JP2003082402A - Setter for sintering hard sintered alloy - Google Patents
Setter for sintering hard sintered alloyInfo
- Publication number
- JP2003082402A JP2003082402A JP2001275024A JP2001275024A JP2003082402A JP 2003082402 A JP2003082402 A JP 2003082402A JP 2001275024 A JP2001275024 A JP 2001275024A JP 2001275024 A JP2001275024 A JP 2001275024A JP 2003082402 A JP2003082402 A JP 2003082402A
- Authority
- JP
- Japan
- Prior art keywords
- setter
- sintering
- oxide
- coating film
- 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
- 238000005245 sintering Methods 0.000 title claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 31
- 239000000956 alloy Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 26
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 22
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 4
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 3
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 3
- 229940075613 gadolinium oxide Drugs 0.000 claims description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 3
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 3
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 3
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 3
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 3
- 229940075624 ytterbium oxide Drugs 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 239000000843 powder Substances 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000004927 fusion Effects 0.000 abstract 1
- 238000003466 welding Methods 0.000 description 18
- 239000011195 cermet Substances 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- -1 lanthanum rare earth metal Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000007750 plasma spraying Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、超硬合金、サーメ
ットなど硬質焼結合金の焼結時に用いる敷板、駒などに
最適なセッターに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a setter most suitable for floor boards, bridges, etc. used during the sintering of hard sintered alloys such as cemented carbide and cermet.
【０００２】[0002]
【従来の技術】従来、超硬合金、サーメットの真空焼結
に用いる敷板には、真空中での安定性，脱炭防止，高温
強度，価格など観点から炭素質材が多く使用されてお
り、その材質選定あるいは表面にカーボンブラック，ア
ルミナ，酸化マグネシウム，窒化アルミニウム，窒化ジ
ルコニウムなどの粉末を塗布することにより焼結体との
反応、溶着を防いでいる。しかし、これらの方法では、
結合相量の多い超硬合金を焼結する場合には、敷板と反
応して溶着，浸炭不良，変形などを招く。また、粉末塗
布では使用回ごとに清掃除去と再塗布を行う必要がある
ため、作業性を著しく落とすと言う問題がある。そこ
で、敷板表面に超硬合金と反応や溶着を起こし難い物質
の被覆膜を形成することが試みられている。2. Description of the Related Art Conventionally, carbonaceous materials are often used for floor plates used for vacuum sintering of cemented carbide and cermet from the viewpoints of stability in vacuum, decarburization prevention, high temperature strength, price, etc. By selecting the material or applying powder of carbon black, alumina, magnesium oxide, aluminum nitride, zirconium nitride, etc. on the surface, reaction with the sintered body and welding are prevented. But with these methods,
When a cemented carbide with a large amount of binder phase is sintered, it reacts with the floor plate and causes welding, poor carburization, deformation, and the like. Further, in powder coating, it is necessary to perform cleaning removal and re-coating after each use, so that there is a problem that workability is significantly reduced. Therefore, it has been attempted to form a coating film of a substance that hardly reacts with or welds on the cemented carbide on the surface of the floor plate.
【０００３】提案されている被覆膜を形成した敷板の代
表的なものとして、特開平７−８９７６９号公報および
特表２０００−５０９１０２号公報がある。[0003] As typical ones of the floorboards on which the coating film has been proposed, there are JP-A-7-89769 and JP-A-2000-509102.
【０００４】[0004]
【発明が解決しようとする課題】特開平７−８９７６９
号公報には、硝酸アルミニウムの水溶液を含浸させた高
純度炭素基板を高温焼結することによって、基板の細孔
にＡｌ2Ｏ3が充填された超硬チップ焼結用トレーが記載
されている。本公報に記載されている焼結用トレーは、
基板細孔中のＡｌ2Ｏ3が容易に脱落しないので、粉末を
再塗布する必要はないものの、焼結時にＡｌ2Ｏ3と超硬
成分とが比較的反応し易いために、寿命が短く、還元生
成したＡｌが超硬合金中に拡散して品質を低下させると
言う問題がある。[Patent Document 1] Japanese Patent Application Laid-Open No. 7-89769
The publication describes a tray for cemented carbide chips in which pores of a high-purity carbon substrate impregnated with an aqueous solution of aluminum nitrate are sintered at high temperature to fill the pores of the substrate with Al 2 O 3 . . The sintering tray described in this publication,
Since Al 2 O 3 in the substrate pores does not easily fall off, there is no need to reapply the powder, but the life is short because Al 2 O 3 and the cemented carbide component react relatively easily during sintering. However, there is a problem that the reduced Al diffuses into the cemented carbide and deteriorates the quality.
