JPH07252555A - Production of sintered cemented carbide containing plate wc - Google Patents
Production of sintered cemented carbide containing plate wcInfo
- Publication number
- JPH07252555A JPH07252555A JP6069978A JP6997894A JPH07252555A JP H07252555 A JPH07252555 A JP H07252555A JP 6069978 A JP6069978 A JP 6069978A JP 6997894 A JP6997894 A JP 6997894A JP H07252555 A JPH07252555 A JP H07252555A
- Authority
- JP
- Japan
- Prior art keywords
- plate
- substance
- cemented carbide
- carbide
- shaped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000000203 mixture Substances 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 239000011812 mixed powder Substances 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 46
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- -1 or W 2 C and WC Co Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 description 12
- 239000007858 starting material Substances 0.000 description 11
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910000599 Cr alloy Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 229910001080 W alloy Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012733 comparative method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 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
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、板状ＷＣ結晶の晶出し
た超硬合金を作製するための板状ＷＣ含有超硬合金の製
造方法に関し、具体的には、超硬合金中に板状ＷＣ結晶
を晶出させることにより、硬さ，靭性，耐摩耗性，耐欠
損性，耐塑性変形性，耐熱亀裂性に優れるようにしたバ
イト，ドリル，エンドミルに代表される切削工具、絞り
型，しごき型，鍛造型などの組成加工工具や打抜き型，
スリッターなどの剪断加工工具に代表される耐摩耗工
具、メカニカルシールや軸受けに代表される摺動材料、
時計側，タイピン，釣具部品に代表される耐腐食・装飾
材料および各種の精密機械部品に代表される構造材料を
作製するための最適な方法となる板状ＷＣ含有超硬合金
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 plate-shaped WC-containing cemented carbide for producing a plate-shaped WC crystallized cemented carbide. A cutting tool typified by a bite, a drill, an end mill, and a drawing die that are made to have excellent hardness, toughness, wear resistance, fracture resistance, plastic deformation resistance, and heat crack resistance by crystallizing a WC-shaped crystal. ， Composite processing tools such as ironing dies and forging dies and punching dies,
Abrasion resistant tools typified by shearing tools such as slitters, sliding materials typified by mechanical seals and bearings,
A method for producing a plate-shaped WC-containing cemented carbide, which is an optimal method for producing a corrosion-resistant / decorative material typified by a watch side, a tie pin, a fishing tackle part, and a structural material typified by various precision machine parts Is.
【０００２】[0002]
【従来の技術】一般に、金属化合物の硬質相と金属の結
合相とでなる超硬合金は、多種多用の用途に実用されて
いる。この従来の超硬合金は、硬さを高めて耐摩耗性を
向上させると靭性の低下および耐欠損性の劣下が生じ、
逆に靭性および耐欠損性を高めると硬さおよび耐摩耗性
が低下するという二律背反的傾向を示すという問題があ
る。この問題を解決するものとしての提案が多数行われ
ている。2. Description of the Related Art Generally, a cemented carbide composed of a hard phase of a metal compound and a binding phase of a metal is put to practical use for various purposes. In this conventional cemented carbide, when hardness is increased to improve wear resistance, toughness is reduced and fracture resistance is deteriorated.
On the contrary, when the toughness and the fracture resistance are increased, there is a problem that the hardness and the wear resistance decrease, which shows an antinomy tendency. Many proposals have been made to solve this problem.
【０００３】これらの提案の１つの方向として、ＷＣの
結晶面による機械的特性の異方性について注目したも
の、具体的には、例えばＷＣ結晶の（００１）面が最高
硬さで、（１００）面方向が最高弾性率を示すことか
ら、（１００）面方向に優先的に成長させ、（００１）
面が発達した三角状または六角状に代表される板状ＷＣ
の存在した超硬合金もしくはその製造方法に関するもの
がある。As one of the directions of these proposals, attention is paid to the anisotropy of mechanical properties due to the crystal plane of WC, specifically, for example, the (001) plane of a WC crystal has the highest hardness and (100 ) The highest elastic modulus is exhibited in the (100) plane direction.
Plate-shaped WC represented by a triangular or hexagonal surface
Of the cemented carbide or the manufacturing method thereof.
【０００４】板状ＷＣに関連する先行技術の代表的なも
のに、特公昭４７−２３０４９号公報，特公昭４７−２
３０５０号公報，特開昭５７−３４００８号公報，特開
平２−４７２３９号公報，特開平２−５１４０８号公
報，特開平２−１３８４３４号公報，特開平２−２７４
８２７号公報および特開平５−３３９６５９号公報があ
る。Typical examples of the prior art relating to the plate-like WC are Japanese Patent Publication No. 47-23049 and Japanese Patent Publication No. 47-2.
No. 3050, No. 57-34008, No. 2-47239, No. 2-51408, No. 2-138434, No. 2-274.
827 and JP-A-5-339659.
