形成するという性質を利用した方法で、超硬
合金の粉砕が容易であるという利点があるが、得られた
粉体は依然としてＷＣであって、本質的には超硬合金の
組成を変えるものではないので、タングステン基焼結合
金の原料としては利用できない。且つ、残留亜鉛の蒸発
等の後処理が必要であるためコスト高である。[0004] The outline of these recycling treatment methods is as follows. The zinc treatment method is a method utilizing the property that molten zinc easily forms an alloy with a cemented carbide Co bonding phase. However, since the obtained powder is still WC and does not essentially change the composition of the cemented carbide, it cannot be used as a raw material for a tungsten-based sintered alloy. In addition, since post-treatment such as evaporation of residual zinc is required, the cost is high.
【０００５】また、コールドストリーム法は、低温脆性
を利用して衝撃破砕する方法で、同様に超硬合金の組成
を変えるものではないので、タングステン基焼結合金の
原料としては利用できない。且つ、冷媒のコストも高
い。Further, the cold stream method is a method of impact crushing utilizing low-temperature brittleness, and does not similarly change the composition of a cemented carbide, and cannot be used as a raw material for a tungsten-based sintered alloy. In addition, the cost of the refrigerant is high.
【０００６】また、カーボン添加高熱処理法は、カーボ
ン添加の状態で２０００℃近く加熱し、冷却する方法
で、タングステン基焼結合金の原料として利用できな
い。且つ、２０００℃近くの加熱を行うため、エネルギ
ーコストが高い。In addition, the carbon-added high heat treatment method is a method of heating and cooling near 2000 ° C. with carbon added, and cannot be used as a raw material for a tungsten-based sintered alloy. In addition, since heating is performed at about 2000 ° C., energy costs are high.
【０００７】また、化学処理法は、焙焼−湿式処理を行
うもので、純度の高いタングステン粉が得られるが、歩
留まりが悪いためコスト高である。In the chemical treatment method, roasting-wet treatment is performed, and a tungsten powder having high purity can be obtained, but the cost is high due to poor yield.
【０００８】以上のように、これらの再利用処理方法の
多くは、超硬原料粉末の形態で再生するか、あるいは、
構成成分をそれぞれ抽出するための方法であって、酸処
理等の化学的プロセスや溶融等の冶金的なプロセスを伴
うことから、再生プロセスが複雑化し、工業的量産に不
向きであってコスト高であるという共通した問題を有し
ていた。As described above, most of these recycling methods involve regenerating in the form of cemented carbide raw material powder,
It is a method for extracting each component, and involves a chemical process such as acid treatment and a metallurgical process such as melting, so that the regeneration process is complicated, unsuitable for industrial mass production, and high cost. Had a common problem.
【０００９】[0009]
【発明が解決しようとする課題】ところで、近年、地球
環境や公害に対する規制が年々厳しくなり、人体に有害
な鉛含有高比重部品の廃止、これに替わる代替品が大き
な課題となっている。前記Ｗ合金は人体無害の高比重金
属であり、係るＰｂ合金の代替えとして注目されている
が、上記処理法の問題よりＷ合金の原料コストがＰｂよ
り遥かに高くなり、これが代替え実用化に際しての大き
な妨げとなっている。By the way, in recent years, regulations on the global environment and pollution have become stricter year by year, and the abolition of lead-containing high-specific-gravity parts harmful to the human body and the replacement thereof have become a major issue. The W alloy is a high specific gravity metal that is harmless to the human body, and is attracting attention as a substitute for the Pb alloy. However, due to the above-described processing method, the raw material cost of the W alloy is much higher than that of Pb. It is a major hindrance.
【００１０】本発明は、ＷＣ−Ｃｏ系超硬スクラップか
ら再生Ｗ−Ｃｏ原料粉末を得るための好適な方法と、こ
の再生Ｗ−Ｃｏ原料粉末を用いた低コストのタングステ
ン基焼結合金の製造方法を提供することを目的としたも
のである。The present invention provides a method for obtaining a recycled W-Co raw material powder from a WC-Co cemented carbide scrap, and a method for producing a low-cost tungsten-based sintered alloy using the recycled W-Co raw material powder. It is intended to provide a method.
【００１１】[0011]
【課題を解決するための手段】本発明は、ＷＣ−Ｃｏ系
超硬スクラップを低コストのタングステン基重合金の原
料として再利用することにより、上記課題を解決するも
のである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems by reusing WC-Co-based superhard scrap as a raw material for low-cost tungsten-based heavy metal.
【００１２】即ち、本発明では、ＷＣ−Ｃｏ系超硬スク
ラップは、ＷＣ主体＋Ｃｏ結合相の組成が主であるが、
酸化性雰囲気中において６００〜１０００℃の温度範囲
で加熱することにより、容易にＷＣ＋ＣｏからＷＯ3 お
よびＣｏＷＯ4 に変えることができる。That is, in the present invention, the composition of the WC-Co-based cemented carbide is mainly composed of a WC main body and a Co binder phase.