【０００５】また、特表２０００−５０９１０２号公報
には、１０μｍ以上の平均厚さで２０ｗｔ％以下のＺｒ
Ｏ2を含有するＹ2Ｏ3膜を被覆したグラファイトトレー
を使用する超硬合金またはサーメットの焼結方法が記載
されている。本公報に記載されている焼結トレーは、Ａ
ｌ2Ｏ3よりは安定なために寿命はかなり改善されるもの
の、未だ高価な被覆処理費に見合わないと言う問題があ
る。In addition, in Japanese Patent Publication No. 2000-509102, Zr of 20 wt% or less with an average thickness of 10 μm or more is disclosed.
A method of sintering cemented carbide or cermet using a graphite tray coated with a Y 2 O 3 film containing O 2 is described. The sintering tray described in this publication is A
Since it is more stable than l 2 O 3 , the life is considerably improved, but there is a problem in that it is not worth the expensive coating treatment cost.
【０００６】本発明の目的は、従来の粉末塗布法の手間
を省き、また被覆膜法での早期劣化を防止することによ
って、経済的に、かつ品質的に安定した製品の焼結を可
能にした硬質焼結合金の焼結用セッターを提供すること
にある。The object of the present invention is to save the time and effort of the conventional powder coating method and prevent the premature deterioration in the coating film method, thereby making it possible to sinter the product economically and stably in quality. Another object of the present invention is to provide a setter for sintering a hard sintered alloy.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、硬質焼結
合金の焼結用セッターに用いる被覆膜の材質を検討して
いたところ、熱力学的に安定な酸化物ほど焼結時に硬質
焼結合金と反応し難いこと、酸化物の中でもランタン系
希土類金属酸化物が最適なこと、ランタン系希土類金属
酸化物を被覆したセッターを用いた硬質焼結合金では溶
着，変形，材質不良がなく、セッターの寿命が著しく長
いと言う知見を得て、本発明を完成するに至ったもので
ある。The inventors of the present invention have investigated the material of the coating film used for the setter for sintering a hard sintered alloy, and found that the more thermodynamically stable oxides are used during sintering. Hard to react with hard sintered alloy, lanthanum rare earth metal oxide is the most suitable among oxides, and hard sinter alloy with setter coated with lanthanum rare earth metal oxide causes welding, deformation, and material defects. However, the present invention has been completed based on the finding that the life of the setter is extremely long.
【０００８】すなわち、本発明の硬質焼結合金の焼結用
セッターは、炭素質材の表面にランタン系希土類金属酸
化物を主成分とする被覆膜を形成してなることを特徴と
するものである。That is, the setter for sintering a hard sintered alloy of the present invention is characterized in that a coating film containing a lanthanum-based rare earth metal oxide as a main component is formed on the surface of a carbonaceous material. Is.
【０００９】ランタン系希土類金属は元素記号Ｌａ，Ｃ
ｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕであるが、本発明の
焼結用セッターにおける被覆膜は、ランタン系希土類金
属酸化物からなるもので、具体的には、ランタン系希土
類金属酸化物の中の少なくとも１種を主成分とし、これ
ら以外に酸化マグネシウム、酸化カルシウム、酸化アル
ミニウム、酸化イットリウム、酸化ジルコニウムなどの
安定な酸化物が添加されていても良く、ランタン系希土
類酸化物は９０重量％以上で、安定な酸化物の添加量は
１０重量％以下が好ましい。ランタン系希土類金属の酸
化物の中でも、酸化エルビウム、酸化イッテルビウム、
酸化ホルミウム、酸化ジスプロシウム、酸化テルビウ
ム、酸化ガドリウムの中の少なくとも１種でかつ、他の
酸化物が添加されていない場合がさらに好ましく、その
中でも酸化エルビウム、酸化イッテルビウム、酸化ジス
プロシウム、酸化ガドリウムの中の少なくとも１種でか
つ、他の酸化物が添加されていない場合がよりいっそう
好ましい。The lanthanum rare earth metal is an element symbol La, C.
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
Although y, Ho, Er, Tm, Yb, and Lu, the coating film in the sintering setter of the present invention is made of a lanthanum-based rare earth metal oxide, specifically, a lanthanum-based rare earth metal oxide. In addition to these, stable oxides such as magnesium oxide, calcium oxide, aluminum oxide, yttrium oxide, and zirconium oxide may be added, and the lanthanum-based rare earth oxide is 90 wt% %, The stable oxide content is preferably 10% by weight or less. Among oxides of lanthanum rare earth metals, erbium oxide, ytterbium oxide,
It is at least one of holmium oxide, dysprosium oxide, terbium oxide, and gadolinium oxide, and it is more preferred that no other oxide is added. It is even more preferable that it is at least one kind and no other oxide is added.