【０００５】[0005]
【発明が解決しようとする課題】板状ＷＣに関連する先
行技術の内、特公昭４７−２３０４９号公報，特公昭４
７−２３０５０号公報には、板状ＷＣを成長させるため
の多孔性の凝集体でなるコロイド状炭化タングステン粉
末とＦｅ，Ｎｉ，Ｃｏまたはこれらの合金の粉末からな
る組成物を出発物質として用いる板状ＷＣ含有超硬合金
の製造方法について記載されている。これら両公報に記
載されている組成物の出発物質は、コロイド状炭化タン
グステン粉末の調整が困難であり、これを用いて超硬合
金を作製する場合には、加熱焼結時における板状ＷＣ結
晶の生成割合が少なく、その粒径および含有量の制御が
困難であり、全製造工程が複雑で高価になるという問題
がある。Among the prior art related to the plate-like WC, Japanese Patent Publication No. 47-23049 and Japanese Patent Publication No.
No. 7-23050, a plate using as a starting material a composition consisting of colloidal tungsten carbide powder made of porous agglomerates for growing plate-like WC and powders of Fe, Ni, Co or their alloys. A method for producing a WC-containing cemented carbide is described. The starting materials for the compositions described in both of these publications are difficult to prepare colloidal tungsten carbide powder, and when a cemented carbide is produced using this, a plate-shaped WC crystal at the time of heat sintering is used. However, there is a problem in that the production ratio is low, it is difficult to control the particle size and content, and the whole manufacturing process is complicated and expensive.
【０００６】また、特開昭５７−３４００８号公報に
は、強粉砕したＷとＣの混合粉末に少量のＦｅ族金属塩
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、双晶炭化タングステンの含有割合が少
なく、かつ分離も困難であること、この粉末を出発物質
として超硬合金を作製すると、超硬合金中の双晶炭化タ
ングステン含有率がさらに少なくなって、その効果が非
常に弱くなるという問題がある。Further, in Japanese Patent Laid-Open No. 57-34008, a small amount of Fe group metal salt is added to a strongly pulverized mixed powder of W and C, which is then heated and carbonized to make the (001) plane a twin plane. A method of manufacturing twinned tungsten carbide bonded as described above is described. The powder obtained by the method described in the publication has a low content of twinned tungsten carbide and is difficult to separate. When a cemented carbide is produced using this powder as a starting material, There is a problem that the content of twinned tungsten carbide is further reduced, and the effect is very weak.
【０００７】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
出発物質として、加熱焼結時に板状ＷＣを晶出させると
いう超硬合金の製造方法について記載されている。そし
て、これら両公報に記載されている炭化タングステンを
過飽和に含有した固溶体組成物の出発物質については、
特開平２−５１４０８号公報に詳細に記載されている。
これら３件の公報に記載されている炭化タングステンを
過飽和に含有した固溶体組成物を用いて超硬合金を作製
する場合に、焼結時における板状ＷＣの生成割合が少な
いこと、組成成分の制限された超硬合金にしか適用でき
ないという問題がある。Further, in JP-A-2-47239 and JP-A-2-138434, a plate is used at the time of heating and sintering using a solid solution of (W, Ti, Ta) C containing tungsten carbide in a supersaturated state as a starting material. It describes a method for producing a cemented carbide, in which crystal-like WC is crystallized. And, regarding the starting material of the solid solution composition containing tungsten carbide in supersaturation described in both these publications,
It is described in detail in JP-A-2-51408.
When a cemented carbide is produced using a solid solution composition containing tungsten carbide in supersaturation described in these three publications, the plate-like WC production rate is small at the time of sintering, and the composition components are limited. There is a problem that it can be applied only to the above-mentioned cemented carbide.
【０００８】次に、特開平２−２７４８２７号公報に
は、使用済みの超硬合金を酸化し、還元した後、炭化し
て得られた組成物粉末を出発物質として用いて、焼結時
に、この出発物質中の微細炭化タングステンを粒成長さ
せて板状ＷＣ結晶とする異方性超硬合金成形体製造用粉
末について記載されている。同公報に記載の組成物粉末
は、この粉末を作製するための製造工程が複雑で高価に
なること、またこの粉末を用いて超硬合金を作製する場
合、板状ＷＣ結晶の生成割合が少なく、その粒径の制御
が困難であるという問題がある。[0008] Next, in Japanese Patent Laid-Open No. 2-274827, the composition powder obtained by oxidizing a used cemented carbide, reducing it, and then carbonizing it is used as a starting material, This document describes a powder for producing an anisotropic cemented carbide compact, in which fine tungsten carbide in the starting material is grain-grown to form a plate-like WC crystal. The composition powder described in the publication has a complicated and expensive manufacturing process for producing the powder, and when a cemented carbide is produced using the powder, the plate-like WC crystal production rate is low. However, there is a problem that it is difficult to control the particle size.
【０００９】その他、特開平５−３３９６５９号公報に
は、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および／またはＮｉ
からなる混合粉末でなる出発物質を用いて、１４５０℃
以上で焼結し、板状ＷＣ結晶を有する超硬合金を作製す
る方法が記載されている。同公報に記載されている出発
物質は、長時間の混合粉砕によって微細で、かつ高歪量
の炭化タングステンの含有した粉末としているために、
不純物量が多くなること、製造工程時間が長くなるこ
と、これを用いて超硬合金を作製する場合、板状ＷＣ結
晶の生成割合が少なく、その粒径の制御も困難であると
いう問題がある。In addition, in JP-A-5-339659, WC of 0.5 μm or less, 3 to 40 wt% of a cubic compound, and 1 to 25 wt% of Co and / or Ni.