By heating in an oxidizing atmosphere at a temperature in the range of 600 to 1000 ° C., WC + Co can be easily changed to WO 3 and CoWO 4 .
【００１３】上記酸化処理にて得られたＷＯ3 とＣｏＷ
Ｏ4 の混合物はスタンプミルやボールミル等によって簡
単に酸化粗粉に粉砕（一次粉砕という）することができ
る。また、この一次粉砕時の平均粒径を６００μｍ以下
（より好ましくは２００μｍ以下）とすると、次工程の
還元処理を効率的、且つ安定的に行うことができる。WO 3 and CoW obtained by the above oxidation treatment
The O 4 mixture can be easily pulverized into oxidized coarse powder by a stamp mill, a ball mill or the like (referred to as primary pulverization). When the average particle size at the time of the primary pulverization is 600 μm or less (more preferably, 200 μm or less), the reduction treatment in the next step can be performed efficiently and stably.
【００１４】一次粉砕して得られた酸化粗粉を水素含有
雰囲気中において６００〜１０００℃の温度範囲で還元
処理することによって、Ｗ＋Ｃｏを主体とする還元粉末
が得られる。得られた還元粉を再粉砕（二次粉砕とい
う）し、微粉末化（平均粒径５μｍ以下が望ましい）す
ることにより、再生Ｗ−Ｃｏ原料粉末を製造することが
できる。本再生処理プロセスは単純で、容易に且つ効率
的な微粉末化が達成でき、工業的量産による低コスト化
が実現できるものである。By subjecting the oxidized coarse powder obtained by the primary pulverization to a reduction treatment in a hydrogen-containing atmosphere at a temperature in the range of 600 to 1000 ° C., a reduced powder mainly composed of W + Co is obtained. The regenerated W-Co raw material powder can be produced by re-pulverizing the obtained reduced powder (referred to as secondary pulverization) and pulverizing the powder (preferably having an average particle diameter of 5 μm or less). The present regeneration process is simple, can easily and efficiently achieve fine powdering, and can realize cost reduction by industrial mass production.
【００１５】また、本発明では、上記のように還元粉を
二次粉砕した後、定量分析を行い、使用目的に応じ前記
再生Ｗ−Ｃｏ原料粉末にＷ粉、Ｎｉ粉、Ｃｏ粉、Ｃｕ
粉、Ｆｅ粉、Ｍｏ粉等を添加して所定の組成になるよう
に調整し、ボールミルにより粉砕・混合・造粒し、圧粉
体にプレス成形した後、焼結することにより安価なタン
グステン基焼結重合金を製造するものである。Further, in the present invention, after the reduced powder is secondarily pulverized as described above, quantitative analysis is performed, and depending on the purpose of use, W powder, Ni powder, Co powder, Cu powder are added to the recycled W-Co raw material powder.
Powder, Fe powder, Mo powder, etc. are added to adjust to a predetermined composition, ground, mixed, and granulated by a ball mill, pressed into a green compact, and then sintered to obtain an inexpensive tungsten base. This is for producing sintered heavy metal.
【００１６】[0016]
【発明の実施の形態】本発明は、ＷＣ−Ｃｏ系超硬スク
ラップを気相反応である酸化−還元法を用いて酸化・還
元する再生Ｗ−Ｃｏ原料粉末の製造法、およびそれらを
用いたタングステン基焼結重合金の製造方法に係わるも
のである。BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a method for producing a recycled W-Co raw material powder for oxidizing and reducing WC-Co-based cemented carbide by an oxidation-reduction method which is a gas phase reaction, and to use the same. The present invention relates to a method for producing a tungsten-based sintered heavy alloy.
【００１７】以下、図１に基づいて本発明の実施形態を
説明する。図１は、本発明に係る再生Ｗ−Ｃｏ原料粉末
の製造工程図である。An embodiment of the present invention will be described below with reference to FIG. FIG. 1 is a production process diagram of a recycled W-Co raw material powder according to the present invention.
【００１８】本工程図によれば、先ず、ＷＣ主体＋５〜
１０％Ｃｏ系超硬スクラップを耐熱ステンレス、あるい
はセラミックス容器に充填し、６００〜１０００℃の酸
化性雰囲気中で加熱することにより、酸化処理を行う。
この時の酸化性雰囲気は常圧、望ましくは、加圧された
酸素ガス、水蒸気、大気の何れかを用いる。特に、酸化
性雰囲気を加圧することにより酸化速度が促進され、効
果的な酸化処理が行える。また、酸化助剤として超硬ス
クラップ中に硝酸ソーダ等のアルカリ類または塩類を少
量添加することにより、酸化速度をさらに促進できる。According to this process chart, first, WC main body +5
An oxidation treatment is performed by filling a 10% Co-based carbide scrap into a heat-resistant stainless steel or ceramic container and heating it in an oxidizing atmosphere at 600 to 1000 ° C.
