JPH07242958A - Composition for powder metallurgy and its production - Google Patents
Composition for powder metallurgy and its productionInfo
- Publication number
- JPH07242958A JPH07242958A JP6064565A JP6456594A JPH07242958A JP H07242958 A JPH07242958 A JP H07242958A JP 6064565 A JP6064565 A JP 6064565A JP 6456594 A JP6456594 A JP 6456594A JP H07242958 A JPH07242958 A JP H07242958A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- carbon
- composition
- weight
- sintered alloy
- 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
- 238000004663 powder metallurgy Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title description 23
- 239000000843 powder Substances 0.000 claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 49
- 239000000956 alloy Substances 0.000 claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 9
- 239000006104 solid solution Substances 0.000 claims abstract description 7
- 150000004767 nitrides Chemical class 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 239000007858 starting material Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 229910052715 tantalum Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、板状の炭化タングステ
ンを晶出させて、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超硬合金またはサーメ
ットに代表される焼結合金を作製するための出発物質と
して適する粉末冶金用組成物およびその製造方法に関す
るものである。FIELD OF THE INVENTION The present invention relates to a cemented carbide or cermet which is excellent in hardness, toughness, wear resistance, fracture resistance, plastic deformation resistance and heat cracking resistance by crystallizing plate-shaped tungsten carbide. The present invention relates to a powder metallurgical composition suitable as a starting material for producing a sintered alloy represented by, and a method for producing the same.
【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またはサーメットに代表される焼
結合金は、多種多用の用途に実用されている。この焼結
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 or a sintered alloy represented by cermet, which is composed of a hard phase of a metal compound and a binder phase of a metal, has been put to practical use for various purposes. In this sintered alloy, if the hardness is increased to improve the wear resistance, the toughness is lowered and the fracture resistance is deteriorated. Conversely, if the toughness and the fracture resistance are increased, the hardness and the wear resistance are reduced. There is a problem of showing 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
の存在した焼結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 ) Since the maximum elastic modulus is in the (100) plane direction, the (100) plane direction is preferentially grown to (001) plane direction.
Plate-shaped WC represented by a triangular or hexagonal surface
Existing sintered alloy or a method for producing the same.
【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、これを用いて焼結合
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 a colloidal tungsten carbide powder, and when a sintered alloy is produced using this, a plate-shaped WC crystal during 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
として焼結合金を作製すると、焼結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 sintered alloy 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は、製造方法が困難であること、こ
れを用いて焼結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
た焼結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 solid solution composition containing tungsten carbide in supersaturation described in both of these publications, Japanese Patent Laid-Open No.
This is described in detail in Japanese Patent No. 51408. The solid solution composition containing tungsten carbide in supersaturation described in these three publications is difficult to produce, and when a sintered alloy is produced using this, the plate-shaped WC during sintering is used. However, there is a problem that the production ratio is small and it can be applied only to a sintered alloy having a limited composition component.
【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焼結合金を作製する場
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 sintered alloy is produced using the powder, the production ratio of plate-like WC crystals is small. 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、これを用いて焼結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 sintered alloy is manufactured using this, the generation ratio of plate-like WC crystals is small and it is difficult to control the particle 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、焼結合金を作製するための出発物
質として用いた場合に、焼結合金中に板状WC結晶を容
易に含有させることができること、その含有量の制御お
よび粒径の制御を容易にすることができること、および
得られる焼結合金が高硬度,耐摩耗性に優れ、かつ高靭
性,耐欠損性に優れるという従来の焼結合金の出発物質
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、長寿命を達成できる粉末冶金用組成物お
よびそ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, when used as a starting material for producing a sintered alloy, a plate-like WC crystal is contained in the sintered alloy. It can be easily contained, the content can be controlled and the grain size can be easily controlled, and the obtained sintered alloy has high hardness and wear resistance, as well as high toughness and fracture resistance. An object of the present invention is to provide a powder metallurgical composition capable of exhibiting a synergistic effect due to high hardness, high toughness, and high strength, which cannot be thought of as a starting material of a conventional sintered alloy, which is excellent, and a long life, and a manufacturing method thereof. 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、用いる出発物質が従来用いられたことのないWと
CとCoの複合炭化物に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 using a composite carbide of W, C and Co which has never been used as the starting material.
