JP2001152203A - Planar crystal tungsten carbide-containing powder and producing method therefor - Google Patents
Planar crystal tungsten carbide-containing powder and producing method thereforInfo
- Publication number
- JP2001152203A JP2001152203A JP33595299A JP33595299A JP2001152203A JP 2001152203 A JP2001152203 A JP 2001152203A JP 33595299 A JP33595299 A JP 33595299A JP 33595299 A JP33595299 A JP 33595299A JP 2001152203 A JP2001152203 A JP 2001152203A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- tungsten carbide
- tungsten
- carbide
- group metal
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 42
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000013078 crystal Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052721 tungsten Inorganic materials 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 150000001247 metal acetylides Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910017488 Cu K Inorganic materials 0.000 claims 1
- 229910017541 Cu-K Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000011812 mixed powder Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- -1 cermets Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
Landscapes
- Ceramic Products (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、板状晶の炭化タン
グステンを含有させることにより、硬さ，靱性，強度，
耐摩耗性，耐欠損性，耐塑性変形性，耐熱亀裂性に優れ
る硬質焼結材料（超硬合金，サーメット，セラミックス
など）を製作するための原料粉末に適する板状晶炭化タ
ングステン含有粉末およびその製造方法に関するもので
ある。BACKGROUND OF THE INVENTION The present invention relates to a method for improving hardness, toughness, strength,
Tungsten carbide containing powder and suitable for raw material powder for producing hard sintered materials (hard alloys, cermets, ceramics, etc.) with excellent wear resistance, fracture resistance, plastic deformation resistance, and heat crack resistance It relates to a manufacturing method.
【０００２】[0002]
【従来の技術】一般に、超硬合金，サーメット，セラミ
ックスなどに代表される硬質焼結材料は、切削工具，耐
摩耗工具および部品など多種多様の用途に実用されてい
る。この硬質焼結材料では硬さを高めて耐摩耗性を向上
させると靱性が低下して耐欠損性が劣化すると言う問題
がある。硬さと靱性を同時に改善する方法として、ＷＣ
粒子を含有した硬質焼結材料では、ＷＣを板状晶化する
方法が種々提案されている。2. Description of the Related Art In general, hard sintered materials represented by cemented carbides, cermets, ceramics and the like have been used in various applications such as cutting tools, wear-resistant tools and parts. This hard sintered material has a problem that when the hardness is increased to improve the wear resistance, the toughness is reduced and the fracture resistance is deteriorated. As a method for simultaneously improving hardness and toughness, WC
For a hard sintered material containing particles, various methods for plate-forming WC have been proposed.
【０００３】板状晶ＷＣに関する先行技術の代表的なも
のに、特開昭５７−３４００８号公報，特開平７−２４
２９５８号公報，特開平２−４７２３９号公報，特開平
２−１３８４３４号公報，特開平５−３３９６５９号公
報，特開平７−２５２５５５号公報，特開平７−２９２
４２６号公報などがある。[0003] Representative examples of the prior art relating to platelet WC include JP-A-57-34008 and JP-A-7-24.
2958, JP-A-2-47239, JP-A-2-138434, JP-A-5-339659, JP-A-7-252555, JP-A-7-292
No. 426, etc.
【０００４】[0004]
【発明が解決しようとする課題】板状晶ＷＣに関連する
先行技術の内、特開昭５７−３４００８号公報には、強
粉砕したＷとＣとの混合粉末に少量の鉄族金属を添加し
た後、加熱・炭化して（００１）面を双晶面として接合
された双晶炭化タングステンの製造方法について記載さ
れている。同公報に記載されている方法により得られる
粉末は、板状のＷＣ結晶を含有するものの、アスペクト
比（最大径／最小径）が小さくて双晶結晶の含有率も少
ないために、この粉末を原料とした硬質焼結材料の硬さ
および靱性の向上効果が少ないと言う問題がある。Among the prior art related to platelet WC, Japanese Patent Application Laid-Open No. 57-34008 discloses that a small amount of iron group metal is added to a mixed powder of strongly pulverized W and C. After that, a method for producing twin tungsten carbide in which the (001) plane is joined by heating and carbonizing as a twin plane is described. Although the powder obtained by the method described in the publication contains plate-like WC crystals, the powder has a small aspect ratio (maximum diameter / minimum diameter) and a small content of twin crystals. There is a problem that the effect of improving the hardness and toughness of the hard sintered material used as the raw material is small.