At this time, the oxidizing atmosphere is at normal pressure, preferably, any of pressurized oxygen gas, water vapor, and air. In particular, when the oxidizing atmosphere is pressurized, the oxidation rate is accelerated, and an effective oxidation treatment can be performed. The oxidation rate can be further enhanced by adding a small amount of an alkali or salt such as sodium nitrate to the cemented carbide scrap as an oxidation aid.
【００１９】また、酸化炉は通常のバッチ型加熱炉が使
用可能であるが、回転式の加熱炉を使用して、酸化され
剥離した酸化粉を連続的に採取できるようにすると効率
的である。係る酸化処理により、容易にＷＣ＋ＣｏをＷ
Ｏ3 およびＣｏＷＯ4 に変えることができる。Although an ordinary batch type heating furnace can be used as the oxidation furnace, it is efficient if a rotary heating furnace is used so that oxidized and separated oxide powder can be continuously collected. . WC + Co can be easily converted to W
It can be changed to O 3 and CoWO 4 .
【００２０】ここで、酸化温度について検討すると、６
００℃以下の酸化性雰囲気中では酸化速度が極端に緩慢
となり、十分な酸化物が得られないこと、また、１００
０℃以上では酸化物の焼結が進み、後工程の一次粉砕が
困難になること等の理由から、好適温度範囲を６００〜
１０００℃としたが、より好ましくは７００〜９００℃
の範囲に設定すると良い。図２に上記酸化温度における
酸化時間と酸化粉回収率のとの関係を示す。尚、本図
は、酸化炉として密閉型バッチ炉を使用し、且つ、酸化
性雰囲気として２ｋｇ／ｃｍ2 に加圧の酸素ガスを用い
た場合の特性を示している。Here, when examining the oxidation temperature, 6
In an oxidizing atmosphere at a temperature of 00 ° C. or less, the oxidation rate becomes extremely slow, and a sufficient oxide cannot be obtained.
If the temperature is 0 ° C. or higher, the sintering of the oxide proceeds, and the primary pulverization in the subsequent step becomes difficult.
1000 ° C., more preferably 700-900 ° C.
It is good to set in the range. FIG. 2 shows the relationship between the oxidation time at the oxidation temperature and the oxide powder recovery rate. This figure shows the characteristics when a closed batch furnace is used as the oxidation furnace and oxygen gas pressurized to 2 kg / cm 2 is used as the oxidizing atmosphere.
【００２１】次に、前記酸化処理にて得られたＷＯ3 ＋
ＣｏＷＯ4 主体の酸化粉を通常の機械式スタンプミル、
ボールミル、またはジョークラッシャ、ロールクラッシ
ャを用いて常温大気中で一次粉砕し、還元用の粗粉とす
る。この一次粉砕時の平均粒径は６００μｍ以下、より
好ましくは２００μｍ以下とすることにより、次工程の
還元処理を確実、且つ効率的に行える。Next, the WO 3 + obtained by the oxidation treatment
CoWO 4 mainly oxidized powder is converted into a normal mechanical stamp mill,
It is first ground in a normal temperature atmosphere using a ball mill, a jaw crusher, or a roll crusher to obtain a coarse powder for reduction. By setting the average particle size at the time of the primary pulverization to 600 μm or less, more preferably 200 μm or less, the reduction treatment in the next step can be performed reliably and efficiently.
【００２２】次いで、一次粉砕して得られた酸化粗粉を
６００〜１０００℃の水素含有雰囲気中で還元処理し、
Ｗ＋Ｃｏ主体の還元粉末を得る。この時の還元雰囲気
は、１００％水素が最も望ましいが、７５％水素含有の
アンモニア分解ガスでも良い。尚、還元炉は通常のバッ
チ炉、あるいはブッシャ式連続炉が使用可能である。Next, the oxidized coarse powder obtained by primary pulverization is reduced in a hydrogen-containing atmosphere at 600 to 1000 ° C.,
A reduced powder mainly composed of W + Co is obtained. The reducing atmosphere at this time is most preferably 100% hydrogen, but may be an ammonia decomposition gas containing 75% hydrogen. As the reduction furnace, a normal batch furnace or a busher-type continuous furnace can be used.
【００２３】ここで、還元温度について検討すると、既
述した酸化処理の場合と同様、６００℃以下の還元性雰
囲気中では還元速度が極端に緩慢となり、残留酸素量が
多くなるため、高純度のＷ＋Ｃｏ粉末が得られないこ
と、また、１０００℃以上では還元粉の焼結が進み、後
工程の二次粉砕が困難になること等の理由から、好適な
還元雰囲気温度を６００〜１０００℃に設定したが、よ
り好ましくは７００〜９００℃である。Considering the reduction temperature, as in the case of the above-described oxidation treatment, the reduction rate becomes extremely slow in a reducing atmosphere at 600 ° C. or lower, and the amount of residual oxygen increases. A suitable reducing atmosphere temperature is set to 600 to 1000 ° C. because W + Co powder cannot be obtained, and sintering of the reduced powder proceeds at 1000 ° C. or higher, and secondary pulverization in the subsequent step becomes difficult. However, the temperature is more preferably 700 to 900 ° C.