Using a starting material consisting of a mixed powder consisting of 1450 ° C.
The method for sintering to produce a cemented carbide having a plate-shaped WC crystal is described above. Since the starting material described in the publication is a powder containing fine and high strain amount tungsten carbide by long-term mixing and pulverization,
There is a problem that the amount of impurities is large, the manufacturing process time is long, and when a cemented carbide is produced using this, the production ratio of plate-like WC crystals is small and it is difficult to control the grain size. .
【００１０】本発明は、上述のような問題点を解決した
もので、具体的には、超硬合金を作製するにあたり、焼
結時に板状ＷＣ結晶を容易に晶出させることができる特
徴のある出発物質を用いて、板状ＷＣ結晶の含有量の制
御およびその粒径の制御を容易にし、高硬度，耐摩耗性
に優れ、かつ高靭性，耐欠損性に優れる超硬合金を得る
ことができる方法であり、従来の方法で得られる超硬合
金では考えられない高硬度，高靭性，高強度によるシナ
ジ効果を発揮し、長寿命となる板状ＷＣ含有超硬合金の
製造方法の提供を目的とするものである。The present invention has solved the above-mentioned problems. Specifically, in producing a cemented carbide, a plate-like WC crystal can be easily crystallized during sintering. To obtain a cemented carbide having a high hardness and wear resistance, a high toughness, and a high fracture resistance by facilitating the control of the content of the plate-like WC crystal and the control of the grain size by using a certain starting material. A method for producing a plate-shaped WC-containing cemented carbide that exhibits a synergistic effect due to high hardness, high toughness, and high strength, which is not possible with conventional cemented carbide obtained by conventional methods, and has a long life. The purpose is.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、長年に亘
り、超硬合金の硬さ、耐摩耗性を低下させずに、強度，
靭性，耐欠損性を向上させるための検討を行っていた
所、板状ＷＣ結晶を含有した超硬合金にするとその目的
が達成される傾向にあること、この超硬合金を得るため
には、用いる出発物質に従来用いられたことのないＷと
ＣとＣｏの複合炭化物またはＷ2ＣとＣｏを含有してお
くと達成されるという知見を得て、本発明を完成するに
至ったものである。For many years, the present inventors have been able to improve the strength, wear resistance and strength of cemented carbide without sacrificing strength and strength.
While conducting studies to improve the toughness and fracture resistance, the purpose tends to be achieved by using a cemented carbide containing a plate-shaped WC crystal. To obtain this cemented carbide, The present invention has been completed based on the finding that it can be achieved by containing a composite carbide of W, C and Co or W 2 C and Co which has never been used as a starting material. is there.
【００１２】すなわち、本発明の板状ＷＣ含有超硬合金
の製造方法は、カーボンおよび／またはグラファイト
０．５〜５．５重量％と、残りが第１物質：Ｃ（炭素元
素）とＷとＣｏ，Ｎｉ，Ｃｒの１種以上とでなる複合炭
化物粉末、第２物質：該複合炭化物粉末とＷ，Ｗ2Ｃ，
ＷＣの１種以上とでなる複合炭化物含有混合物、第３物
質：Ｗ2Ｃ、またはＷ2ＣおよびＷＣとＣｏ，Ｎｉ，Ｃｒ
の１種以上とでなる複合炭化物前駆体混合物から選ばれ
た少なくとも１種の板状ＷＣ含有形成物質とからなる混
合粉末を成形後、真空中または非酸化性ガス雰囲気中で
１２００〜１６００℃に加熱焼結することを特徴とする
方法である。That is, in the method for producing a plate-shaped WC-containing cemented carbide of the present invention, 0.5 to 5.5% by weight of carbon and / or graphite and the balance of the first substance: C (elemental carbon) and W. Composite carbide powder consisting of at least one of Co, Ni and Cr, second substance: the composite carbide powder and W, W 2 C,
Composite carbide containing mixture consisting of one or more WC, third substance: W 2 C, or W 2 C and WC with Co, Ni, Cr
Of at least one plate-like WC-containing forming material selected from the composite carbide precursor mixture consisting of at least one of the above, and then molded into a vacuum or a non-oxidizing gas atmosphere at 1200 to 1600 ° C. This is a method characterized by heating and sintering.