【０００５】また、特開平７−２４２９５８号公報に
は、Ｗと炭素とＣｏ，Ｎｉ，Ｃｒの１種以上でなる複合
炭化物を含有した粉末冶金用組成物とその製造方法が記
載されている。同公報に記載されている組成物は、焼結
過程での化学反応により板状晶ＷＣを焼結合金中に含有
させるものではあるが、板状晶ＷＣのアスペクト比，含
有率が低く、また焼結工程での昇温速度，加熱保持の温
度・時間，雰囲気などの焼結条件によってバラツキを生
じ易いために、得られる硬質焼結材料の硬さおよび靱性
の向上効果が少なくて、性能が安定しないと言う問題が
ある。Japanese Patent Application Laid-Open No. Hei 7-242958 describes a powder metallurgy composition containing a composite carbide comprising W, carbon, and at least one of Co, Ni and Cr, and a method for producing the same. Although the composition described in this publication contains platelet WC in a sintered alloy by a chemical reaction in the sintering process, the aspect ratio and content of platelet WC are low. Variations are likely to occur depending on the sintering conditions such as the rate of temperature rise in the sintering process, the temperature and time of heating and holding, and the atmosphere. Therefore, the effect of improving the hardness and toughness of the obtained hard sintered material is small and the performance is low. There is a problem that it is not stable.
【０００６】さらに、特開平２−４７２３９号公報およ
び特開平２−１３８４３４号公報には、炭化タングステ
ンを過飽和に含有した（Ｗ，Ｔｉ，Ｔａ）Ｃの固溶体を
出発原料として、加熱焼結時間に板状晶ＷＣを晶出させ
ると言う超硬合金の製造方法が記載されている。そし
て、特開平５−３３９６５９号公報には、長時間粉砕に
よって得られる０．５μｍ以下のＷＣと３〜４０重量％
の立方晶系化合物と１〜２５重量％のＣｏ，Ｎｉとから
なる混合粉末を焼結すると言う板状晶ＷＣを含有する超
硬合金の製造方法が記載されている。さらには、特開平
７−２５２５５５号公報には、Ｗと炭素とＣｏ，Ｎｉ，
Ｃｒの１種以上でなる複合炭化物あるいはＷ2ＣとＣ
ｏ，Ｎｉ，Ｃｒの１種以上とでなる混合物を含有した出
発原料を焼結すると言う板状晶ＷＣ含有超硬合金の製造
方法が、特開平７−２９２４２６号公報には、結合相形
成粉末（鉄族金属）と炭素源とＷあるいはＷ＋ＷＣとの
混合粉末を加熱・焼結する際、鉄族金属と炭素とＷから
なる複合炭化物を生成させる第１過程と、この複合炭化
物から板状晶ＷＣを生成させる第２過程とからなる板状
晶ＷＣ含有超硬合金の製法が記載されている。これらに
記載された板状晶ＷＣ含有超硬合金の製法は、焼結過程
での晶出，異常粒成長，化学反応などを利用した方法
で、いずれも粉末をプレス成形して嵩密度を上げた後に
焼結するもので、焼結途中で生成する板状晶ＷＣにとっ
て粒成長するための十分な成長空間がないために、板状
晶ＷＣが安定して形成されない、板状晶ＷＣのアスペク
ト比，含有率が低い、得られる超硬合金の組成が限定さ
れる、などの問題がある。Further, JP-A-2-47239 and JP-A-2-138434 disclose that a solid solution of (W, Ti, Ta) C containing tungsten carbide in a supersaturated state is used as a starting material, and the heating and sintering time is reduced. A method for producing a cemented carbide that crystallizes platelet WC is described. JP-A-5-339659 discloses that WC of 0.5 μm or less obtained by long-time pulverization and 3 to 40% by weight are used.
A method for producing a cemented carbide containing a plate-like crystal WC, which sinters a mixed powder consisting of a cubic compound and 1 to 25% by weight of Co and Ni. Further, Japanese Patent Application Laid-Open No. 7-252555 discloses that W, carbon, Co, Ni,
Composite carbides of one or more types of Cr or W 2 C and C
Japanese Patent Application Laid-Open No. 7-292426 discloses a method for producing a plate-shaped WC-containing cemented carbide in which a starting material containing a mixture of at least one of o, Ni, and Cr is sintered. (1) When heating and sintering a mixed powder of (iron group metal), a carbon source, and W or W + WC, a first step of forming a composite carbide composed of iron group metal, carbon, and W, and a plate-like crystal from the composite carbide A method for producing a plate-shaped WC-containing cemented carbide comprising a second step of producing WC is described. The methods for producing plate-shaped WC-containing cemented carbides described in these publications utilize crystallization, abnormal grain growth, and chemical reactions during the sintering process. After the sintering, the platelet WC generated during the sintering does not have a sufficient growth space for grain growth, so that the platelet WC is not stably formed. There are problems such as a low ratio, a low content, and a limited composition of the resulting cemented carbide.