【００２４】次いで、前記したＷ＋Ｃｏ主体の還元粉末
をボールミルにて平均粒径５μｍ以下の微粉末に再粉砕
（二次粉砕という）した後、定量分析による組成同定を
行い、使用目的に応じてＷ粉、Ｎｉ粉、Ｃｏ粉、Ｃｕ
粉、Ｆｅ粉、Ｍｏ粉等を添加して組成調整した後、混
合、造粒などの工程を経て、タングステン基焼結重合金
の原料を得ることができる。Next, the above-mentioned reduced powder mainly composed of W + Co is re-pulverized into a fine powder having an average particle diameter of 5 μm or less (referred to as secondary pulverization) by a ball mill, and the composition is identified by quantitative analysis. Powder, Ni powder, Co powder, Cu
After adjusting the composition by adding powder, Fe powder, Mo powder, and the like, a raw material of tungsten-based sintered heavy metal can be obtained through steps such as mixing and granulation.
【００２５】尚、本実施形態では、超硬合金チップのス
クラップ再生について説明したが、その他、上記超硬合
金チップの作製時に発生する超硬合金用素材スクラップ
や超硬合金回収粉塵等のスクラップ再生に際しても勿論
適用可能である。In this embodiment, the description has been given of the scrap recycling of the cemented carbide chip. However, in addition to the above, the scrap recycling such as the cemented carbide material scrap and the dust collected from the cemented carbide generated when the cemented carbide chip is manufactured. In this case, it is of course applicable.
【００２６】[0026]
【実施例】次に、本発明の実施例を説明する。Next, an embodiment of the present invention will be described.
【００２７】実施例１ １０×１０×５ｍｍ程度の大きさのＷＣ−６％Ｃｏ系超
硬合金チップ状スクラップ１００Ｋｇを耐熱ステンレス
製炉体が備えた回転型電気加熱炉内に充填し、空気を連
続送風しながら通電昇温し、９００℃の酸化性雰囲気中
で約２時間加熱・酸化し、得られた酸化物をスタンプミ
ルにて約１５分間粉砕（一次粉砕）して表１に示すよう
な粒度分布のＷＯ3 ＋ＣｏＷＯ4 酸化粗粉を得た。Example 1 A rotary electric heating furnace equipped with a heat-resistant stainless steel furnace was charged with 100 kg of WC-6% Co cemented carbide chip-shaped scrap having a size of about 10 × 10 × 5 mm, and was filled with air. The temperature was increased while applying continuous air, heated and oxidized in an oxidizing atmosphere at 900 ° C. for about 2 hours, and the obtained oxide was pulverized (primary pulverization) with a stamp mill for about 15 minutes, as shown in Table 1. WO 3 + CoWO 4 oxidized coarse powder having an excellent particle size distribution was obtained.
【表１】 次に、前記ＷＯ3 ＋ＣｏＷＯ4 酸化粗粉を耐熱ステンレ
ス製トレーに充填し、アンモニア分解ガス（７５％Ｈ2
＋２５％Ｎ2 ）による９００℃の還元性囲気中にて約４
時間還元処理を行い、得られた還元粉をボールミルにて
約５時間再粉砕（二次粉砕）して平均粒径が５μｍ前後
のＷ−Ｃｏ粉末を得た。[Table 1] Next, the WO 3 + CoWO 4 oxidized coarse powder was filled in a heat-resistant stainless steel tray, and ammonia decomposition gas (75% H 2
+ 25% N 2 ) in a reducing atmosphere at 900 ° C. for about 4
The resulting reduced powder was re-ground (secondary grinding) for about 5 hours in a ball mill to obtain a W-Co powder having an average particle size of about 5 μm.
【００２８】このようにして得られたＷ−Ｃｏ粉末は、
Ｃｏが６．３重量％で、残りの殆どがＷであって、残留
酸素は０．６０重量％以下、残留トータル・炭素量は
０．１重量％以下といったような高品質の微粉末である
ことが確認された。The W-Co powder thus obtained is
Co is 6.3% by weight, most of the remaining is W, high quality fine powder with residual oxygen of 0.60% by weight or less and residual total carbon content of 0.1% by weight or less. It was confirmed that.
【００２９】次いで、この再生Ｗ−Ｃｏ粉末にＮｉ粉３
重量％と、Ｃｕ粉２重量％を添加して混合・造粒し、６
ｔｏｎ／ｃｍ2 の圧力で圧粉体にプレス成形した後、ブ
ッシャ型連続焼結炉により、１４００〜１４５０℃のア
ンモニア分解ガス中で約２５分間焼結・冷却し、焼結体
（タングステン基焼結重合金）を得た。Next, Ni powder 3 was added to the recycled W-Co powder.