【００１３】本発明の製造方法における板状ＷＣ形成物
質は、第１物質，第２物質，第３物質の中の少なくとも
１種からなり、これらの第１物質，第２物質，および第
３物質のそれぞれが焼結時に主として添加されているカ
ーボンおよび／またはグラファイトと反応し、板状ＷＣ
結晶の晶出とＣｏ，Ｎｉ，Ｃｒの中の１種以上とでなる
結合相の形成に寄与するものである。この板状ＷＣ形成
物質の内、第１物質は、具体的には、例えばＣｏ3Ｗ9Ｃ
4，Ｃｏ2Ｗ4Ｃ ，Ｃｏ3Ｗ3Ｃ ，Ｃｏ6Ｗ6Ｃ ，Ｎｉ2Ｗ
4Ｃ，（Ｎｉ，Ｃｒ）2Ｗ4Ｃの複合炭化物粉末を挙げる
ことができ、これらの複合炭化物の少なくとも１種から
なることが好ましいことである。また、第２物質は、第
１物質である複合炭化物粉末の少なくとも１種とＷ，Ｗ
2Ｃ，ＷＣの中の１種以上とでなる複合炭化物含有混合
物でなり、第３物質は、Ｗ2Ｃ、またはＷ2ＣおよびＷＣ
とＣｏ，Ｎｉ，Ｃｒの１種以上からなる複合炭化物前駆
体混合物でなり、好ましくはＷ2Ｃが５０重量％以上で
なる第３物質であり、この複合炭化物前駆体混合物が加
熱焼結時に１度上述の第１物質である複合炭化物を形成
するものである。Plate-like WC product in the production method of the present invention
The quality is at least the first substance, the second substance, and the third substance.
It consists of one type, these first substance, second substance, and
Each of the three substances is mainly added during sintering.
Plate-like WC that reacts with carbon and / or graphite
It consists of crystallization of crystals and one or more of Co, Ni and Cr.
It contributes to the formation of a binder phase. This plate-shaped WC formation
Of the materials, the first material is, for example, Co3W9C
Four, Co2WFourC , Co3W3C , Co6W6C , Ni2W
FourC, (Ni, Cr)2WFourList C composite carbide powder
From at least one of these composite carbides
Is preferred. Also, the second substance is
At least one compound carbide powder that is one substance and W, W
2Composite carbide containing mixture consisting of one or more of C and WC
The third substance is W2C or W2C and WC
And composite carbide precursor consisting of at least one of Co, Ni and Cr
A body mixture, preferably W2When C is 50% by weight or more
Is a third substance, and this composite carbide precursor mixture is added.
Once formed by thermal sintering to form the above-mentioned first substance, composite carbide
To do.
【００１４】本発明の製造方法により得られる板状ＷＣ
含有超硬合金の諸特性に大きく支障がない程度ならば、
板状ＷＣ形成物質として存在している複合炭化物粉末，
Ｗ，Ｗ2Ｃ，ＷＣのＷ元素に代えてＭｏを置換した物質
として用いることも好ましいことである。また、板状Ｗ
Ｃ形成物質は、第１物質，第２物質，第３物質をそれぞ
れ単一に選定しても充分にその効果が高く好ましいが、
板状ＷＣ形成物質を作製する工程を簡略にするなどか
ら、第１物質と第３物質との混合物、または第２物質と
第３物質との混合物として用いることも好ましいことで
ある。Plate-like WC obtained by the manufacturing method of the present invention
As long as the various properties of the contained cemented carbide are not significantly affected,
A composite carbide powder present as a plate-like WC forming substance,
It is also preferable to use as a substance in which Mo is substituted in place of the W element of W, W 2 C and WC. Also, plate-shaped W
As for the C-forming substance, even if the first substance, the second substance, and the third substance are individually selected, their effects are sufficiently high and preferable.
It is also preferable to use it as a mixture of the first substance and the third substance or a mixture of the second substance and the third substance because the process of producing the plate-like WC forming substance is simplified.
【００１５】板状ＷＣ形成物質とカーボンおよび／また
はグラファイトとの混合粉末から板状ＷＣ含有超硬合金
を作製すると、板状ＷＣ結晶の晶出量が非常に高く、そ
の結果、得られる板状ＷＣ含有超硬合金がより高硬度，
高靭性，高強度となり好ましいが、さらに高温時におけ
る板状ＷＣ含有超硬合金の硬さ，耐摩耗性，強度，靭
性，耐熱性，耐衝撃性，耐溶着性などの諸特性を高める
ために、次のような製造方法によって板状ＷＣ含有超硬
合金を得ることも好ましいことである。When a plate-shaped WC-containing cemented carbide is prepared from a mixed powder of a plate-shaped WC-forming substance and carbon and / or graphite, the plate-shaped WC crystals have a very high crystallization amount, resulting in the plate-shaped WC crystal. WC-containing cemented carbide has higher hardness,
High toughness and high strength are preferable, but in order to further improve various properties such as hardness, wear resistance, strength, toughness, heat resistance, impact resistance, and welding resistance of the plate-shaped WC-containing cemented carbide at high temperature. It is also preferable to obtain a plate-shaped WC-containing cemented carbide by the following manufacturing method.
【００１６】すなわち、本発明の板状ＷＣ含有超硬合金
の製造方法は、カーボンおよび／またはグラファイト
０．５〜５．５重量％と、板状ＷＣ含有形成物質４０重
量％以上と、残りが周期律表の４ａ，５ａ，６ａ族金属
の炭化物，窒化物およびこれらの相互固溶体、並びにＣ
ｏ，Ｎｉ，Ｃｒ，Ｗの中の少なくとも１種の補足物質と
からなる混合粉末を成形後、真空中または非酸化性ガス
中で１２００〜１６００℃に加熱焼結する方法である。That is, according to the method for producing a plate-shaped WC-containing cemented carbide of the present invention, 0.5 to 5.5% by weight of carbon and / or graphite, 40% by weight or more of the plate-shaped WC-containing forming substance, and the balance Carbides, nitrides and mutual solid solutions of metals of groups 4a, 5a and 6a of the periodic table, and C
This is a method in which a mixed powder consisting of at least one supplementary substance selected from among o, Ni, Cr, and W is molded and then heated and sintered at 1200 to 1600 ° C. in a vacuum or a non-oxidizing gas.