【００１０】本発明における被覆膜は、厚みが０．０１
ｍｍ未満では硬質焼結合金が基材と反応，溶着を起こし
易くて使用寿命が短く、１ｍｍを超えて大きくなると膜
の剥離や亀裂発生により硬質焼結合金が基材と反応，溶
着を起こし易いため、０．０１ｍｍ〜１ｍｍが好まし
い。また、気孔率が３０％を超えて大きくなると焼結時
に液相金属が膜中に浸透して反応，溶着を起こし易くな
る。The coating film in the present invention has a thickness of 0.01.
If it is less than mm, the hard sintered alloy easily reacts with the base material to cause welding, and the service life is short. If it exceeds 1 mm, the hard sintered alloy easily reacts with the base material and causes welding due to film peeling or cracking. Therefore, 0.01 mm to 1 mm is preferable. Further, when the porosity exceeds 30% and becomes large, the liquid phase metal easily permeates into the film during the sintering to easily cause reaction and welding.
【００１１】また、被覆膜は、基材との間にＷ，Ｍｏな
どの高融点金属やＡｌ2Ｏ3，ＺｒＯ2，Ｙ2Ｏ3などの他
酸化物からなる中間層を設けても良く、元素の異なるラ
ンタン系希土類金属酸化物の多層膜で構成されても良
い。The coating film may be provided with an intermediate layer between the base material and a refractory metal such as W or Mo or another oxide such as Al 2 O 3 , ZrO 2 or Y 2 O 3. Alternatively, it may be composed of a multilayer film of lanthanum rare earth metal oxides having different elements.
【００１２】本発明における硬質焼結合金は、周期律表
第４ａ，５ａ，６ａ族元素の炭化物，窒化物と鉄族金属
とを主成分とするもので、具体的には、各種組成の超硬
合金あるいはサーメットを挙げることができる。The hard sintered alloy according to the present invention is mainly composed of carbides and nitrides of elements of groups 4a, 5a and 6a of the Periodic Table and iron group metals. Hard alloys or cermets can be mentioned.
【００１３】本発明の焼結用セッターにおける基材は、
炭素質材からなるもので、具体的には、黒鉛質あるいは
カーボン質の炭素材を挙げることができる。The base material in the sintering setter of the present invention is
It is made of a carbonaceous material, and specifically, a graphitic or carbonaceous carbon material can be mentioned.
【００１４】本発明の焼結用セッターにおける被覆膜の
形成方法として、溶射法、ＣＶＤ法、塗布粉末やアルコ
キシド膜の焼成法などを挙げることができる。その中で
もプラズマ溶射法は、高融点のランタン系希土類金属酸
化物でも緻密で密着性の良好な皮膜が形成できるので好
ましい。Examples of the method for forming the coating film in the sintering setter of the present invention include a thermal spraying method, a CVD method, a firing method for coating powder and an alkoxide film. Among them, the plasma spraying method is preferable because it is possible to form a dense and good adhesive film even with a high melting point lanthanum rare earth metal oxide.
【００１５】[0015]
【作用】本発明の硬質焼結合金の焼結用セッターは、炭
素質材の表面に形成された被覆膜が、焼結時に起こる硬
質超硬合金と炭素質材との反応，溶着を防止する作用を
し、被覆膜を構成するランタン系希土類金属酸化物が、
優れた耐溶着性を発揮してセッター寿命を向上させる作
用をしている。The function of the setter for sintering a hard sintered alloy of the present invention is that the coating film formed on the surface of the carbonaceous material prevents the reaction and welding between the hard cemented carbide and the carbonaceous material occurring during sintering. The lanthanum-based rare earth metal oxide that acts to
It has excellent welding resistance and has the function of improving the setter life.