2% by weight of Cu powder and 2% by weight of Cu powder.
After press-molding into a green compact at a pressure of ton / cm 2 , it is sintered and cooled in an ammonia decomposition gas at 1400 to 1450 ° C. for about 25 minutes by a busher-type continuous sintering furnace to obtain a sintered body (tungsten-based sintered). (Coupling gold).
【００３０】この焼結体は、密度が１７．０ｇ／ｃｍ3
以上、ビーカッス硬さが３００以上、抗折強度が１５０
Ｋｇ／ｍｍ2 以上が得られており、これは、通常のＷ粉
を用いた同組成のタングステン基焼結重合金と比べても
特性的に何ら劣るものではなく、人体無害の高比重部品
として、例えば、自動車のホイルバランサ、ダイキャス
ト用成形金型、或いは携帯電話機の振動子等に適用する
ことにより、従来の鉛含有高比重部品の代替えとして十
分使用に供し得るものである。This sintered body has a density of 17.0 g / cm 3.
As described above, the Beakus hardness is 300 or more, and the bending strength is 150
Kg / mm 2 or more is obtained, which is not inferior in characteristics even when compared with tungsten-based sintered heavy alloy of the same composition using ordinary W powder, and as a high specific gravity part harmless to the human body. For example, when applied to a wheel balancer of an automobile, a molding die for die casting, a vibrator of a mobile phone, or the like, it can be sufficiently used as a substitute for a conventional lead-containing high specific gravity part.
【００３１】実施例２ １０×１０×５ｍｍ程度の大きさのＷＣ−６％Ｃｏ系超
硬合金チップ状スクラップ１０Ｋｇずつを耐熱ステンレ
ス製トレーに載せて密閉型酸化炉内に充填し、２Ｋｇ／
ｃｍ2 まで加圧した酸素ガスを導入しながら通電昇温
し、９００℃の酸化性雰囲気中で約２４時間加熱・酸化
し、得られた酸化物を１００℃以下まで冷却した後、ス
タンプミルにて約１５分間粉砕して表２に示すような粒
度分布のＷＯ3 ＋ＷＣｏＯ4 酸化粗粉を得た。Example 2 10 kg of WC-6% Co cemented carbide chip-shaped scrap having a size of about 10 × 10 × 5 mm was placed on a heat-resistant stainless steel tray and charged into a closed oxidation furnace.
The temperature was increased while introducing oxygen gas pressurized to 2 cm 2, heated and oxidized in an oxidizing atmosphere at 900 ° C. for about 24 hours, and the obtained oxide was cooled to 100 ° C. or less, and then was subjected to a stamp mill. And crushed for about 15 minutes to obtain WO 3 + WCoO 4 oxidized coarse powder having a particle size distribution as shown in Table 2.
【表２】 次に、このＷＯ3 ＋ＷＣｏＯ4 酸化粗粉を前記実施例１
と同様の還元処理を行い５μｍ前後のＷ−Ｃｏ粉末を得
た。この場合も、残留酸素は０．６０重量％以下、残留
トータル・炭素量は０．１重量％以下、Ｃｏは６．３重
量％含有、残りがＷで、実施例１と同様に高品質の微粉
末が再生できた。[Table 2] Next, this WO 3 + WCoO 4 oxidized coarse powder was used in Example 1 described above.
The same reduction treatment as described above was performed to obtain a W-Co powder of about 5 μm. Also in this case, the residual oxygen is 0.60% by weight or less, the residual total carbon content is 0.1% by weight or less, Co contains 6.3% by weight, and the balance is W. Fine powder could be regenerated.
【００３２】また、この再生Ｗ−Ｃｏ粉末を用いた焼結
体も前記実施例１と同様の特性が得られた。The sintered body using the recycled W-Co powder also had the same characteristics as in the first embodiment.
【００３３】[0033]
【発明の効果】以上説明したように、請求項１に記載の
発明によれば、超硬合金スクラップから再生Ｗ−Ｃｏ原
料粉末を製造するに際し、ＷＣ−Ｃｏ系超硬合金スクラ
ップを６００℃以上の酸化性雰囲気中で酸化した後、一
次粉砕を行い、さらに、６００〜１０００℃の水素含有
還元性雰囲気中でＷ−Ｃｏ粉に還元した後、二次粉砕を
行って微粉末化するようにしたので、従来実施されてい
た諸処理方法に伴う複雑な化学的、あるいは冶金的プロ
セスを無くし、再生処理プロセスを単純化できるため、
容易に且つ効率的に高品質の微粉末化が達成でき、工業
的量産による低コストが実現可能となる。As described above, according to the first aspect of the present invention, when producing the recycled W-Co raw material powder from the cemented carbide scrap, the WC-Co-based cemented carbide scrap is heated to 600 ° C. or more. After oxidizing in an oxidizing atmosphere, primary pulverization is performed, and further reduced to W-Co powder in a hydrogen-containing reducing atmosphere at 600 to 1000 ° C., and then secondary pulverized to be finely pulverized. As a result, the complicated chemical or metallurgical processes involved in the various treatment methods conventionally used can be eliminated, and the regeneration process can be simplified.