【００１７】この、本発明の製造方法における補足物質
は、具体的には、例えばＴｉＣ，ＺｒＣ，ＨｆＣ，Ｖ
Ｃ，ＮｂＣ，ＴａＣ，Ｃｒ3Ｃ2，Ｍｏ2Ｃ，ＷＣ，Ｔｉ
Ｎ，ＺｒＮ，ＨｆＮ，ＶＮ，ＮｂＮ，ＴａＮ，ＣｒＮ，
（Ｗ，Ｔｉ）Ｃ，（Ｗ，Ｔｉ，Ｔａ）Ｃ，（Ｗ，Ｔｉ，
Ｔａ，Ｎｂ）Ｃ，Ｔｉ（Ｃ，Ｎ），（Ｗ，Ｔｉ）（Ｃ，
Ｎ），（Ｗ，Ｎｂ，Ｚｒ）（Ｃ，Ｎ），（Ｗ，Ｔｉ，Ｔ
ａ）（Ｃ，Ｎ），（Ｗ，Ｔｉ，Ｔａ，Ｎｂ）（Ｃ，
Ｎ），Ｃｏ，Ｎｉ，Ｃｒ，Ｗ，Ｃｏ・Ｎｉ合金，Ｃｏ・
Ｃｒ合金，Ｎｉ・Ｃｒ合金，Ｃｏ・Ｎｉ・Ｃｒ合金，Ｃ
ｏ・Ｗ合金，Ｃｏ・Ｃｒ・Ｗ合金を挙げることができ
る。The supplementary substance in the production method of the present invention is specifically, for example, TiC, ZrC, HfC, V.
C, NbC, TaC, Cr 3 C 2 , Mo 2 C, WC, Ti
N, ZrN, HfN, VN, NbN, TaN, CrN,
(W, Ti) C, (W, Ti, Ta) C, (W, Ti,
Ta, Nb) C, Ti (C, N), (W, Ti) (C,
N), (W, Nb, Zr) (C, N), (W, Ti, T
a) (C, N), (W, Ti, Ta, Nb) (C,
N), Co, Ni, Cr, W, Co / Ni alloy, Co /
Cr alloy, Ni / Cr alloy, Co / Ni / Cr alloy, C
Examples include o.W alloys and Co.Cr.W alloys.
【００１８】本発明の製造方法における混合粉末中のカ
ーボンおよび／またはグラファイトが０．５重量％未満
になると、加熱焼結時に板状ＷＣ形成物質から板状ＷＣ
結晶の晶出への交換率が減少し、逆に５．５重量％を超
えて多くなると、得られる板状ＷＣ含有超硬合金中にフ
リーカーボンが多量に存在するようになり、合金の諸特
性の低下が顕著となる。また、カーボンおよび／または
グラファイトと補足物質と板状ＷＣ形成物質とでなる混
合粉末の場合に、混合粉末中の板状ＷＣ形成物質が４０
重量％未満になると、得られる板状ＷＣ含有超硬合金中
における板状ＷＣ結晶の晶出量が少なく、合金の諸特性
の向上に対する効果が弱くなる。When the amount of carbon and / or graphite in the mixed powder in the production method of the present invention is less than 0.5% by weight, the plate-like WC-forming substance is converted into the plate-like WC during heating and sintering.
When the rate of exchange of crystals for crystallization decreases and conversely increases more than 5.5% by weight, a large amount of free carbon will be present in the obtained plate-shaped WC-containing cemented carbide, resulting in various alloy contents. The deterioration of the characteristics becomes remarkable. In the case of a mixed powder composed of carbon and / or graphite, a supplementary substance and a plate-like WC forming substance, the plate-like WC forming substance in the mixed powder is 40
If it is less than wt%, the amount of plate-like WC crystals crystallized in the obtained plate-like WC-containing cemented carbide will be small, and the effect of improving various properties of the alloy will be weakened.
【００１９】本発明の製造方法における真空中または非
酸化性ガス中とは、例えば混合粉末を加圧成形して得ら
れた成形体が酸化されない程度の真空雰囲気、または水
素ガス，不活性ガス，窒素ガスに代表される非酸化性ガ
ス雰囲気を挙げることができる。勿論、ホットプレスで
焼結すること、または焼結後、熱間静水圧処理（ＨＩ
Ｐ）すること、さらには成形体の作製では、従来の加圧
成形，鋳入成形，押出し成形に代表される粉末冶金の成
形法を用いることができる。The vacuum or the non-oxidizing gas in the production method of the present invention means, for example, a vacuum atmosphere in which a compact obtained by press-molding a mixed powder is not oxidized, or hydrogen gas, an inert gas, A non-oxidizing gas atmosphere represented by nitrogen gas can be mentioned. Of course, sintering by hot pressing, or hot isostatic pressing (HI) after sintering.