【００１６】[0016]
【実施例１】気孔率が５％でカーボン質からなる炭素材
の平板表面に、表１に示した化合物の顆粒状焼成粉末を
用いたプラズマ溶射法で被覆膜を形成させることによ
り、本発明品１〜６と比較品１〜６の焼結用セッターを
作製した。得られた被覆膜の厚みと気孔率の測定結果を
表１に併記した。尚、プラズマ溶射条件は、ガス：窒素
＋水素、電流：５００Ａ、電圧：７０Ｖなどであり、膜
厚みは溶射時間で調整した。Example 1 A coating film was formed on a flat plate surface of a carbonaceous material having a porosity of 5% and made of a carbonaceous material by a plasma spraying method using granular fired powders of the compounds shown in Table 1, Invention setters 1 to 6 and comparative setters 1 to 6 were prepared for sintering. The measurement results of the thickness and the porosity of the obtained coating film are also shown in Table 1. The plasma spraying conditions were gas: nitrogen + hydrogen, current: 500 A, voltage: 70 V, and the film thickness was adjusted by the spraying time.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【実施例２】実施例１で得られた本発明品１〜６と比較
品１〜６の焼結用セッターを用い、下記に示す材質と形
状の超硬合金およびサーメット製チップが得られる混合
粉末のプレス成形体を真空焼結し、各セッターとチップ
が反応，溶着を起こして使用不能となるまでの回数を求
めた。その結果を表２に示す。
超硬合金（Ａ） 組成（重量％）：８８ＷＣ−２ＴｉＣ
−４ＴａＣ−６Ｃｏ、形状：ＩＳＯのＳＮＭＡ１２０４
０８
超硬合金（Ｂ） 組成（重量％）：８０ＷＣ−２０Ｃ
ｏ、形状：約５０×５０×１０ｍｍ
サーメット（Ｃ） 組成（重量％）：５５ＴｉＣＮ−１
５ＷＣ−１０ＴａＣ−５Ｍｏ2Ｃ−７Ｃｏ−８Ｎｉ、形
状：ＩＳＯのＳＮＭＡ１２０４０８[Example 2] Using the setters for sintering of the present invention products 1 to 6 and the comparative products 1 to 6 obtained in Example 1, a mixture for obtaining cemented carbide and cermet chips having the following materials and shapes The powder press-molded product was vacuum-sintered, and the number of times until each setter and chip reacted and welded and became unusable was determined. The results are shown in Table 2. Cemented Carbide (A) Composition (wt%): 88WC-2TiC
-4TaC-6Co, shape: ISO SNMA1204
08 cemented carbide (B) composition (% by weight): 80WC-20C
o, shape: about 50 × 50 × 10 mm cermet (C) composition (% by weight): 55TiCN-1
5WC-10TaC-5Mo 2 C- 7Co-8Ni, Form: ISO SNMA120408
【００１９】[0019]
【表２】 [Table 2]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１３年９月１２日（２００１．９．１
２）[Submission date] September 12, 2001 (2001.9.1)
2)
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】硬質焼結合金の焼結用セッターTitle: Setter for sintering hard sintered alloy
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は、超硬合金、サーメ
ットなど硬質焼結合金の焼結時に用いる敷板、駒などに
最適なセッターに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a setter most suitable for floor boards, bridges, etc. used during the sintering of hard sintered alloys such as cemented carbide and cermet.
【０００２】[0002]
【従来の技術】従来、超硬合金、サーメットの真空焼結
に用いる敷板には、真空中での安定性，脱炭防止，高温
強度，価格など観点から炭素質材が多く使用されてお
り、その材質選定あるいは表面にカーボンブラック，ア
ルミナ，酸化マグネシウム，窒化アルミニウム，窒化ジ
ルコニウムなどの粉末を塗布することにより焼結体との
反応、溶着を防いでいる。しかし、これらの方法では、
結合相量の多い超硬合金を焼結する場合には、敷板と反
応して溶着，浸炭不良，変形などを招く。また、粉末塗
布では使用回ごとに清掃除去と再塗布を行う必要がある
ため、作業性を著しく落とすと言う問題がある。そこ
で、敷板表面に超硬合金と反応や溶着を起こし難い物質
の被覆膜を形成することが試みられている。2. Description of the Related Art Conventionally, carbonaceous materials are often used for floor plates used for vacuum sintering of cemented carbide and cermet from the viewpoints of stability in vacuum, decarburization prevention, high temperature strength, price, etc. By selecting the material or applying powder of carbon black, alumina, magnesium oxide, aluminum nitride, zirconium nitride, etc. on the surface, reaction with the sintered body and welding are prevented. But with these methods,
When a cemented carbide with a large amount of binder phase is sintered, it reacts with the floor plate and causes welding, poor carburization, deformation, and the like. Further, in powder coating, it is necessary to perform cleaning removal and re-coating after each use, so that there is a problem that workability is significantly reduced. Therefore, it has been attempted to form a coating film of a substance that hardly reacts with or welds on the cemented carbide on the surface of the floor plate.
【０００３】提案されている被覆膜を形成した敷板の代
表的なものとして、特開平７−８９７６９号公報および
特表２０００−５０９１０２号公報がある。[0003] As typical ones of the floorboards on which the coating film has been proposed, there are JP-A-7-89769 and JP-A-2000-509102.