High quality pulverization can be achieved easily and efficiently, and low cost can be realized by industrial mass production.
【００３４】また、請求項２に記載の発明によれば、前
記再生Ｗ−Ｃｏ粉を焼結することのより、低コストのタ
ングステン基焼結重合金を製造することができる。この
タングステン基焼結重合金は通常のＷ粉を用いた同組成
の超硬合金と比べて特性的にも何等遜色はなく、低コス
トの高比重部品として自動車のホイルバランサ、ダイキ
ャスト用金型材、或いは携帯電話機の振動子等の用途に
好適であり、従来の鉛含有高比重部品の代替品として十
分使用に供し得るものである。Further, according to the second aspect of the present invention, by sintering the recycled W-Co powder, a low cost tungsten-based sintered heavy metal can be manufactured. This tungsten-based sintered heavy alloy is not inferior in characteristics to ordinary cemented carbide of the same composition using W powder, and is a low-cost, high-specific-gravity part for automobile wheel balancers and die-casting mold materials. Alternatively, it is suitable for applications such as a vibrator of a mobile phone, and can be sufficiently used as a substitute for a conventional lead-containing high specific gravity part.
【図１】本発明に係る再生Ｗ−Ｃｏ原料粉末の製造工程
を示す図である。FIG. 1 is a view showing a process for producing a recycled W—Co raw material powder according to the present invention.
【図２】超硬チップスクラップの酸化処理時間と酸化粉
回収率の関係を示す図である。FIG. 2 is a diagram showing the relationship between the oxidation treatment time of carbide chip scrap and the oxide powder recovery rate.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年１１月２５日（１９９９．１１．
２５）[Submission date] November 25, 1999 (1999.11.
25)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１１】[0011]
【課題を解決するための手段】本発明は、ＷＣ−Ｃｏ系
超硬スクラップを低コストのタングステン基重合金の原
料として再利用することにより、上記課題を解決するも
のであり、請求項１に記載の発明は、ＷＣ−Ｃｏ系超硬
合金スクラップを６００〜１０００℃の酸化性雰囲気中
で酸化した後、一次粉砕を行い平均粒径を６００μｍ以
下とし、さらに、６００〜１０００℃の水素含有還元性
雰囲気中でＷ−Ｃｏ粉に還元した後、二次粉砕を行って
微粉末化することを特徴とするものである。この際に、
請求項２に記載の発明は、上記酸化を、７００℃〜９０
０℃の酸化性雰囲気中で行なった後に、平均粒径が２０
０μｍ以下となるように一次粉砕することを特徴とする
ものである。また、請求項３に記載の発明は、ＷＣ−Ｃ
ｏ系超硬合金スクラップを６００〜１０００℃の酸化性
雰囲気中で酸化した後、一次粉砕を行い平均粒径を６０
０μｍ以下とし、さらに６００〜１０００℃の水素含有
還元性雰囲気中でＷ−Ｃｏ粉に還元した後、二次粉砕を
行って微粉末化してＷ−Ｃｏ原料粉末を再生し、次い
で、この再生Ｗ−Ｃｏ原料粉末を使用することを特徴と
するものであり、さらに請求項４に記載の発明は、上記
酸化を、７００℃〜９００℃の酸化性雰囲気中で行なっ
た後に、平均粒径が２００μｍ以下となるように一次粉
砕することを特徴とするものである。 The present invention SUMMARY OF], by reusing the WC-Co-based cemented carbide scrap as a low-cost tungsten-based polymer alloy of the starting state, and are not to solve the above problems, according to claim 1 The invention described in (1) is a WC-Co based carbide
Alloy scrap in an oxidizing atmosphere at 600 to 1000 ° C
After primary oxidation, primary pulverization is performed to reduce the average particle size to 600 μm or less.
Below, and hydrogen-containing reducing property at 600-1000 ° C
After reducing to W-Co powder in the atmosphere, secondary grinding is performed
It is characterized by being pulverized. At this time,
In the invention according to claim 2, the oxidation is performed at a temperature of 700 ° C to 90 ° C.
After performing in an oxidizing atmosphere at 0 ° C., the average particle size is 20
The primary pulverization is performed so as to be 0 μm or less.
Things. The third aspect of the present invention provides a WC-C
O-based cemented carbide scrap is oxidizable at 600-1000 ° C
After being oxidized in an atmosphere, primary pulverization is performed to obtain an average particle size of 60.
0 μm or less, and further containing hydrogen at 600 to 1000 ° C.
After reduction to W-Co powder in a reducing atmosphere, secondary pulverization
To make fine powder to regenerate the W-Co raw material powder,
The use of the recycled W-Co raw material powder is characterized in that
The invention according to claim 4 is the above-mentioned invention.
Oxidation is performed in an oxidizing atmosphere at 700 ° C. to 900 ° C.