【0012】すなわち、本発明の粉末冶金用組成物は、
Wと炭素とCo,Ni,Crの1種以上でなる複合炭化
物粉末を含有していることを特徴とするものである。こ
の複合炭化物粉末を構成しているWと炭素とCo,N
i,Crの1種以上とのそれぞれの比率は、Wが70〜
90重量%と炭素が0.5〜3.0重量%と残りがC
o,Ni,Crの1種以上とでなる場合が好ましく、特
に、Co3W9C4,Co2W4C ,Co3W3C ,Co6W6
C ,Ni2W4C,(Ni,Cr)2W4Cの中の少なくと
も1種でなる複合炭化物粉末が好ましいものである。That is, the composition for powder metallurgy of the present invention is
Composite carbonization consisting of W, carbon and one or more of Co, Ni and Cr
It is characterized in that it contains a substance powder. This
W, carbon, Co, and N that constitute the composite carbide powder of
The ratio of each of i and Cr to one or more kinds of W is 70 to
90% by weight, 0.5 to 3.0% by weight of carbon, and the balance C
It is preferable that it is one or more of o, Ni, and Cr.
To Co3W9CFour, Co2WFourC , Co3W3C , Co6W6
C , Ni2WFourC, (Ni, Cr)2WFourAt least in C
Also, a composite carbide powder consisting of one kind is preferable.
【0013】この、複合炭化物粉末をそのまま焼結合金
を得るための粉末冶金用組成物として用いることもでき
るが、この場合には得られる焼結合金の組成成分が極端
に限定されることになる。そこで、この複合炭化物粉末
を10重量%以上と、残りがカーボン,グラファイト,
金属,合金,セラミックスの中の少なくとも1種の焼結
合金形成補足粉末とからなる粉末冶金用組成物にしてお
くことが好ましい。このときの焼結合金形成補足粉末
は、硬質相と結合相とからなる焼結合金の内の硬質相を
形成するための物質および結合相を形成するための物質
の一方または両方を含んでもよく、具体的には、例えば
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であるTiC,Zr
C,HfC,TaC,NbC,VC,WC,Cr3C2,
Mo2C、,TiN,Ti(C,N),(Ti,W)
C,(Ti,W)(C,N),(Ti,Ta,W)C,
(Ti,Ta,W)(C,N),(Ti,Ta,Nb,
W)C,Ti(C,O),TiO 2,Ti(N,O),
Ti(C,N,O)を代表例とするもの、並びにCo,
Ni,Cr,V,Wおよびこれらの相互合金,カーボ
ン,グラファイトの中の少なくとも1種の粉末からなる
ものが特に好ましい。This composite carbide powder is used as it is as a sintered alloy.
Can also be used as a composition for powder metallurgy to obtain
However, in this case, the compositional components of the sintered alloy obtained are extremely
Will be limited to. Therefore, this composite carbide powder
Is 10% by weight or more, the rest is carbon, graphite,
Sintering of at least one of metals, alloys and ceramics
A composition for powder metallurgy comprising an alloy forming supplementary powder
Is preferred. Powder for forming sintered alloy at this time
Is a hard phase in a sintered alloy consisting of a hard phase and a binder phase.
Substances for forming and substances for forming a bonded phase
One or both of the above may be included, and specifically, for example,
Carbides, nitrides of 4a, 5a, 6a group metals of the periodic table,
Oxides and their mutual solid solutions TiC, Zr
C, HfC, TaC, NbC, VC, WC, Cr3C2,
Mo2C, TiN, Ti (C, N), (Ti, W)
C, (Ti, W) (C, N), (Ti, Ta, W) C,
(Ti, Ta, W) (C, N), (Ti, Ta, Nb,
W) C, Ti (C, O), TiO 2, Ti (N, O),
Ti (C, N, O) as a typical example, Co,
Ni, Cr, V, W and their mutual alloys, carbo
It consists of at least one kind of powder in graphite
Those are particularly preferable.