【０００４】[0004]
【発明が解決しようとする課題】特開平７−８９７６９
号公報には、硝酸アルミニウムの水溶液を含浸させた高
純度炭素基板を高温焼結することによって、基板の細孔
にＡｌ2Ｏ3が充填された超硬チップ焼結用トレーが記載
されている。本公報に記載されている焼結用トレーは、
基板細孔中のＡｌ2Ｏ3が容易に脱落しないので、粉末を
再塗布する必要はないものの、焼結時にＡｌ2Ｏ3と超硬
成分とが比較的反応し易いために、寿命が短く、還元生
成したＡｌが超硬合金中に拡散して品質を低下させると
言う問題がある。[Patent Document 1] Japanese Patent Application Laid-Open No. 7-89769
The publication describes a tray for cemented carbide chips in which pores of a high-purity carbon substrate impregnated with an aqueous solution of aluminum nitrate are sintered at high temperature to fill the pores of the substrate with Al 2 O 3 . . The sintering tray described in this publication,
Since Al 2 O 3 in the substrate pores does not easily fall off, there is no need to reapply the powder, but the life is short because Al 2 O 3 and the cemented carbide component react relatively easily during sintering. However, there is a problem that the reduced Al diffuses into the cemented carbide and deteriorates the quality.
【０００５】また、特表２０００−５０９１０２号公報
には、１０μｍ以上の平均厚さで２０ｗｔ％以下のＺｒ
Ｏ2を含有するＹ2Ｏ3膜を被覆したグラファイトトレー
を使用する超硬合金またはサーメットの焼結方法が記載
されている。本公報に記載されている焼結トレーは、Ａ
ｌ2Ｏ3よりは安定なために寿命はかなり改善されるもの
の、未だ高価な被覆処理費に見合わないと言う問題があ
る。In addition, in Japanese Patent Publication No. 2000-509102, Zr of 20 wt% or less with an average thickness of 10 μm or more is disclosed.
A method of sintering cemented carbide or cermet using a graphite tray coated with a Y 2 O 3 film containing O 2 is described. The sintering tray described in this publication is A
Since it is more stable than l 2 O 3 , the life is considerably improved, but there is a problem in that it is not worth the expensive coating treatment cost.
【０００６】本発明の目的は、従来の粉末塗布法の手間
を省き、また被覆膜法での早期劣化を防止することによ
って、経済的に、かつ品質的に安定した製品の焼結を可
能にした硬質焼結合金の焼結用セッターを提供すること
にある。The object of the present invention is to save the time and effort of the conventional powder coating method and prevent the premature deterioration in the coating film method, thereby making it possible to sinter the product economically and stably in quality. Another object of the present invention is to provide a setter for sintering a hard sintered alloy.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、硬質焼結
合金の焼結用セッターに用いる被覆膜の材質を検討して
いたところ、熱力学的に安定な酸化物ほど焼結時に硬質
焼結合金と反応し難いこと、酸化物の中でもランタン系
希土類金属酸化物が最適なこと、ランタン系希土類金属
酸化物を被覆したセッターを用いた硬質焼結合金では溶
着，変形，材質不良がなく、セッターの寿命が著しく長
いと言う知見を得て、本発明を完成するに至ったもので
ある。The inventors of the present invention have investigated the material of the coating film used for the setter for sintering a hard sintered alloy, and found that the more thermodynamically stable oxides are used during sintering. Hard to react with hard sintered alloy, lanthanum rare earth metal oxide is the most suitable among oxides, and hard sinter alloy with setter coated with lanthanum rare earth metal oxide causes welding, deformation, and material defects. However, the present invention has been completed based on the finding that the life of the setter is extremely long.
【０００８】すなわち、本発明の硬質焼結合金の焼結用
セッターは、炭素質材の表面にランタン系希土類金属酸
化物を主成分とする被覆膜を形成してなることを特徴と
するものである。That is, the setter for sintering a hard sintered alloy of the present invention is characterized in that a coating film containing a lanthanum-based rare earth metal oxide as a main component is formed on the surface of a carbonaceous material. Is.