After that, the primary powder is adjusted so that the average particle size becomes 200 μm or less.
It is characterized by crushing.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１４】一次粉砕して得られた酸化粗粉を水素含有
雰囲気中において６００〜１０００℃の温度範囲で還元
処理することによって、Ｗ＋Ｃｏを主体とする還元粉末
が得られる。そして、請求項１または２に記載の発明に
よれば、得られた還元粉を再粉砕（二次粉砕という）
し、微粉末化（平均粒径５μｍ以下が望ましい）するこ
とにより、再生Ｗ−Ｃｏ原料粉末を製造することができ
る。本再生処理プロセスは単純で、容易に且つ効果的な
微粉末化が達成でき、工業的量産による低コスト化が実
現できるものである。By subjecting the oxidized coarse powder obtained by the primary pulverization to a reduction treatment in a hydrogen-containing atmosphere at a temperature in the range of 600 to 1000 ° C., a reduced powder mainly composed of W + Co is obtained. The invention according to claim 1 or 2
According to it, the obtained reduced powder is reground (called secondary grinding)
Then, by making the powder into a fine powder (preferably having an average particle diameter of 5 μm or less), a recycled W—Co raw material powder can be produced. The present regeneration process is simple, can easily and effectively achieve fine powdering, and can achieve cost reduction by industrial mass production.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Correction target item name] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１５】また、請求項３または４に係る本発明で
は、上記のように還元粉を二次粉砕した後、定量分析を
行い、使用目的に応じ前記再生Ｗ−Ｃｏ原料粉末にＷ
粉、Ｎｉ粉、Ｃｏ粉、Ｃｕ粉、Ｆｅ粉、Ｍｏ粉等を添加
して所定の組成になるように調整し、ボールミルにより
粉砕・混合・造粒し、圧粉体にプレス成形した後、焼結
することにより安価なタングステン基焼結重合金を製造
するものである。In the present invention according to claim 3 or 4, after the reduced powder is secondarily pulverized as described above, quantitative analysis is performed, and W is added to the recycled W-Co raw material powder according to the purpose of use.
Powder, Ni powder, Co powder, Cu powder, Fe powder, Mo powder, etc. are added to adjust to a predetermined composition, crushed / mixed / granulated by a ball mill, and pressed into a green compact, By sintering, an inexpensive tungsten-based sintered heavy metal is manufactured.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３３[Correction target item name] 0033
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３３】[0033]
【発明の効果】以上説明したように、請求項１または２
に記載の発明によれば、超硬合金スクラップから再生Ｗ
−Ｃｏ原料粉末を製造するに際し、ＷＣ−Ｃｏ系超硬合
金スクラップを６００〜１０００℃の酸化性雰囲気中で
酸化した後、一次粉砕を行い平均粒径を６００μｍ以下
とし、さらに、６００〜１０００℃の水素含有還元性雰
囲気中でＷ−Ｃｏ粉に還元した後、二次粉砕を行って微
粉末化するようにしたので、従来実施されていた諸処理
方法に伴う複雑な化学的、あるいは冶金的プロセスを無
くし、再生処理プロセスを単純化できるため、容易に且
つ効果的に高品質のＷ−Ｃｏ微粉末化が達成でき、工業
的量産による低コストが実現可能となる。As described above, claim 1 or claim 2
According to the invention described in the above, the recycled W from the cemented carbide scrap
-In producing Co raw material powder, WC-Co cemented carbide scrap is oxidized in an oxidizing atmosphere at 600 to 1000 ° C , and then primary pulverized to have an average particle size of 600 µm or less.
And then, further, after reduction to the W-Co powder in a hydrogen containing reducing atmosphere of 600 to 1000 ° C., since such fine powdered performing secondary crushing, due to various processing method which is conventionally carried out Eliminates complicated chemical or metallurgical processes and simplifies the regeneration process, making it possible to easily and effectively achieve high-quality W-Co fine powder, and achieve low cost by industrial mass production. Become.