【０００７】本発明は、上記のような問題点を解決した
もので、具体的には、鉄族金属とＷとＣとからなる複合
炭化物，鉄族金属とＷまたはＷ2Ｃ，鉄族金属とＷとか
らなる金属間化合物または合金などと炭素との混合粉末
を、プレス成形などの加圧を行わない嵩密度の低い状態
で加熱処理することにより、板状晶ＷＣのアスペクト比
が大で含有率の高い炭化タングステン粉末を安定的かつ
安価に製造することを可能にし、これを硬質焼結材料に
添加・分散させることにより、硬さと靱性を同時に向上
させることのできる板状晶炭化タングステン含有粉末お
よびその製造方法の提供を目的とする。The present invention has solved the above-mentioned problems, and more specifically, a composite carbide comprising an iron group metal and W and C, an iron group metal and W or W 2 C, an iron group metal By heating a mixed powder of carbon and an intermetallic compound or alloy composed of and W in a state of low bulk density without pressurizing such as press molding, the aspect ratio of platelet WC is large. It is possible to manufacture tungsten carbide powder with high content stably and inexpensively, and by adding and dispersing it to hard sintered material, it can improve hardness and toughness at the same time. It is intended to provide a powder and a method for producing the powder.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、長年に亘
り、硬質焼結材料の硬さと靱性を同時に改善する方法と
そのための原材料粉末について検討していた所、アスペ
クト比の大きな板状晶ＷＣを硬質焼結材料中に分散させ
ると硬さと靱性が同時に向上すること、板状晶ＷＣを硬
質焼結材料中に分散させるには、アスペクト比と含有率
の高い板状晶ＷＣ粉末を一旦製造してから硬質焼結材料
の原料粉として添加することが最適なこと、アスペクト
比と含有率の高い板状晶ＷＣ粉末を得るには、鉄族金属
とＷとＣとの組合せからなる単体あるいは種々の化合物
の混合粉末をプレス成形などの加圧を行わない嵩密度の
低い状態で加熱処理すること、混合粉末の嵩密度が低い
と板状晶ＷＣの核生成後の粒子成長過程で成長空間が十
分にあるためにアスペクト比と含有割合の高い板状晶炭
化タングステン含有粉末が得られると言う知見を得て、
本発明を完成するに至ったものである。SUMMARY OF THE INVENTION The present inventors have studied a method for simultaneously improving the hardness and toughness of a hard sintered material and a raw material powder for the same for many years. When WC is dispersed in a hard sintered material, hardness and toughness are improved at the same time. Once it is manufactured, it is optimal to add it as a raw material powder of a hard sintered material. To obtain a plate-like WC powder having a high aspect ratio and a high content, a combination of iron group metal and W and C is required. A single powder or a mixed powder of various compounds is heat-treated in a state of low bulk density without pressurizing such as press molding. If the bulk density of the mixed powder is low, the particle growth process after nucleation of plate-like crystal WC. Because there is enough growth space, And aspect ratio and high content tabular crystals tungsten carbide-containing powder is obtained a finding that say obtained,
The present invention has been completed.
【０００９】[0009]
【発明の実施の形態】本発明の板状晶炭化タングステン
含有粉末は、炭化タングステンの平均粒子径が０．０１
〜１０μｍであって、最小長さに対する最大長さの比が
３．０以上でなる板状晶ＷＣを炭化タングステン全体に
対して５０体積％以上含有することを特徴とするもので
ある。BEST MODE FOR CARRYING OUT THE INVENTION The plate-like tungsten carbide-containing powder of the present invention has an average particle size of tungsten carbide of 0.01.
The plate-like crystal WC having a ratio of the maximum length to the minimum length of 3.0 μm or more and 3.0 or more is contained by 50% by volume or more based on the whole tungsten carbide.
【００１０】本発明の板状晶炭化タングステン含有粉末
における炭化タングステンの平均粒子径は、０．０１μ
ｍ未満では、添加した硬質焼結材料の焼結過程で異常粒
成長を起こして均一に板状晶ＷＣが分散できず、逆に１
０μｍを超えて大きくなると、硬質焼結材料中で欠陥と
して作用するために強度低下を引き起こすので、０．０
１〜１０μｍと定めた。また、最小長さに対する最大長
さの比（アスペクト比）は、３．０以上未満では硬質焼
結材料での靱性改善効果が低いため３．０以上と定め
た。４〜１０の範囲であることが、より好ましい。さら
に、板状結晶の含有率が５０体積％未満では硬質焼結材
料での硬さと靱性の向上効果が小さいので５０体積％以
上と定めた。The average particle diameter of tungsten carbide in the powder of the present invention containing the plate-like tungsten carbide is 0.01 μm.
If it is less than m, abnormal grain growth occurs during the sintering process of the added hard sintering material, and the plate-like crystal WC cannot be uniformly dispersed.
When the thickness exceeds 0 μm, the strength decreases because it acts as a defect in the hard sintered material.
It was determined as 1 to 10 μm. When the ratio of the maximum length to the minimum length (aspect ratio) is less than 3.0 or more, the effect of improving the toughness of the hard sintered material is low, so that the ratio is set to 3.0 or more. More preferably, it is in the range of 4 to 10. Furthermore, when the content of the plate-like crystal is less than 50% by volume, the effect of improving the hardness and toughness of the hard sintered material is small, so that the content is set to 50% by volume or more.