In P), and further in the production of the molded body, a conventional powder metallurgy molding method represented by pressure molding, casting molding, and extrusion molding can be used.
【００２０】[0020]
【作用】本発明の製造方法は、混合粉中に存在させた板
状ＷＣ形成物質とカーボンおよび／またはグラファイト
が加熱焼結時に反応し、板状ＷＣ結晶の晶出作用とＣ
ｏ，Ｎｉ，Ｃｒの１種以上を主成分とする結合相に分解
する作用をしているものである。In the production method of the present invention, the plate-like WC-forming substance present in the mixed powder reacts with carbon and / or graphite during heating and sintering, and the crystallization action of plate-like WC crystals and C
It has a function of decomposing into a binder phase containing at least one of o, Ni, and Cr as the main components.
【００２１】[0021]
【実施例１】市販されている平均粒径０．５μｍのＷ、
平均粒径１〜２μｍのＮｉ，Ｃｏ，Ｃｒ3Ｃ2、平均粒径
０．０２μｍのカーボンブラック（表中Ｃと記す）の各
粉末を用いて、表１に示した配合組成に秤量し、アセト
ン溶媒と超硬合金製ボールと共にステンレス製ポットに
挿入し、４８時間の混合粉砕後、乾燥して板状ＷＣ形成
物質作製用混合物を得た。これらの混合物をカーボンボ
ードに挿入し、雰囲気圧力１０-2Ｔｏｒｒの真空炉中で
１４００℃，１時間焼成して表１に示した板状ＷＣ形成
物質（イ）〜（ヘ）を得た。こうして得た（イ）〜
（ヘ）の粉末をＸ線回折法で同定し、内部添加法により
組成成分を定量し、その結果を表１に併記した。Example 1 Commercially available W having an average particle size of 0.5 μm,
Each powder of Ni, Co, Cr 3 C 2 having an average particle diameter of 1 to 2 μm and carbon black having an average particle diameter of 0.02 μm (referred to as C in the table) was weighed to have a composition shown in Table 1, The mixture was put into a stainless steel pot together with an acetone solvent and a cemented carbide ball, mixed and pulverized for 48 hours, and then dried to obtain a mixture for producing a plate-like WC forming substance. These mixtures were inserted into a carbon board and fired in a vacuum furnace with an atmospheric pressure of 10 -2 Torr at 1400 ° C for 1 hour to obtain the plate-like WC-forming substances (a) to (f) shown in Table 1. I got it like this
The powder of (f) was identified by the X-ray diffraction method, the composition components were quantified by the internal addition method, and the results are also shown in Table 1.
【００２２】こうして得た板状ＷＣ形成物質（イ）〜
（ヘ）と上述のＮｉ，Ｃｏ，Ｃｒ3Ｃ2，カーボンブラッ
クと平均粒径２．０μｍＷＣの各粉末とを用いて、表２
に示した配合組成に秤量し、アセトン溶媒と超硬合金製
ボールと共にステンレス製ポットに挿入し、４８時間の
混合粉砕後、乾燥して混合粉末を得た。Plate-like WC-forming material (a) thus obtained
(F) and the above-mentioned Ni, Co, Cr 3 C 2 , carbon black and each powder having an average particle diameter of 2.0 μmWC, Table 2
The mixture composition was weighed, inserted into a stainless steel pot together with an acetone solvent and a cemented carbide ball, mixed and pulverized for 48 hours, and then dried to obtain a mixed powder.
【００２３】こうして得た混合粉末を金型に充填し、２
ｔ／ｃｍ2の加圧でもって約５．５×９．５×２９ｍｍ
の圧粉成形体を作製し、アルミナとカーボンの繊維から
なるシート上に圧粉成形体を設置し、雰囲気圧力１０-2
Ｔｏｒｒの真空中で表２に併記する温度で１時間加熱し
て本発明の方法による試料１〜７および比較法による試
料１〜６の超硬合金を得た。The mixed powder thus obtained was filled in a mold, and 2
About 5.5 × 9.5 × 29mm with pressure of t / cm 2
Of the alumina and carbon fibers were placed on the sheet, and the atmospheric pressure was adjusted to 10 -2.
In a vacuum of Torr, heating was performed for 1 hour at the temperatures shown in Table 2 together to obtain cemented carbides of Samples 1 to 7 according to the method of the present invention and Samples 1 to 6 according to the comparative method.
【００２４】こうして得た超硬合金を＃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、抗折力（ＪＩＳ法）を測定し
て、その結果を表３に示した。次に、これらの超硬合金
の一面を１μｍのダイヤモンドペーストでラップ加工し
た後、ビッカース硬さ（荷重２０ｋｇｆ）と破壊靭性値
Ｋ1ｃ（ＩＭ法，荷重２０ｋｇｆ）を測定し、その結果
を表３に併記した。また、ラップ加工面を電子顕微鏡観
察し、組織写真の画像処理装置にてＷＣの平均粒径およ
び最大径と最小径との比（アスペクト比）が２．０以上
である板状ＷＣ結晶のＷＣ全体に対する体積比を求め
て、その結果を表３に併記した。The cemented carbide thus obtained was wet-ground with a # 230 diamond grindstone to obtain 4.0 × 8.0 × 25.