【0014】また、複合炭化物粉末は、焼結時に硬質相
としての主として板状WC結晶を晶出させるためのもの
であり、一部がCo,Ni,Crの1種以上でなる結合
相を形成するためのものであるが、100%の複合炭化
物粉末とするには製造時の調整に大変シビア性を要求さ
れること、および焼結時における板状WC結晶の晶出率
を高めるために、複合炭化物粉末10重量%以上と、残
りW,W2C,WCの中の少なくとも1種を含み、かつ
全炭素量が0.5〜5.5重量%にある板状WC形成混
合物からなる粉末冶金用組成物とすることが好ましいこ
とである。この板状WC形成混合物をそのまま焼結合金
を得るための粉末冶金用組成物として用いることもでき
るが、この場合には得られる焼結合金の組成成分が極端
に限定されることになる。The composite carbide powder is mainly for crystallizing a plate-like WC crystal as a hard phase during sintering, and a part thereof forms a binder phase composed of one or more of Co, Ni and Cr. However, in order to obtain a 100% composite carbide powder, it is required to have a very severe degree of adjustment during production, and in order to increase the crystallization rate of the plate-like WC crystal during sintering, Powder composed of a plate-like WC-forming mixture containing 10% by weight or more of composite carbide powder and at least one of the remaining W, W 2 C, and WC, and having a total carbon content of 0.5 to 5.5% by weight. It is preferred to have a metallurgical composition. This plate-like WC forming mixture can be used as it is as a composition for powder metallurgy to obtain a sintered alloy, but in this case, the compositional components of the obtained sintered alloy are extremely limited.
【0015】そこで、この板状WC形成混合物を50重
量%以上と、残りがカーボン,グラファイト,金属,合
金,セラミックスの中の少なくとも1種の焼結合金形成
補足粉末とからなる粉末冶金用組成物にしておくことが
好ましい。この板状WC形成混合物が粉末冶金用組成物
全体に対して、50重量%未満になる場合、または板状
WC形成混合物全体に対して、複合炭化物粉末が10重
量%未満になる場合、もしくは板状WC形成混合物にお
ける全炭素量が0.5重量%未満になると焼結時に金属
Wが増加し、逆に全炭素量が5.5重量%を超えて多く
なると非板状WC結晶が増加するもので、これらすべて
について相対的に、焼結時に板状WC結晶が低下し、硬
さおよび靭性の向上効果が著しく低下することから、そ
れぞれ粉末冶金用組成物全体に対する板状WC形成混合
物を50重量%以上、板状WC形成混合物全体に対する
複合炭化物粉末を10重量%以上、板状WC形成混合物
の全炭素量を0.5〜5.5重量%と定めたものであ
る。Therefore, a composition for powder metallurgy comprising 50% by weight or more of this plate-like WC forming mixture and the balance of at least one kind of sintered alloy forming supplementary powder among carbon, graphite, metal, alloy and ceramics. It is preferable that When the plate-like WC forming mixture is less than 50% by weight based on the whole powder metallurgy composition, or when the composite carbide powder is less than 10% by weight based on the whole plate-like WC forming mixture, or the plate When the total carbon content in the WC-forming mixture is less than 0.5% by weight, the amount of metal W increases during sintering, and conversely, when the total carbon content exceeds 5.5% by weight, the non-plate-like WC crystals increase. With respect to all of these, since the plate-like WC crystal is reduced during sintering and the effect of improving hardness and toughness is remarkably decreased, 50% of the plate-like WC forming mixture is added to the entire powder metallurgy composition. It is defined that the amount of the composite carbide powder is 10% by weight or more with respect to the entire plate-like WC forming mixture, and the total carbon amount of the plate-like WC forming mixture is 0.5 to 5.5% by weight.
【0016】本発明の粉末冶金用組成物は、従来から行
われている粉体粉末冶金の製造方法、具体的には、気相
混合法,固相混合法,液相混合法による混合と加熱焼成
と混合粉砕の各工程を経て作製することができるが、次
の方法で行うと簡易で、かつ品質管理上においても容易
である。The composition for powder metallurgy of the present invention comprises a conventional method for producing powder powder metallurgy, specifically, mixing and heating by a vapor phase mixing method, a solid phase mixing method, a liquid phase mixing method. Although it can be produced through each step of firing and mixing and pulverization, the following method is simple and easy in quality control.