【０００９】ランタン系希土類金属は元素記号Ｌａ，Ｃ
ｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕであるが、本発明の
焼結用セッターにおける被覆膜は、ランタン系希土類金
属酸化物からなるもので、具体的には、ランタン系希土
類金属酸化物の中の少なくとも１種を主成分とし、これ
ら以外に酸化マグネシウム、酸化カルシウム、酸化アル
ミニウム、酸化イットリウム、酸化ジルコニウムなどの
安定な酸化物が添加されていても良く、ランタン系希土
類酸化物は９０重量％以上で、安定な酸化物の添加量は
１０重量％以下が好ましい。ランタン系希土類金属の酸
化物の中でも、酸化エルビウム、酸化イッテルビウム、
酸化ホルミウム、酸化ジスプロシウム、酸化テルビウ
ム、酸化ガドリウムの中の少なくとも１種でかつ、他の
酸化物が添加されていない場合がさらに好ましく、その
中でも酸化エルビウム、酸化イッテルビウム、酸化ジス
プロシウム、酸化ガドリウムの中の少なくとも１種でか
つ、他の酸化物が添加されていない場合がよりいっそう
好ましい。The lanthanum rare earth metal is an element symbol La, C.
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
Although y, Ho, Er, Tm, Yb, and Lu, the coating film in the sintering setter of the present invention is made of a lanthanum-based rare earth metal oxide, specifically, a lanthanum-based rare earth metal oxide. In addition to these, stable oxides such as magnesium oxide, calcium oxide, aluminum oxide, yttrium oxide, and zirconium oxide may be added, and the lanthanum-based rare earth oxide is 90 wt% %, The stable oxide content is preferably 10% by weight or less. Among oxides of lanthanum rare earth metals, erbium oxide, ytterbium oxide,
It is at least one of holmium oxide, dysprosium oxide, terbium oxide, and gadolinium oxide, and it is more preferred that no other oxide is added. It is even more preferable that it is at least one kind and no other oxide is added.
【００１０】本発明における被覆膜は、厚みが０．０１
ｍｍ未満では硬質焼結合金が基材と反応，溶着を起こし
易くて使用寿命が短く、１ｍｍを超えて大きくなると膜
の剥離や亀裂発生により硬質焼結合金が基材と反応，溶
着を起こし易いため、０．０１ｍｍ〜１ｍｍが好まし
い。また、気孔率が３０％を超えて大きくなると焼結時
に液相金属が膜中に浸透して反応，溶着を起こし易くな
る。The coating film in the present invention has a thickness of 0.01.
If it is less than mm, the hard sintered alloy easily reacts with the base material to cause welding, and the service life is short. If it exceeds 1 mm, the hard sintered alloy easily reacts with the base material and causes welding due to film peeling or cracking. Therefore, 0.01 mm to 1 mm is preferable. Further, when the porosity exceeds 30% and becomes large, the liquid phase metal easily permeates into the film during the sintering to easily cause reaction and welding.
【００１１】また、被覆膜は、基材との間にＷ，Ｍｏな
どの高融点金属やＡｌ2Ｏ3，ＺｒＯ2，Ｙ2Ｏ3などの他
酸化物からなる中間層を設けても良く、元素の異なるラ
ンタン系希土類金属酸化物の多層膜で構成されても良
い。The coating film may be provided with an intermediate layer between the base material and a refractory metal such as W or Mo or another oxide such as Al 2 O 3 , ZrO 2 or Y 2 O 3. Alternatively, it may be composed of a multilayer film of lanthanum rare earth metal oxides having different elements.
【００１２】本発明における硬質焼結合金は、周期律表
第４ａ，５ａ，６ａ族元素の炭化物，窒化物と鉄族金属
とを主成分とするもので、具体的には、各種組成の超硬
合金あるいはサーメットを挙げることができる。The hard sintered alloy according to the present invention is mainly composed of carbides and nitrides of elements of groups 4a, 5a and 6a of the Periodic Table and iron group metals. Hard alloys or cermets can be mentioned.
【００１３】本発明の焼結用セッターにおける基材は、
炭素質材からなるもので、具体的には、黒鉛質あるいは
カーボン質の炭素材を挙げることができる。The base material in the sintering setter of the present invention is
It is made of a carbonaceous material, and specifically, a graphitic or carbonaceous carbon material can be mentioned.
【００１４】本発明の焼結用セッターにおける被覆膜の
形成方法として、溶射法、ＣＶＤ法、塗布粉末やアルコ
キシド膜の焼成法などを挙げることができる。その中で
もプラズマ溶射法は、高融点のランタン系希土類金属酸
化物でも緻密で密着性の良好な皮膜が形成できるので好
ましい。Examples of the method for forming the coating film in the sintering setter of the present invention include a thermal spraying method, a CVD method, a firing method for coating powder and an alkoxide film. Among them, the plasma spraying method is preferable because it is possible to form a dense and good adhesive film even with a high melting point lanthanum rare earth metal oxide.