【００１１】本発明の板状晶炭化タングステン含有粉末
は、板状晶ＷＣも含めた炭化タングステン全体に対して
５０体積％未満が下記の（ａ），（ｂ），（ｃ）の中か
ら選ばれた１種以上であると、硬質焼結材料を製造する
上で組成調整以外に利点となる場合がある。 （ａ）鉄族金属とタングステンと炭素とからなる複合炭
化物の中の１種以上 （ｂ）鉄族金属，タングステン，炭化二タングステンの
中の１種以上 （ｃ）周期律表の４ａ，５ａ，６ａ族金属の炭化物（但
し、炭化タングステンを除く），窒化物，酸化物および
これらの相互固溶体の中の１種以上 具体的な利点として、（ａ）および（ｂ）を含有する
と、焼結過程で反応して板状晶ＷＣのアスペクト比を高
め、（ｃ）を含有すると、焼結過程で板状晶ＷＣの異常
成長を抑制して均一・微細に分散させることができる場
合がある。ここで、（ａ）の複合炭化物として具体的に
は、Ｃｏ3Ｗ9Ｃ4，Ｃｏ2Ｗ4Ｃ，Ｃｏ3Ｗ3Ｃ，Ｃｏ6Ｗ6
Ｃ，Ｎｉ2Ｗ4Ｃ，ＦｅＷ3Ｃ，Ｆｅ4Ｗ2Ｃなどを挙げる
ことができる。また、（ｃ）の立方晶系化合物として、
具体的には、Ｃｒ3Ｃ2，Ｍｏ2Ｃ，ＶＣ，ＮｂＣ，Ｔａ
Ｃ，ＴｉＣ，（ＷＴｉ）Ｃ，（ＷＴｉＴａ）（ＣＮ），
ＴｉＮ，ＴｉＯ，（ＷＴｉ）（ＣＯ） などを挙げるこ
とができる。[0011] In the powder of the present invention, less than 50% by volume of the whole tungsten carbide including the platelet WC is selected from the following (a), (b) and (c). When one or more types are used, there may be advantages other than the composition adjustment in producing a hard sintered material. (A) at least one kind of composite carbide composed of iron group metal, tungsten and carbon; (b) at least one kind of iron group metal, tungsten, and ditungsten carbide; (c) 4a, 5a, One or more of group 6a metal carbides (excluding tungsten carbide), nitrides, oxides, and mutual solid solutions thereof. As a specific advantage, when (a) and (b) are contained, the sintering process When the aspect ratio of the platelet WC is increased to contain (c), the abnormal growth of the platelet WC during the sintering process can be suppressed and the platelet WC can be uniformly and finely dispersed. Here, specifically, as the composite carbide of (a), Co 3 W 9 C 4 , Co 2 W 4 C, Co 3 W 3 C, Co 6 W 6
C, Ni 2 W 4 C, FeW 3 C, Fe 4 W 2 C and the like can be mentioned. Further, as the cubic compound (c),
Specifically, Cr 3 C 2 , Mo 2 C, VC, NbC, Ta
C, TiC, (WTi) C, (WTiTa) (CN),
TiN, TiO, (WTi) (CO) and the like can be mentioned.
【００１２】本発明の板状晶炭化タングステン含有粉末
の炭化タングステンは、Ｃｕ−Ｋα線によるＸ線回折曲
線における（１０１）結晶面のピーク強度をｈ（１０
１）と表し、（００１）結晶面のピーク強度をｈ（００
１）と表したとき、ｈ（００１）／ｈ（１０１）≧０．
６０であると、ＷＣ結晶は（００１）面が最も高硬度で
あるために、硬質焼結材料の硬さがより高まるので好ま
しい。[0012] The tungsten carbide of the plate-like tungsten carbide-containing powder of the present invention has a peak intensity of the (101) crystal plane in the X-ray diffraction curve by Cu-Kα ray of h (10).
1), and the peak intensity of the (001) crystal plane is h (00)
1), h (001) / h (101) ≧ 0.
It is preferable that the WC crystal has a hardness of 60 because the (001) plane has the highest hardness and the hardness of the hard sintered material is further increased.