【0017】すなわち、本発明の製造方法は、Co,C
o含有化合物,Ni,Ni含有化合物,Cr,Cr含有
化合物,CoとNiとCrの2種以上の合金の中の少な
くとも1種のCo,Ni,Cr供給粉末と、WおよびW
含有化合物のW供給粉末と、炭素および/または炭素含
有化合物の炭素供給粉末とでなる混合粉末を真空,還元
性ガス,浸炭性ガス,不活性ガスの中の少なくとも1種
の雰囲気中で加熱保持して、Wと炭素とCo,Ni,C
rの1種以上とでなる複合炭化物粉末、もしくは該複合
炭化物粉末10重量%以上と、残りがW,W2C,WC
の中の少なくとも1種を含み、かつ全炭素量が0.5〜
5.5重量%にある板状WC形成混合物を得る方法であ
る。こうして得た複合炭化物粉末10重量%以上に、カ
ーボン,グラファイト,金属,合金,セラミックスの中
の少なくとも1種の焼結合金形成補足粉末を加えて混合
し、本発明の組成物とする方法、または板状WC形成混
合物50重量%以上に、上述の焼結合金形成補足粉末を
加えて混合し、本発明の組成物とする方法である。That is, the manufacturing method of the present invention is made of Co, C
O-containing compound, Ni, Ni-containing compound, Cr, Cr-containing compound, Co and at least one Co, Ni, Cr feed powder among two or more alloys of Ni and Cr, and W and W
A mixed powder consisting of W-containing powder of a containing compound and carbon and / or carbon-containing powder of a carbon-containing compound is heated and held in an atmosphere of at least one of vacuum, reducing gas, carburizing gas and inert gas. Then, W, carbon, Co, Ni, C
a composite carbide powder consisting of at least one of r, or 10% by weight or more of the composite carbide powder and the rest W, W 2 C, WC
Containing at least one of the total carbon content of 0.5 to
This is a method of obtaining a plate-like WC forming mixture in an amount of 5.5% by weight. A method of preparing the composition of the present invention by adding 10% by weight or more of the composite carbide powder thus obtained to at least one supplementary powder for forming a sintered alloy of carbon, graphite, metal, alloy, and ceramics, and mixing it, or This is a method for preparing the composition of the present invention by adding 50% by weight or more of the plate-like WC forming mixture to the above supplementary powder for forming a sintered alloy and mixing the mixture.
【0018】この本発明の製造方法におけるCo含有化
合物,Ni含有化合物,W含有化合物,Cr含有化合物
は、具体的には、例えばCoO,Co3O4,CoC
O3,Co(COO)2,Co(C5H7O2)2のCo含有
化合物、NiO,Ni(NO3)2のNi含有化合物、W
O2,WO3,H2WO3,5(NH4)212WO35H2O
のW含有化合物、Cr3C2,Cr7C3,Cr23C6,C
r2O3のCr含有化合物に代表される酸化物,炭化物,
塩,金属有機物を挙げることができ、炭素含有化合物
は、セルロース,澱粉,合成樹脂の粉末を挙げることが
できる。また、Co,Ni,Cr供給粉末とW供給粉末
として、両者の含有化合物、具体的には例えばCoWO
4の複合酸化物を用いること、さらには、Co,Ni,
Cr供給粉末とW供給粉末と炭素供給粉末として、H2
WO3とCo(OH)2とコロイド状カーボンとの共沈物
を用いることもできる。これらの中でもCo,Ni,C
r供給粉末とW供給粉末は、Co酸化物,Ni酸化物,
W酸化物およびこれらの複合酸化物として用いること、
炭素供給粉末はカーボンおよび/またはグラファイトと
して用いることが高純度および微粒粉のものが得られや
すく、製造工程上の品質管理が容易で、総合的に廉価に
なるので好ましい。Specific examples of the Co-containing compound, Ni-containing compound, W-containing compound and Cr-containing compound in the production method of the present invention include, for example, CoO, Co 3 O 4 , CoC.
O 3 , Co (COO) 2 , Co (C 5 H 7 O 2 ) 2 Co-containing compound, NiO, Ni (NO 3 ) 2 Ni-containing compound, W
O 2 , WO 3 , H 2 WO 3 , 5 (NH 4 ) 2 12 WO 3 5H 2 O
W-containing compound, Cr 3 C 2, Cr 7 C 3, Cr 23 C 6, C
oxides and carbides represented by Cr-containing compounds of r 2 O 3 ,
Salts and metal organic compounds may be mentioned, and examples of the carbon-containing compound may include cellulose, starch and synthetic resin powders. Further, as Co, Ni, Cr supply powder and W supply powder, a compound containing both, specifically, for example, CoWO
4 using a composite oxide, and further Co, Ni,
H 2 as Cr supply powder, W supply powder and carbon supply powder
A coprecipitate of WO 3 , Co (OH) 2 and colloidal carbon can also be used. Among these, Co, Ni, C
r supply powder and W supply powder are Co oxide, Ni oxide,
Use as a W oxide and a composite oxide thereof,
It is preferable to use carbon supply powder as carbon and / or graphite because it is easy to obtain high purity and fine powder, quality control in the manufacturing process is easy, and the cost is comprehensively low.