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３４[Correction target item name] 0034
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３４】また、請求項３または４の記載の発明によ
れば、前記再生Ｗ−Ｃｏ粉を焼結することにより、低コ
ストのタングステン基焼結重合金を製造することができ
る。このタングステン基焼結重合金は通常のＷ粉を用い
た同組成の超硬合金と比べて特性的にも何等遜色はな
く、低コストの高比重部品として自動車のホイルバラン
サ、ダイキャスト用金型材、或いは携帯電話機の振動子
等の用途に好適であり、従来の鉛含有高比重部品の代替
品として十分使用に供し得るものである。According to the third or fourth aspect of the present invention,
Then, by sintering the recycled W-Co powder, a low cost tungsten-based sintered heavy metal can be manufactured. This tungsten-based sintered heavy alloy is not inferior in characteristics to ordinary cemented carbide of the same composition using W powder, and is a low-cost, high-specific-gravity part for automobile wheel balancers and die-casting mold materials. Alternatively, it is suitable for applications such as a vibrator of a mobile phone, and can be sufficiently used as a substitute for a conventional lead-containing high specific gravity part.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２２Ｃ 27/04 １０１ Ｃ２２Ｃ 27/04 １０１ 32/00 32/00 Ｗ // Ｃ２２Ｂ 7/00 Ｃ２２Ｂ 7/00 Ａ (72)発明者 中井 崇 静岡県裾野市千福46番地の１ 株式会社東 富士製作所内 Ｆターム(参考） 4K001 AA07 AA29 BA22 CA15 DA10 4K017 AA04 BA04 BB06 CA07 EA03 EA08 EH01 EH18 FB06 4K018 AA20 BA04 BA09 BB08 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C22C 27/04 101 C22C 27/04 101 32/00 32/00 W // C22B 7/00 C22B 7/00 A (72) Inventor Takashi Nakai 46-1, Chifuku, Susono City, Shizuoka Prefecture F-term in Higashi Fuji Manufacturing Co., Ltd. 4K001 AA07 AA29 BA22 CA15 DA10 4K017 AA04 BA04 BB06 CA07 EA03 EA08 EH01 EH18 FB06 4K018 AA20 BA04 BA09 BB08
Claims (2)
０℃以上の酸化性雰囲気中で酸化した後、一次粉砕を行
い、さらに、６００〜１０００℃の水素含有還元性雰囲
気中でＷ−Ｃｏ粉に還元した後、二次粉砕を行って微粉
末化することを特徴とする超硬合金スクラップからの再
生Ｗ−Ｃｏ原料粉末の製造方法。1. A WC-Co cemented carbide scrap of 60
After being oxidized in an oxidizing atmosphere of 0 ° C. or more, primary pulverization is performed, and further reduced to W—Co powder in a hydrogen-containing reducing atmosphere at 600 to 1000 ° C., and then secondary pulverized to form a fine powder. A method for producing recycled W-Co raw material powder from cemented carbide scrap.
０℃以上の酸化性雰囲気中で酸化した後、一次粉砕を行
い、さらに６００〜１０００℃の水素含有還元性雰囲気
中でＷ−Ｃｏ粉に還元した後、二次粉砕を行って微粉末
化してＷ−Ｃｏ原料粉末を再生し、次いで、この再生Ｗ
−Ｃｏ原料粉末を使用することを特徴とするタングステ
ン基焼結重合金の製造方法。2. A WC-Co cemented carbide scrap of 60
After being oxidized in an oxidizing atmosphere of 0 ° C. or more, primary pulverization is performed, and further reduced to W—Co powder in a hydrogen-containing reducing atmosphere at 600 to 1000 ° C., and then secondary pulverized to be finely pulverized. The W-Co raw material powder is regenerated, and then the regenerated W
-A method for producing tungsten-based sintered heavy metal, characterized by using Co raw material powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP795099A JP3056476B1 (en) | 1999-01-14 | 1999-01-14 | Method for producing recycled W—Co raw material powder from cemented carbide scrap and method for producing tungsten-based sintered heavy alloy using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP795099A JP3056476B1 (en) | 1999-01-14 | 1999-01-14 | Method for producing recycled W—Co raw material powder from cemented carbide scrap and method for producing tungsten-based sintered heavy alloy using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP3056476B1 JP3056476B1 (en) | 2000-06-26 |
| JP2000204404A true JP2000204404A (en) | 2000-07-25 |
Family
ID=11679784
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP795099A Expired - Fee Related JP3056476B1 (en) | 1999-01-14 | 1999-01-14 | Method for producing recycled W—Co raw material powder from cemented carbide scrap and method for producing tungsten-based sintered heavy alloy using the same |
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| JP (1) | JP3056476B1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100700197B1 (en) * | 2005-07-30 | 2007-03-27 | 한국기계연구원 | Process for Manufacturing Sintered Materials Containing Cobalt Component |
| KR101007155B1 (en) | 2008-10-29 | 2011-01-12 | 한국기계연구원 | Fabrication of fine Fe-Ni powder made by oxidation-reduction treatment process using Fe-Ni metal scrap |
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| KR100700197B1 (en) * | 2005-07-30 | 2007-03-27 | 한국기계연구원 | Process for Manufacturing Sintered Materials Containing Cobalt Component |
| KR101007155B1 (en) | 2008-10-29 | 2011-01-12 | 한국기계연구원 | Fabrication of fine Fe-Ni powder made by oxidation-reduction treatment process using Fe-Ni metal scrap |
| US8685137B2 (en) | 2009-10-26 | 2014-04-01 | Minpro Aktiebolag | Recycling of tungsten carbides |
| WO2011053231A1 (en) * | 2009-10-26 | 2011-05-05 | Minpro Aktiebolag | Recycling of tungsten carbides |
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| CN102665973B (en) * | 2009-10-26 | 2014-07-16 | 明普罗公司 | Recycling of tungsten carbides |
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