【００１３】本発明の板状晶炭化タングステン含有粉末
の製法は、下記の（ａ），（ｄ），（ｅ）の中から選ば
れた１種以上の組成物粉末と炭素粉末とを、場合によっ
ては（ｆ）をも混合した後、真空あるいは非酸化性雰囲
気中で１０７３〜１８７３Ｋに加熱することを特徴とす
る製造方法である。 （ａ）鉄族金属とタングステンと炭素とからなる複合炭
化物 （ｄ）鉄族金属とタングステン金属及び／又は炭化二タ
ングステンとの混合物 （ｅ）鉄族金属とタングステンとからなる金属間化合物
および合金 （ｆ）周期律表の４ａ，５ａ，６ａ族金属の炭化物，窒
化物，酸化物およびこれらの相互固溶体[0013] The method for producing the platelet-shaped tungsten carbide-containing powder of the present invention comprises the steps of: preparing a powder of one or more compositions selected from the following (a), (d) and (e); In some cases, after mixing (f), the mixture is heated to 1073 to 1873K in a vacuum or non-oxidizing atmosphere. (A) Composite carbide of iron group metal, tungsten and carbon (d) Mixture of iron group metal and tungsten metal and / or ditungsten carbide (e) Intermetallic compound and alloy of iron group metal and tungsten ( f) Carbides, nitrides, oxides of metals belonging to groups 4a, 5a and 6a of the periodic table and their mutual solid solutions
【００１４】本発明の板状晶炭化タングステン含有粉末
の製法において、（ｅ）の金属間化合物および合金とし
て、具体的には、ＷＣｏ3，Ｗ6Ｃｏ7，ＷＮｉ4などおよ
び２０重量％以上のＷを含有する合金を挙げることがで
きる。また、炭素粉末として、具体的には、黒鉛，カー
ボンブラック，コークス，炭素前駆体などを挙げること
ができ、中でも黒鉛はアスペクト比の高い板状晶ＷＣが
得られるので好ましい。In the method for producing the powder of plate-like tungsten carbide according to the present invention, as the intermetallic compound and alloy (e), specifically, WCo 3 , W 6 Co 7 , WNi 4, etc. An alloy containing W can be given. Specific examples of the carbon powder include graphite, carbon black, coke, and a carbon precursor. Among them, graphite is preferable because a plate-like crystal WC having a high aspect ratio can be obtained.
【００１５】本発明の板状晶炭化タングステン含有粉末
の製法において、粉末の混合は各種混合機で行えるが、
乾式の振動ボールミルであると均一な混合とハンドリン
グが容易なので好ましい。また、混合粉を加熱処理する
際のボート充填は、出来るだけ嵩密度を低くして充填す
ると、粒成長空間が確保されてアスペクト比の大きな板
状晶ＷＣが得られるので好ましい。加熱処理の雰囲気が
真空であると、雰囲気からの反応が抑制され、固相同士
の拡散によって化学反応が進行するために、アスペクト
比の大きな板状晶ＷＣが得られるので好ましい。さら
に、加熱処理の温度は、１０７３Ｋ未満では化学反応が
起こり難くいために未反応物が多く残留し、逆に１８７
３Ｋを超えて高くなると固化して塊状となること、著し
く粗大な粒子となること、アスペクト比が低下するなど
の問題を生じるために、１０７３〜１８７３Ｋと定め
た。[0015] In the method for producing the plate-like tungsten carbide-containing powder of the present invention, the powder can be mixed by various mixers.
A dry vibrating ball mill is preferable because uniform mixing and handling are easy. In addition, it is preferable to fill the boat with the heat treatment of the mixed powder by lowering the bulk density as much as possible, since a grain growth space is secured and a plate-like crystal WC having a large aspect ratio is obtained. It is preferable that the atmosphere of the heat treatment be a vacuum because a reaction from the atmosphere is suppressed and a chemical reaction proceeds by diffusion between solid phases, so that a plate-like crystal WC having a large aspect ratio is obtained. Further, when the temperature of the heat treatment is less than 1073 K, a large amount of unreacted substances remains because a chemical reaction is unlikely to occur.
If the temperature is higher than 3K, solidification becomes a mass, extremely coarse particles are formed, and the aspect ratio is reduced.
【００１６】[0016]
【作用】本発明の板状晶炭化タングステン含有粉末およ
びその製造方法は、鉄族金属とＷとＣとからなる複合炭
化物，鉄族金属とＷまたはＷ2Ｃ，鉄族金属とＷとから
なる金属間化合物または合金などと炭素との混合粉末
が、加熱により化学反応を起こして板状晶ＷＣを形成す
る作用をし、混合粉末をプレス成形せずに嵩密度を低く
して充填することが、生成した板状晶ＷＣの成長に伴う
合体を阻止してアスペクト比の大きな板状晶ＷＣを高い
割合で含有させる炭化タングステンを形成する作用を
し、得られた板状晶炭化タングステン含有粉末が硬質焼
結材料に添加することにより硬さと靱性を同時に改善す
る作用をしているものである。According to the present invention, there is provided a powdered tungsten carbide containing platelet and a method for producing the same, comprising a composite carbide comprising an iron group metal and W and C, an iron group metal and W or W 2 C, and an iron group metal and W. A mixed powder of carbon and an intermetallic compound or alloy acts to form a plate-like crystal WC by causing a chemical reaction by heating, and it is possible to fill the mixed powder with low bulk density without press molding. The platelet-like tungsten carbide-containing powder acts to prevent the coalescence accompanying the growth of the platelet-like WC formed and to form tungsten carbide containing a large proportion of the platelet-like WC having a large aspect ratio. When added to a hard sintered material, it functions to simultaneously improve hardness and toughness.