【0019】本発明の製造方法における雰囲気は、非酸
化性であればどのような雰囲気でも良く、加熱するとき
の温度範囲に応じて雰囲気を変えることも好ましいこと
である。具体的な雰囲気は、例えばH2,CO,CH4,
N2,Arおよびこれらの混合ガス、または真空状態、
さらには大気を遮断した雰囲気状態を挙げることができ
る。The atmosphere in the manufacturing method of the present invention may be any atmosphere as long as it is non-oxidizing, and it is also preferable to change the atmosphere according to the temperature range for heating. The specific atmosphere is, for example, H 2 , CO, CH 4 ,
N 2 , Ar and mixed gas thereof, or vacuum state,
Further, an atmosphere state in which the air is cut off can be mentioned.
【0020】本発明の製造方法における加熱は、上述し
たCo,Ni,Cr供給粉末とW供給粉末と炭素供給粉
末におけるそれぞれの種類,粒径,配合組成,加熱時の
雰囲気により異なるが、800〜1600℃が好まし
く、特に複合炭化物粉末の生成率を高めて、かつ粒成長
抑制および硬く固結するのを防止するために900〜1
400℃が特に好ましい。The heating in the manufacturing method of the present invention varies depending on the type, particle size, composition, and heating atmosphere of the above-mentioned Co, Ni, Cr supply powder, W supply powder, and carbon supply powder. 1600 ° C. is preferable, and 900 to 1 is particularly used in order to increase the production rate of the composite carbide powder, suppress grain growth, and prevent hard consolidation.
400 ° C. is particularly preferred.
【0021】本発明の製造方法における最重要点は、最
終的に得られる組成物の全炭素量が0.5〜5.5重量
%になるように、Co,Ni,Cr供給粉末とW供給粉
末と炭素供給粉末との種類および配合量,加熱時の雰囲
気、加熱温度について調整する必要がある。具体的に
は、例えばN2ガス中でCoOとWO3と炭素との混合粉
末を加熱する場合には、酸化物の還元に必要な量の炭素
を追加混合し、逆にH2とCH4の混合ガス中で金属Co
と金属Wと炭素との混合粉末を加熱する場合には、CH
4ガスによる浸炭量に相当するカーボンを減じて混合す
れば良い。The most important point in the manufacturing method of the present invention is to supply Co, Ni, Cr powder and W so that the total carbon content of the finally obtained composition is 0.5 to 5.5% by weight. It is necessary to adjust the type and blending amount of the powder and the carbon supply powder, the atmosphere during heating, and the heating temperature. Specifically, for example, when heating a mixed powder of CoO, WO 3, and carbon in N 2 gas, carbon is additionally mixed in an amount necessary for reducing the oxide, and conversely H 2 and CH 4 are added. Metal Co in a mixed gas of
When heating a mixed powder of metal W and carbon, CH
It suffices to reduce the carbon equivalent to the amount of carburization by 4 gases and mix.
【0022】[0022]
【作用】本発明の粉末冶金用組成物は、複合炭化物粉末
および板状WC形成混合物が加熱焼結反応により焼結合
金中で板状WC結晶の形成とCo,Ni,Crを主成分
とする結合相の形成を行う作用をし、これらの複合炭化
物粉末または板状WC形成混合物の他に、焼結して目的
の焼結合金の組成成分となるように添加する焼結合金補
足粉末が焼結合金における板状WC結晶以外の硬質相の
形成作用と結合相量の調整作用となるものである。In the composition for powder metallurgy of the present invention, the composite carbide powder and the plate-like WC forming mixture form plate-like WC crystals in the sintered alloy by the heating and sintering reaction and contain Co, Ni and Cr as the main components. In addition to the composite carbide powder or the plate-like WC forming mixture, which acts to form a binder phase, a sintered alloy supplementary powder which is added so as to be sintered to become a composition component of an intended sintered alloy is burned. It serves to form a hard phase other than the plate-shaped WC crystal in the bonded gold and to adjust the amount of the bonded phase.