【００１５】[0015]
【作用】本発明の硬質焼結合金の焼結用セッターは、炭
素質材の表面に形成された被覆膜が、焼結時に起こる硬
質超硬合金と炭素質材との反応，溶着を防止する作用を
し、被覆膜を構成するランタン系希土類金属酸化物が、
優れた耐溶着性を発揮してセッター寿命を向上させる作
用をしている。The function of the setter for sintering a hard sintered alloy of the present invention is that the coating film formed on the surface of the carbonaceous material prevents the reaction and welding between the hard cemented carbide and the carbonaceous material occurring during sintering. The lanthanum-based rare earth metal oxide that acts to
It has excellent welding resistance and has the function of improving the setter life.
【００１６】[0016]
【実施例１】気孔率が５％でカーボン質からなる炭素材
の平板表面に、表１に示した化合物の顆粒状焼成粉末を
用いたプラズマ溶射法で被覆膜を形成させることによ
り、本発明品１〜６と比較品１〜６の焼結用セッターを
作製した。得られた被覆膜の厚みと気孔率の測定結果を
表１に併記した。尚、プラズマ溶射条件は、ガス：窒素
＋水素、電流：５００Ａ、電圧：７０Ｖなどであり、膜
厚みは溶射時間で調整した。Example 1 A coating film was formed on a flat plate surface of a carbonaceous material having a porosity of 5% and made of a carbonaceous material by a plasma spraying method using granular fired powders of the compounds shown in Table 1, Invention setters 1 to 6 and comparative setters 1 to 6 were prepared for sintering. The measurement results of the thickness and the porosity of the obtained coating film are also shown in Table 1. The plasma spraying conditions were gas: nitrogen + hydrogen, current: 500 A, voltage: 70 V, and the film thickness was adjusted by the spraying time.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【実施例２】実施例１で得られた本発明品１〜６と比較
品１〜６の焼結用セッターを用い、下記に示す材質と形
状の超硬合金およびサーメット製チップが得られる混合
粉末のプレス成形体を真空焼結し、各セッターとチップ
が反応，溶着を起こして使用不能となるまでの回数を求
めた。その結果を表２に示す。
超硬合金（Ａ） 組成（重量％）：８８ＷＣ−２ＴｉＣ
−４ＴａＣ−６Ｃｏ、形状：ＩＳＯのＳＮＭＡ１２０４
０８
超硬合金（Ｂ） 組成（重量％）：８０ＷＣ−２０Ｃ
ｏ、形状：約５０×５０×１０ｍｍ
サーメット（Ｃ） 組成（重量％）：５５ＴｉＣＮ−１
５ＷＣ−１０ＴａＣ−５Ｍｏ2Ｃ−７Ｃｏ−８Ｎｉ、形
状：ＩＳＯのＳＮＭＡ１２０４０８[Example 2] Using the setters for sintering of the present invention products 1 to 6 and the comparative products 1 to 6 obtained in Example 1, a mixture for obtaining cemented carbide and cermet chips having the following materials and shapes The powder press-molded product was vacuum-sintered, and the number of times until each setter and chip reacted and welded and became unusable was determined. The results are shown in Table 2. Cemented Carbide (A) Composition (wt%): 88WC-2TiC
-4TaC-6Co, shape: ISO SNMA1204
08 cemented carbide (B) composition (% by weight): 80WC-20C
o, shape: about 50 × 50 × 10 mm cermet (C) composition (% by weight): 55TiCN-1
5WC-10TaC-5Mo 2 C- 7Co-8Ni, Form: ISO SNMA120408
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【発明の効果】上述したように本発明の硬質焼結合金の
焼結用セッターは、炭素質材の表面に形成された被覆膜
が、焼結時に起こる硬質超硬合金と炭素質材との反応，
溶着を防止する。被覆膜を構成するランタン系希土類金
属酸化物が、優れた耐溶着性を示すためセッター寿命を
向上させるという効果を発揮するものである。As described above, in the setter for sintering a hard sintered alloy of the present invention, the coating film formed on the surface of the carbonaceous material is composed of the hard cemented carbide and the carbonaceous material that occur during sintering. Reaction of,
Prevents welding. The lanthanum-based rare earth metal oxide forming the coating film exhibits an excellent resistance to welding and thus exhibits the effect of improving the setter life.
Claims (4)
化物を主成分とする被覆膜を形成してなることを特徴と
する硬質焼結合金の焼結用セッター。1. A setter for sintering a hard sintered alloy, characterized in that a coating film containing a lanthanum-based rare earth metal oxide as a main component is formed on the surface of a carbonaceous material.