【００１７】[0017]
【実施例１】市販されている平均粒子径が１．２μｍの
Ｃｏ2Ｗ4Ｃ，０．５μｍのＷ（Ｗ1と記す），３．０μ
ｍのＷ（Ｗ2と記す），２．３μｍのＷ2Ｃ，３．４μｍ
のＷ 2Ｆｅ3，１．２μｍのＣｏ，１．７μｍのＮｉ，
０．０２μｍのカーボンブラック（Ｃと記す），５．５
μｍの黒鉛（Ｇと記す），１．７μｍのＣｒ3Ｃ2，０．
５μｍのＶＣ，１．０μｍのＴａＣ，１．５μｍの（Ｗ
ＴｉＴａ）Ｃの複合炭化物（重量比でＷＣ／ＴｉＣ／Ｔ
ａＣ＝５０／２０／３０），０．０７μｍのＴｉＯ2の
各粉末を用い、表１に示した配合組成に秤量して、ステ
ンレス製ポットに鉄製ボールと共に装入して振動ボール
ミル機を用いて乾式で２時間混合した。この混合粉末を
１００＃の篩を通過させて解した後、黒鉛製ルツボに粗
に挿入し、表１に併記した雰囲気と温度で１時間の加処
理を行って、本発明品１〜１０および比較品１〜６を得
た。但し、比較品２の混合は他と異なり、ステンレス製
ポットにアセトン溶媒と超硬合金製ボールと共に挿入
し、７２時間の混合粉砕を行った後、乾燥して混合粉末
を得た。また、比較品５は、得られた混合粉末を金型に
充填し、１９６ＭＰａの圧力でプレス成形して圧粉成形
体とした後に加熱処理を行った。Example 1 Commercially available particles having an average particle diameter of 1.2 μm
CoTwoWFourC, 0.5 μm W (W13.0 μ)
m W (WTwo), W of 2.3 μmTwoC, 3.4 μm
W TwoFeThree, 1.2 μm Co, 1.7 μm Ni,
0.02 μm carbon black (denoted as C), 5.5
μm graphite (denoted as G), 1.7 μm CrThreeCTwo, 0.
5 μm VC, 1.0 μm TaC, 1.5 μm (W
TiTa) C composite carbide (WC / TiC / T in weight ratio)
aC = 50/20/30), 0.07 μm TiOTwoof
Each powder was weighed to the composition shown in Table 1 and
Vibration ball inserted in a stainless steel pot together with an iron ball
The mixture was dry-mixed for 2 hours using a mill. This mixed powder
After passing through a 100 # sieve and unraveling, coarsely put into a graphite crucible.
And treated for 1 hour at the atmosphere and temperature described in Table 1.
To obtain inventive products 1 to 10 and comparative products 1 to 6
Was. However, the mixture of the comparative product 2 is different from the others and made of stainless steel
Insert acetone solvent and cemented carbide ball into pot
And after mixing and grinding for 72 hours, dry and mix powder
I got Comparative product 5 is obtained by mixing the obtained mixed powder in a mold.
Filling, press molding with pressure of 196MPa and compacting
After the body was formed, a heat treatment was performed.
【００１８】[0018]
【表１】 注） ＊ 比較品２は混合の方法条件が異なる ＊＊比
較品５は圧粉成形体[Table 1] Note) * Comparative product 2 has different mixing method conditions ** Comparative product 5 is a green compact
【００１９】こうして得た本発明品１〜１０及び比較品
１〜６の加熱処理粉末（但し、比較品４は塊状、比較品
５は焼結体）を解砕し、一部の粉末を走査電子顕微鏡に
よる観察とＸ線回折を行った。写真撮影と画像処理装置
によって測定したＷＣの平均粒径と全ＷＣに対する板状
晶ＷＣ（最長径／最短径の比が３以上）の体積割合を表
２に示す。また、Ｘ線回折での内部標準法を用いた成分
組成とＷＣのピーク比：ｈ（００１）／ｈ（１０１）を
求め、その結果を表２に併記した。The heat-treated powders of the present invention products 1 to 10 and comparative products 1 to 6 (comparative product 4 is a lump, comparative product 5 is a sintered body) are crushed, and a part of the powder is scanned. Observation with an electron microscope and X-ray diffraction were performed. Table 2 shows the average particle diameter of WC and the volume ratio of platelet WC (the ratio of longest diameter / shortest diameter of 3 or more) to all WC measured by photography and an image processing apparatus. In addition, the composition ratio of the component and the peak ratio of WC using the internal standard method in X-ray diffraction: h (001) / h (101) were determined, and the results are also shown in Table 2.
【００２０】[0020]
【表２】 [Table 2]
【００２１】[0021]
【実施例２】実施例１で得られた本発明品５および９の
粉末を５％塩酸水溶液に１時間浸した後、洗浄し、乾燥
して本発明品１１および１２の粉末を得た。実施例１に
記載した方法で粉末特性を測定した結果、Ｃｏが除去さ
れている以外は同一であった。Example 2 The powders of the present invention products 5 and 9 obtained in Example 1 were immersed in a 5% aqueous hydrochloric acid solution for 1 hour, washed and dried to obtain the powders of the present invention products 11 and 12. The powder properties were measured by the method described in Example 1 and were the same except that Co was removed.