【0023】[0023]
【実施例】市販されている平均粒径1.0μmのW、1
0μmのWO3、1〜2μmのCo,Ni,Cr3C2、
(W,Ti,Ta)Cの複合炭化物(重量比でWC/T
iC/TaC=50/20/30、WTTと表中に記
す)、0.1μmのCoO、0.03μmのTiO2、
0.5μmのCoWO4および0.02μmのカーボン
ブラック(Cと表中に記す)の各粉末を用いて、表1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時間の混合
粉砕後、乾燥して混合粉末を得た。これらの混合粉末を
カーボンボードに挿入し、表1に併記した雰囲気、温度
で1時間加熱・保持して本発明品1〜13および比較品
1〜4の焼結合金用組成物粉末を得た。EXAMPLES Commercially available W having an average particle size of 1.0 μm, 1
0 μm WO 3 , 1-2 μm Co, Ni, Cr 3 C 2 ,
(W, Ti, Ta) C composite carbide (WC / T by weight ratio)
iC / TaC = 50/20/30, written as WTT in the table), 0.1 μm CoO, 0.03 μm TiO 2 ,
Powders of 0.5 μm CoWO 4 and 0.02 μm carbon black (denoted as C in the table) were used to weigh the compounding composition shown in Table 1, and an acetone solvent and a cemented carbide ball were placed in a stainless steel pot. It was inserted together, mixed and pulverized for 12 hours, and then dried to obtain a mixed powder. These mixed powders were inserted into a carbon board and heated and held at the atmospheres and temperatures shown in Table 1 for 1 hour to obtain composition powders for sintered alloys of Inventive Products 1 to 13 and Comparative Products 1 to 4. .
【0024】得られた各粉末の全炭素量を測定した後、
X線回折装置を用いて生成物を同定し、また内部添加法
で組成を定量した。これらの結果を表2に示した。After measuring the total carbon content of each of the obtained powders,
The product was identified using an X-ray diffractometer, and the composition was quantified by the internal addition method. The results are shown in Table 2.
【0025】次に、本発明品1,3,5,6,7,8,
11,12,13および比較品1〜4の各組成物粉末、
上記カーボンブラック,(W,Ti,Ta)C粉末およ
び市販されている平均粒子径1〜2μmのTaC,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、48時間の混合粉砕後、乾燥して混合粉末を
得た。こうして得た混合粉末の効果を調べるために、こ
れらの混合粉末を金型に充填し、2ton/cm2の加
圧でもって約5.5×9.5×29mmの圧粉成形体と
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10-2Torrの真空中で
表3に併記する温度で1時間加熱・保持して本発明品1
4〜24および比較品5〜8の超硬合金を得た。Next, the products of the present invention 1, 3, 5, 6, 7, 8,
Each composition powder of 11, 12, 13 and comparative products 1 to 4,
The above carbon black, (W, Ti, Ta) C powder and commercially available TaC and WC having an average particle size of 1 to 2 μm
Each powder was weighed to the blending composition shown in Table 3, 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. In order to examine the effect of the mixed powder thus obtained, these mixed powders were filled in a mold, and a powder compact having a size of about 5.5 × 9.5 × 29 mm was formed by applying a pressure of 2 ton / cm 2. This invention product 1 was prepared by placing a powder compact on a sheet made of carbon fiber and carbon fiber, and heating and holding at a temperature shown in Table 3 for 1 hour in a vacuum with an atmospheric pressure of 10 -2 Torr.
Cemented carbides of 4 to 24 and comparative products 5 to 8 were obtained.
【0026】こうして得た超硬合金試料を#230のダ
イヤモンド砥石で湿式研削加工し、4.0×8.0×2
5.0mmの試料を作製して抗折力(JIS法)を測定
した。また、試料の一面を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:20k
gf)と破壊靭性値:K1c(IM法,荷重:20kg
f)を測定した。さらに、ラップ加工面について電子顕
微鏡にて組織写真を撮り、画像処理装置にて全WCの平
均粒子径およびWC粒子の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のWC全体に対
する体積割合を求めた。これらの結果を表4に示す。ま
た、上記組織写真により測定したおおよその焼結合金組
成を表3に併記した。The cemented carbide sample thus obtained was wet-ground with a # 230 diamond grindstone to obtain 4.0 × 8.0 × 2.