エルビウム、酸化イッテルビウム、酸化ホルミウム、酸
化ジスプロシウム、酸化テルビウム、酸化ガドリウムの
中の少なくとも１種であることを特徴とする請求項１記
載の硬質焼結合金の焼結用セッター。2. The hard material according to claim 1, wherein the lanthanum-based rare earth metal oxide is at least one selected from erbium oxide, ytterbium oxide, holmium oxide, dysprosium oxide, terbium oxide, and gadolinium oxide. A setter for sintering sintered alloys.
ａ，６ａ族元素の炭化物，窒化物と鉄族金属とが主成分
であることを特徴とする請求項１又は２記載の硬質焼結
合金の焼結用セッター。3. The hard sintered alloy is produced according to the periodic table Nos. 4a and 5 of the periodic table.
The setter for sintering a hard sintered alloy according to claim 1 or 2, wherein carbides and nitrides of a and 6a group elements and an iron group metal are main components.
で、かつ気孔率が３０％以下であることを特徴とする請
求項１又は２記載の硬質焼結合金の焼結用セッター。4. The coating film has a thickness of 0.01 to 1 mm.
And a porosity of not more than 30%. 3. A setter for sintering a hard sintered alloy according to claim 1, wherein the setter has a porosity of 30% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001275024A JP3865363B2 (en) | 2001-09-11 | 2001-09-11 | Setter for sintering hard sintered alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001275024A JP3865363B2 (en) | 2001-09-11 | 2001-09-11 | Setter for sintering hard sintered alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003082402A true JP2003082402A (en) | 2003-03-19 |
| JP3865363B2 JP3865363B2 (en) | 2007-01-10 |
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| JP2001275024A Expired - Lifetime JP3865363B2 (en) | 2001-09-11 | 2001-09-11 | Setter for sintering hard sintered alloys |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004332013A (en) * | 2003-05-01 | 2004-11-25 | Hitachi Tool Engineering Ltd | Coated graphite tray |
| JP2004332012A (en) * | 2003-05-01 | 2004-11-25 | Shin Etsu Chem Co Ltd | Heat resistant jig and heat treatment / sintering method |
| JP2005285854A (en) * | 2004-03-26 | 2005-10-13 | Tdk Corp | Setter for sintering sintered magnet and manufacturing method of sintered magnet using same |
| US7507481B2 (en) | 2002-11-20 | 2009-03-24 | Shin-Etsu Chemical Co., Ltd. | Heat resistant coated member, making method, and treatment using the same |
| JP2015054812A (en) * | 2013-09-13 | 2015-03-23 | 三井金属鉱業株式会社 | Baking jig and method for manufacturing the baking jig |
| CN114082949A (en) * | 2021-10-08 | 2022-02-25 | 厦门金鹭特种合金有限公司 | Interlayer for high-temperature sintering of hard alloy and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073794A (en) * | 2001-06-18 | 2003-03-12 | Shin Etsu Chem Co Ltd | Heat resistant coating |
-
2001
- 2001-09-11 JP JP2001275024A patent/JP3865363B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073794A (en) * | 2001-06-18 | 2003-03-12 | Shin Etsu Chem Co Ltd | Heat resistant coating |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7507481B2 (en) | 2002-11-20 | 2009-03-24 | Shin-Etsu Chemical Co., Ltd. | Heat resistant coated member, making method, and treatment using the same |
| KR101168422B1 (en) | 2002-11-20 | 2012-07-25 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Making Method of Heat Resistant Coated Member |
| JP2004332013A (en) * | 2003-05-01 | 2004-11-25 | Hitachi Tool Engineering Ltd | Coated graphite tray |
| JP2004332012A (en) * | 2003-05-01 | 2004-11-25 | Shin Etsu Chem Co Ltd | Heat resistant jig and heat treatment / sintering method |
| JP2005285854A (en) * | 2004-03-26 | 2005-10-13 | Tdk Corp | Setter for sintering sintered magnet and manufacturing method of sintered magnet using same |
| JP2015054812A (en) * | 2013-09-13 | 2015-03-23 | 三井金属鉱業株式会社 | Baking jig and method for manufacturing the baking jig |
| CN114082949A (en) * | 2021-10-08 | 2022-02-25 | 厦门金鹭特种合金有限公司 | Interlayer for high-temperature sintering of hard alloy and manufacturing method thereof |
| CN114082949B (en) * | 2021-10-08 | 2024-02-20 | 厦门金鹭特种合金有限公司 | Interlayer for high-temperature sintered hard alloy and manufacturing method thereof |
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| JP3865363B2 (en) | 2007-01-10 |
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