【００２２】[0022]
【実施例３】次に、実施例１で使用したＣｏ，（ＷＴｉ
Ｔａ）Ｃ，Ｃｒ３Ｃ２，ＶＣ、実施例１で得られた本発
明品１，２，３，８および比較品１，２，３、実施例２
で得られた本発明品１１、市販されている平均粒子径が
１．５μｍのＷＣの各粉末を用いて、表３に示す配合組
成に秤量し、ステンレス製ポットにアセトン溶媒と超硬
合金製ボールと共に挿入し、１２時間混合粉砕後、乾燥
して混合粉末を得た。これらの粉末を金型に充填し、１
９６ＭＰａの圧力でもって約５．５×９．５×２９ｍｍ
の圧粉成形体を作製し、アルミナとカーボン繊維からな
るシート上に設置し、雰囲気圧力１０Ｐａの真空中で、
表３に併記した温度でもって１時間加熱保持して、本発
明による試料Ａ〜Ｅと比較用の試料Ａ〜Ｅを得た。[Embodiment 3] Next, Co, (WTi
Ta) C, Cr3C2, VC, products 1, 2, 3, and 8 of the present invention obtained in Example 1, and comparative products 1, 2, 3, and Example 2.
The product 11 of the present invention obtained in the above was weighed to the composition shown in Table 3 using each commercially available WC powder having an average particle size of 1.5 μm, and the acetone solvent and the cemented carbide alloy were placed in a stainless steel pot. It was inserted together with a ball, mixed and pulverized for 12 hours, and dried to obtain a mixed powder. A mold is filled with these powders, and 1
About 5.5 × 9.5 × 29mm with 96MPa pressure
Is prepared and placed on a sheet made of alumina and carbon fiber, and in a vacuum at an atmospheric pressure of 10 Pa,
The sample was heated and held at the temperature shown in Table 3 for 1 hour to obtain samples A to E according to the present invention and samples A to E for comparison.
【００２３】[0023]
【表３】 [Table 3]
【００２４】こうして得た本発明によるＡ〜Ｅおよび比
較用によるＡ〜Ｅの焼結合金を＃２３０のダイヤモンド
砥石で湿式研削加工し、４．０×８．０×２５．０ｍｍ
の形状に作製し、ＪＩＳ法による抗折力を測定して、そ
の結果を表４に示した。また、同試料の１面を０．３μ
ｍのダイヤモンドペーストでラップ加工した後、ビッカ
ース圧子を用いた荷重：１９６Ｎでの硬さおよび破壊靱
性値Ｋ1C（ＩＭ法）を測定し、その結果を表４に併記し
た。さらに、各試料のラップ面について電子顕微鏡にて
組織写真を撮り、画像処理装置を使用してＷＣの平均粒
径と全ＷＣに対する板状晶ＷＣ（最長径／最短径の比が
３以上）の体積割合を測定した。結果を表４に併記し
た。The thus obtained sintered alloys A to E according to the present invention and A to E according to the comparative example are wet-ground with a # 230 diamond grindstone to obtain 4.0 × 8.0 × 25.0 mm.
And the bending force was measured by the JIS method. The results are shown in Table 4. In addition, one side of the same sample was 0.3 μm.
After lapping with a diamond paste of m, the hardness and the fracture toughness value K1C (IM method) at a load of 196 N using a Vickers indenter were measured, and the results are also shown in Table 4. Further, a photograph of the structure of the lap surface of each sample was taken with an electron microscope, and the average particle size of WC and the ratio of platelet WC to the total WC (the ratio of longest diameter / shortest diameter was 3 or more) were measured using an image processing apparatus. The volume ratio was measured. The results are shown in Table 4.
【００２５】[0025]
【表４】 [Table 4]
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G001 BA12 BA13 BA24 BA37 BA60 BA61 BA67 BC11 BC13 BC54 BD18 4K018 AD06 BA04 BA09 BA11 BB01 BB04 KA14 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G001 BA12 BA13 BA24 BA37 BA60 BA61 BA67 BC11 BC13 BC54 BD18 4K018 AD06 BA04 BA09 BA11 BB01 BB04 KA14
Claims (4)
タングステン粉末において、最小長さに対する最大長さ
の比が３．０以上でなる板状結晶を５０体積％以上含有
することを特徴とする板状晶炭化タングステン含有粉
末。1. A tungsten carbide powder having an average particle diameter of 0.01 to 10 μm, wherein 50% by volume or more of a plate-like crystal having a ratio of a maximum length to a minimum length of 3.0 or more is contained. Powder containing tungsten carbide.