A 5.0 mm sample was prepared and the transverse rupture strength (JIS method) was measured. Also, after laminating one surface of the sample with 1 μm diamond paste, Vickers hardness (load: 20 k
gf) and fracture toughness value: K 1 c (IM method, load: 20 kg
f) was measured. Further, a structure photograph of the lapping surface is taken with an electron microscope, and a plate having an average particle diameter of all WC and a ratio of the maximum diameter to the minimum diameter of WC particles (aspect ratio) of 2.0 or more by an image processing apparatus. The volume ratio of the WC to the whole WC was determined. The results are shown in Table 4. Further, Table 3 also shows the approximate composition of the sintered alloy measured by the above-mentioned micrograph.
【0027】[0027]
【表1】 [Table 1]
【0028】[0028]
【表2】 [Table 2]
【0029】[0029]
【表3】 [Table 3]
【0030】[0030]
【表4】 [Table 4]
【0031】[0031]
【発明の効果】本発明の粉末冶金用組成物は、これを用
いて焼結合金、特に超硬合金を作製した場合に、従来か
ら用いられている超硬合金用組成物に比べて、板状WC
結晶の晶出比率が顕著に高く、同一組成成分の超硬合金
で対比した場合に、従来の超硬合金に比べて硬さが1.
2〜1.8GPa高く、抗折力が0.1〜0.2GPa
高く、破壊靭性値が0.1〜0.4GPa高くなるとい
う、従来の超硬合金では達成できないかった同一組成成
分における硬さ,抗折力および破壊靭性値の3特性を向
上させることができるという優れた効果がある。The composition for powder metallurgy of the present invention, when used for producing a sintered alloy, particularly a cemented carbide, is superior to the composition for cemented carbide that has been conventionally used. WC
The crystallization ratio of crystals is remarkably high, and when compared with cemented carbides having the same compositional components, the hardness is 1. compared to conventional cemented carbides.
2 to 1.8 GPa higher and bending strength of 0.1 to 0.2 GPa
The fracture toughness value is increased by 0.1 to 0.4 GPa, which is not possible with conventional cemented carbides, and can improve hardness, transverse rupture strength and fracture toughness value in the same composition. There is an excellent effect.
【0032】また、本発明の粉末冶金用組成物製造方法
は、従来の板状WC結晶を晶出するための組成物の製造
方法に比べて、簡易に製造できること、組成物全体の含
有炭素量の調整が容易であること、製造工程上の品質も
容易であるという効果がある。Further, the method for producing a composition for powder metallurgy of the present invention can be produced more easily than the conventional method for producing a composition for crystallizing a plate-shaped WC crystal, and the carbon content of the entire composition can be increased. Is easy to adjust, and the quality in the manufacturing process is also easy.
Claims (8)
でなる複合炭化物粉末を含有していることを特徴とする
粉末冶金用組成物。1. A composition for powder metallurgy, comprising W, carbon, and a composite carbide powder containing at least one of Co, Ni, and Cr.
%と炭素0.5〜3.0重量%と残りCo,Ni,Cr
の1種以上とからなることを特徴とする請求項1記載の
粉末冶金用組成物。2. The composite carbide powder contains 70 to 90% by weight of W, 0.5 to 3.0% by weight of carbon, and the balance Co, Ni, Cr.
2. The composition for powder metallurgy according to claim 1, comprising one or more of
10重量%以上と、残りがカーボン,グラファイト,金
属,合金,セラミックスの中の少なくとも1種の焼結合
金形成補足粉末からなることを特徴とする粉末冶金用組
成物。3. The composite carbide powder according to claim 1 or 2, which is 10% by weight or more, and the balance is at least one kind of sintered alloy forming supplementary powder among carbon, graphite, metal, alloy and ceramics. A composition for powder metallurgy.
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、並びにCo,Ni,Cr,V,
Wおよびこれらの相互合金,カーボン,グラファイトの
中の少なくとも1種の粉末からなることを特徴とする請
求項3記載の粉末冶金用組成物。4. The supplementary powder for forming a sintered alloy comprises carbides, nitrides, oxides and their mutual solid solutions of 4a, 5a and 6a metals of the periodic table, and Co, Ni, Cr, V,
4. The composition for powder metallurgy according to claim 3, comprising at least one kind of powder of W and mutual alloys thereof, carbon and graphite.