It was manufactured in a shape of 0 mm, and the transverse rupture strength (JIS method) was measured. The results are shown in Table 3. Next, after laminating one surface of these cemented carbide with 1 μm diamond paste, Vickers hardness (load 20 kgf) and fracture toughness value K 1 c (IM method, load 20 kgf) were measured, and the results are shown in a table. Also described in 3. The lapped surface was observed with an electron microscope, and the average grain size of WC and the ratio of the maximum diameter to the minimum diameter (aspect ratio) of the WC of a plate-like WC crystal with an image processing apparatus of a structure photograph of 2.0 or more were measured. The volume ratio to the whole was determined, and the results are also shown in Table 3.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【表３】 [Table 3]
【００２８】[0028]
【実施例２】実施例１で用いた板状ＷＣ形成物質（イ）
〜（ヘ）とＷ，Ｎｉ，Ｃｏ，Ｃｒ3Ｃ2，カーボンブラッ
ク，ＷＣの他に、平均粒径１〜２μｍのＴａＣ，（Ｗ，
Ｔｉ，Ｔａ）Ｃ（重量比で、ＷＣ／ＴｉＣ／ＴａＣ＝５
０／２０／３０、表中ＷＴＴと記す）の各粉末を用い
て、表４に示した配合組成に秤量し、表４に併記した焼
結温度以外は実施例１と同様に行って焼結し、本発明の
方法による試料８〜１８および比較法による試料７〜８
の超硬合金を得た。Example 2 Plate-like WC forming material (a) used in Example 1
- (f) and W, Ni, Co, Cr 3 C 2, carbon black, in addition to WC, TaC having an average particle size of 1 to 2 [mu] m, (W,
Ti, Ta) C (weight ratio: WC / TiC / TaC = 5)
0/20/30, referred to as WTT in the table) was used to weigh the compounding composition shown in Table 4, and sintering was performed in the same manner as in Example 1 except for the sintering temperature also shown in Table 4. Samples 8-18 according to the method of the invention and samples 7-8 according to the comparative method
To obtain a cemented carbide.
【００２９】こうして得た本発明による試料８〜１８お
よび比較による試料７〜１６について、実施例１と同様
にしてそれぞれの合金組成成分を調べて、その結果を表
４に併記した。さらに、実施例１と同様にして、本発明
による試料８〜１８および比較による試料７〜１６につ
いて、抗折力，硬さ，破壊靭性値，ＷＣ平均粒径および
全ＷＣ中の板状ＷＣ結晶の含有比率を調べて、その結果
を表５に示した。The alloy compositions of the samples 8 to 18 according to the present invention and the samples 7 to 16 according to the comparison thus obtained were examined in the same manner as in Example 1, and the results are also shown in Table 4. Further, in the same manner as in Example 1, with respect to the samples 8 to 18 according to the present invention and the samples 7 to 16 according to the comparison, the transverse rupture strength, the hardness, the fracture toughness value, the WC average grain size and the plate-like WC crystals in all WCs. The content ratio of was investigated and the results are shown in Table 5.
【００３０】[0030]
【表４】 [Table 4]
【００３１】[0031]
【表５】 [Table 5]
【００３２】[0032]
【発明の効果】本発明の板状ＷＣ含有超硬合金の製造方
法は、焼結時に板状ＷＣ結晶を晶出し、焼結後には板状
ＷＣ結晶の含有率の高い超硬合金にすることができるこ
と、およびＷＣとＣｏ，Ｎｉ，Ｃｒの１種以上の結合相
とでなる板状ＷＣ含有超硬合金から、さらに補足物質を
添加することにより広範囲の組成成分でなる板状ＷＣ含
有超硬合金を得ることができること、そして得られる板
状ＷＣ含有超硬合金が同一組成成分でなる従来の超硬合
金に比べて、抗折力で０．１〜０．８ＧＰａ，硬さで
０．６〜３．２ＧＰａ，Ｋ1ｃで０．１〜１．５ＭＰａ
・ｍ3/2も向上するという強度，硬さ，靭性を同時に高
めることがきるという優れた効果がある。According to the method for producing a plate-shaped WC-containing cemented carbide of the present invention, plate-shaped WC crystals are crystallized at the time of sintering, and after sintering, a cemented carbide having a high plate-shaped WC crystal content is obtained. And a plate-like WC-containing cemented carbide composed of a wide range of compositional components by adding a supplementary substance from a plate-like WC-containing cemented carbide composed of WC and one or more binder phases of Co, Ni and Cr. It is possible to obtain an alloy, and the plate-like WC-containing cemented carbide obtained has a transverse rupture strength of 0.1 to 0.8 GPa and a hardness of 0.6 as compared with a conventional cemented carbide having the same composition components. ~3.2GPa, with K 1 c 0.1~1.5MPa
・ It has an excellent effect that strength, hardness, and toughness can be increased at the same time by improving m 3/2 .