タングステンを５０体積％以上含有し、残りが下記の
（ａ），（ｂ），（ｃ）の中から選ばれた１種以上でな
る炭化タングステン含有粉末において、該炭化タングス
テンは最小長さに対する最大長さの比が３．０以上でな
る板状結晶を炭化タングステン全体に対して５０体積％
以上含有することを特徴とする板状晶炭化タングステン
含有粉末。 （ａ）鉄族金属とタングステンと炭素とからなる複合炭
化物の中の１種以上 （ｂ）鉄族金属，タングステン，炭化二タングステンの
中の１種以上 （ｃ）周期律表の４ａ，５ａ，６ａ族金属の炭化物（但
し、炭化タングステンを除く），窒化物，酸化物および
これらの相互固溶体の中の１種以上2. It contains at least 50% by volume of tungsten carbide having an average particle diameter of 0.01 to 10 μm, and the remainder is at least one selected from the following (a), (b) and (c): In the tungsten carbide-containing powder, the tungsten carbide has a plate-like crystal having a ratio of a maximum length to a minimum length of 3.0 or more in a volume ratio of 50% by volume to the whole tungsten carbide.
A powder containing platelet-shaped tungsten carbide, characterized by containing the above. (A) at least one kind of composite carbide composed of iron group metal, tungsten and carbon; (b) at least one kind of iron group metal, tungsten, and ditungsten carbide; (c) 4a, 5a, At least one of carbides of group 6a metals (excluding tungsten carbide), nitrides, oxides and mutual solid solutions thereof
α線によるＸ線回折曲線における（１０１）結晶面のピ
ーク強度をｈ（１０１）と表し、（００１）結晶面のピ
ーク強度をｈ（００１）と表したとき、ｈ（００１）／
ｈ（１０１）≧０．６０であることを特徴とする請求項
１又は２記載の板状晶炭化タングステン含有粉末。3. The method according to claim 1, wherein the tungsten carbide powder is Cu-K
When the peak intensity of the (101) crystal plane in the X-ray diffraction curve by α-rays is represented by h (101) and the peak intensity of the (001) crystal plane is represented by h (001), h (001) /
The plate-like tungsten carbide-containing powder according to claim 1, wherein h (101) ≧ 0.60.
選ばれた１種以上の組成物粉末と炭素粉末とを、場合に
よっては（ｆ）をも混合した後、真空あるいは非酸化性
雰囲気中で１０７３〜１８７３Ｋに加熱することを特徴
とする請求項１，２又は３記載の板状晶炭化タングステ
ン含有粉末の製造方法。 （ａ）鉄族金属とタングステンと炭素とからなる複合炭
化物 （ｄ）鉄族金属とタングステン金属及び／又は炭化二タ
ングステンとの混合物 （ｅ）鉄族金属とタングステンとからなる金属間化合物
および合金 （ｆ）周期律表の４ａ，５ａ，６ａ族金属の炭化物，窒
化物，酸化物およびこれらの相互固溶体4. After mixing at least one kind of composition powder selected from the following (a), (d) and (e) with carbon powder, and possibly mixing (f), vacuum 4. The method for producing plate-like tungsten carbide-containing powder according to claim 1, wherein the powder is heated to 1073 to 1873K in a non-oxidizing atmosphere. (A) Composite carbide of iron group metal, tungsten and carbon (d) Mixture of iron group metal and tungsten metal and / or ditungsten carbide (e) Intermetallic compound and alloy of iron group metal and tungsten ( f) Carbides, nitrides, oxides of metals belonging to groups 4a, 5a and 6a of the periodic table and their mutual solid solutions
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33595299A JP4165850B2 (en) | 1999-11-26 | 1999-11-26 | Plate-like tungsten carbide-containing powder and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33595299A JP4165850B2 (en) | 1999-11-26 | 1999-11-26 | Plate-like tungsten carbide-containing powder and method for producing the same |
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| JP2001152203A true JP2001152203A (en) | 2001-06-05 |
| JP4165850B2 JP4165850B2 (en) | 2008-10-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008522027A (en) * | 2005-06-27 | 2008-06-26 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | Sintered cemented carbide using vanadium as gradient forming element |
| CN113699406A (en) * | 2021-08-30 | 2021-11-26 | 四川轻化工大学 | High-strength and high-toughness extra-coarse-grain WC hard alloy with average grain size larger than 8 microns and preparation method thereof |
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1999
- 1999-11-26 JP JP33595299A patent/JP4165850B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008522027A (en) * | 2005-06-27 | 2008-06-26 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | Sintered cemented carbide using vanadium as gradient forming element |
| JP4842962B2 (en) * | 2005-06-27 | 2011-12-21 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | Sintered cemented carbide using vanadium as gradient forming element |
| CN113699406A (en) * | 2021-08-30 | 2021-11-26 | 四川轻化工大学 | High-strength and high-toughness extra-coarse-grain WC hard alloy with average grain size larger than 8 microns and preparation method thereof |
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| JP4165850B2 (en) | 2008-10-15 |
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