10重量%以上と、残りがW,W2C,WCの中の少な
くとも1種を含み、かつ全炭素量が0.5〜5.5重量
%にある板状WC形成混合物からなることを特徴とする
粉末冶金用組成物。5. The composite carbide powder according to claim 1 or 2 containing 10% by weight or more, and the balance containing at least one of W, W 2 C and WC, and having a total carbon amount of 0.5 to 5. A composition for powder metallurgy comprising 5% by weight of a plate-like WC-forming mixture.
重量%以上と、残りがカーボン,グラファイト,金属,
合金,セラミックスの中の少なくとも1種の焼結合金形
成補足粉末からなることを特徴とする粉末冶金用組成
物。6. The plate-like WC forming mixture 50 according to claim 5.
% Or more, the rest is carbon, graphite, metal,
A composition for powder metallurgy, comprising at least one kind of powder for forming a sintered alloy, which is an alloy or a ceramic.
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、並びにCo,Ni,Cr,V,
Wおよびこれらの相互合金,カーボン,グラファイトの
中の少なくとも1種の粉末からなることを特徴とする請
求項6記載の粉末冶金用組成物。7. The supplementary powder for forming a sintered alloy comprises carbides, nitrides, oxides and mutual solid solutions of 4a, 5a and 6a metals of the periodic table, and Co, Ni, Cr, V,
7. The composition for powder metallurgy according to claim 6, comprising at least one kind of powder selected from W and mutual alloys thereof, carbon and graphite.
化合物,Cr,Cr含有化合物,CoとNiとCrの2
種以上の合金の中の少なくとも1種のCo,Ni,Cr
供給粉末と、Wおよび/またはW含有化合物のW供給粉
末と、炭素および/または炭素含有化合物の炭素供給粉
末とでなる混合粉末を真空,還元性ガス,浸炭性ガス,
不活性ガスの中の少なくとも1種の雰囲気中で加熱保持
して、Wと炭素とCo,Ni,Crの1種以上とでなる
複合炭化物粉末、もしくは該複合炭化物粉末10重量%
以上と、残りW,W2C,WCの中の少なくとも1種を
含み、かつ全炭素量が0.5〜5.5重量%にある板状
WC形成混合物とすることを特徴とする粉末冶金用組成
物の製造方法。8. Co, Co-containing compound, Ni, Ni-containing compound, Cr, Cr-containing compound, Co, Ni and Cr
At least one Co, Ni, Cr in one or more alloys
A mixed powder consisting of a feed powder, a W feed powder of W and / or a W-containing compound, and a carbon feed powder of carbon and / or a carbon-containing compound is vacuumed, reducing gas, carburizing gas,
Composite carbide powder consisting of W, carbon, and one or more of Co, Ni, and Cr, or 10% by weight of the composite carbide powder, which is heated and held in at least one atmosphere of an inert gas.
Powder metallurgy characterized by the above, and a plate-like WC-forming mixture containing at least one of the remaining W, W 2 C, and WC, and having a total carbon amount of 0.5 to 5.5% by weight. For producing a composition for use.
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JP6064565A JP2978052B2 (en) | 1994-03-07 | 1994-03-07 | Composition for powder metallurgy and method for producing the same |
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 |
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JP6064565A JP2978052B2 (en) | 1994-03-07 | 1994-03-07 | Composition for powder metallurgy and method for producing the same |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1292862C (en) * | 2005-01-12 | 2007-01-03 | 哈尔滨工业大学 | Method for adding carbon nanometer tube adjustable hard alloy carbon content |
KR20220007565A (en) * | 2020-07-10 | 2022-01-18 | 신정민 | Metal binder for cemented carbide, manufacturing method thereof, and cemented carbide manufactured using the same |
CN115815597A (en) * | 2022-10-31 | 2023-03-21 | 成都美奢锐新材料有限公司 | Hard alloy burning-back device and hard alloy burning-back method |
-
1994
- 1994-03-07 JP JP6064565A patent/JP2978052B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1292862C (en) * | 2005-01-12 | 2007-01-03 | 哈尔滨工业大学 | Method for adding carbon nanometer tube adjustable hard alloy carbon content |
KR20220007565A (en) * | 2020-07-10 | 2022-01-18 | 신정민 | Metal binder for cemented carbide, manufacturing method thereof, and cemented carbide manufactured using the same |
CN115815597A (en) * | 2022-10-31 | 2023-03-21 | 成都美奢锐新材料有限公司 | Hard alloy burning-back device and hard alloy burning-back method |
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JP2978052B2 (en) | 1999-11-15 |
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