Claims (3)
５．５重量％と、残りが下記第１物質，第２物質，およ
び第３物質から選ばれた少なくとも１種の板状ＷＣ含有
形成物質とからなる混合粉末を成形後、真空中または非
酸化性ガス雰囲気中で１２００〜１６００℃に加熱焼結
することを特徴とする板状ＷＣ含有超硬合金の製造方
法。 第１物質：Ｃ（炭素元素）とＷとＣｏ，Ｎｉ，Ｃｒの１
種以上とでなる複合炭化物粉末 第２物質：該複合炭化物粉末とＷ，Ｗ2Ｃ，ＷＣの１種
以上とでなる複合炭化物含有混合物 第３物質：Ｗ2Ｃ，またはＷ2ＣおよびＷＣとＣｏ，Ｎ
ｉ，Ｃｒの１種以上とでなる複合炭化物前駆体混合物1. Carbon and graphite 0.5 to
After forming a mixed powder of 5.5% by weight and the balance of at least one plate-like WC-containing forming substance selected from the following first substance, second substance and third substance, in a vacuum or non-oxidizing A method for producing a plate-shaped WC-containing cemented carbide, which comprises heat-sintering at 1200 to 1600 ° C. in a reactive gas atmosphere. 1st substance: C (carbon element), W and 1 of Co, Ni, Cr
Composite carbide powder consisting of one or more second substances: Composite carbide-containing mixture consisting of the composite carbide powder and one or more of W, W 2 C and WC Third substance: W 2 C, or W 2 C and WC Co, N
Composite carbide precursor mixture consisting of at least one of i and Cr
０．５〜５．５重量％と、請求項１記載の板状ＷＣ含有
形成物質４０重量％以上と、残りが周期律表の４ａ，５
ａ，６ａ族金属の炭化物，窒化物およびこれらの相互固
溶体、並びにＣｏ，Ｎｉ，Ｃｒ，Ｗの中の少なくとも１
種の補足物質とからなる混合粉末を成形後、真空中また
は非酸化性ガス中で１２００〜１６００℃に加熱焼結す
ることを特徴とする板状ＷＣ含有超硬合金の製造方法。2. 0.5 to 5.5% by weight of carbon and / or graphite, 40% by weight or more of the plate-like WC-containing forming material according to claim 1, and the rest 4a, 5 of the periodic table.
Carbides, nitrides and their mutual solid solutions of a and 6a group metals, and at least one of Co, Ni, Cr and W
A method for producing a plate-shaped WC-containing cemented carbide, which comprises heating a mixed powder comprising a seed supplementary material to 1200 to 1600 ° C. in a vacuum or a non-oxidizing gas after molding.
4，Ｃｏ2Ｗ4Ｃ ，Ｃｏ3Ｗ3Ｃ ，Ｃｏ6Ｗ6Ｃ ，Ｎｉ2Ｗ
4Ｃ，（Ｃｏ，Ｃｒ）6Ｗ6Ｃ，（Ｎｉ，Ｃｒ）2Ｗ4Ｃの
中の少なくとも１種の複合炭化物でなる第１物質、また
は該複合炭化物とＷ，Ｗ2Ｃ，ＷＣの１種以上とでなる
第２物質であることを特徴とする請求項１または２記載
の板状ＷＣ含有超硬合金の製造方法。3. The plate-shaped WC-containing forming material is Co.3W9C
Four, Co2WFourC , Co3W3C , Co6W6C , Ni2W
FourC, (Co, Cr)6W6C, (Ni, Cr)2WFourOf C
A first substance consisting of at least one compound carbide in
Is the composite carbide and W, W2One or more of C and WC
It is a 2nd substance, The claim 1 or 2 characterized by the above-mentioned.
Of the plate-shaped WC-containing cemented carbide.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6069978A JP2947707B2 (en) | 1994-03-14 | 1994-03-14 | Method for producing plate-like WC-containing cemented carbide |
| TW084108233A TW368522B (en) | 1994-03-07 | 1995-08-08 | Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6069978A JP2947707B2 (en) | 1994-03-14 | 1994-03-14 | Method for producing plate-like WC-containing cemented carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07252555A true JPH07252555A (en) | 1995-10-03 |
| JP2947707B2 JP2947707B2 (en) | 1999-09-13 |
Family
ID=13418266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6069978A Expired - Lifetime JP2947707B2 (en) | 1994-03-07 | 1994-03-14 | Method for producing plate-like WC-containing cemented carbide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2947707B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318040A (en) * | 2021-12-29 | 2022-04-12 | 江西理工大学 | A kind of rare earth cemented carbide and preparation method thereof |
| KR20250071657A (en) * | 2023-11-15 | 2025-05-22 | 전북대학교산학협력단 | Cemented carbide alloy with improved hardness and fracture toughness and its manufacturing method |
-
1994
- 1994-03-14 JP JP6069978A patent/JP2947707B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318040A (en) * | 2021-12-29 | 2022-04-12 | 江西理工大学 | A kind of rare earth cemented carbide and preparation method thereof |
| CN114318040B (en) * | 2021-12-29 | 2023-04-07 | 江西理工大学 | Rare earth-added hard alloy and preparation method thereof |
| KR20250071657A (en) * | 2023-11-15 | 2025-05-22 | 전북대학교산학협력단 | Cemented carbide alloy with improved hardness and fracture toughness and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2947707B2 (en) | 1999-09-13 |
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