JP3865363B2 - Setter for sintering hard sintered alloys - Google Patents
Setter for sintering hard sintered alloys Download PDFInfo
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- JP3865363B2 JP3865363B2 JP2001275024A JP2001275024A JP3865363B2 JP 3865363 B2 JP3865363 B2 JP 3865363B2 JP 2001275024 A JP2001275024 A JP 2001275024A JP 2001275024 A JP2001275024 A JP 2001275024A JP 3865363 B2 JP3865363 B2 JP 3865363B2
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- oxide
- sintering
- setter
- hard sintered
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Description
【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。
【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。
【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。
【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。
【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ＺｒＯ2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、Ａｌ2Ｏ3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。
【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。
【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。
【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。
【０００９】
ランタン系希土類金属は元素記号Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，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。
【００１０】
本発明における被覆膜は、厚みが０．０１ｍｍ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。
【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。
【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。
【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。
【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。
【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。
【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。
【００１７】
【表１】
【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ＳＮＭＡ１２０４０８
超硬合金（Ｂ） 組成（重量％）：８０ＷＣ−２０Ｃｏ、形状：約５０×５０×１０ｍｍ
サーメット（Ｃ） 組成（重量％）：５５ＴｉＣＮ−１５ＷＣ−１０ＴａＣ−５Ｍｏ2Ｃ−７Ｃｏ−８Ｎｉ、形状：ＩＳＯのＳＮＭＡ１２０４０８
【００１９】
【表２】
【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。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a setter that is most suitable for a base plate, a piece, and the like used when sintering a hard sintered alloy such as cemented carbide or cermet.
[0002]
[Prior art]
Conventionally, carbonaceous materials have been used for the base plates used for vacuum sintering of cemented carbides and cermets from the viewpoints of stability in vacuum, prevention of decarburization, high temperature strength, and cost. By applying powders such as carbon black, alumina, magnesium oxide, aluminum nitride, and zirconium nitride, the reaction with the sintered body and welding are prevented. However, in these methods, when a cemented carbide with a large amount of binder phase is sintered, it reacts with the base plate, causing welding, carburization failure, deformation, and the like. Further, in powder coating, there is a problem that workability is remarkably reduced because it is necessary to perform cleaning removal and re-coating every use. Therefore, attempts have been made to form a coating film of a substance that hardly reacts or welds with the cemented carbide on the surface of the floor plate.
[0003]
As representative examples of the base plate on which the coating film has been proposed, there are JP-A-7-89769 and JP-T 2000-509102.
[0004]
[Problems to be solved by the invention]
Japanese Laid-Open Patent Publication No. 7-89769 discloses a carbide chip sintering tray in which a high-purity carbon substrate impregnated with an aqueous solution of aluminum nitrate is sintered at a high temperature to fill the pores of the substrate with Al 2 O 3. Is described. Sintering trays described in this publication, since the Al 2 O 3 in the substrate pores do not easily fall off, but again there is no need for applying the powders, carbide and Al 2 O 3 during sintering component Is relatively easy to react, and thus there is a problem that the life is short, and the reduction-generated Al diffuses into the cemented carbide and deteriorates the quality.
[0005]
In addition, JP 2000-509102 A discloses a cemented carbide or cermet sintering method using a graphite tray coated with a Y 2 O 3 film containing ZrO 2 having an average thickness of 10 μm or more and 20 wt% or less. Is described. The sintered tray described in this publication has a problem that although it is more stable than Al 2 O 3 and thus its life is considerably improved, it still does not meet the cost of expensive coating treatment.
[0006]
The object of the present invention is to eliminate the trouble of the conventional powder coating method, and to prevent premature deterioration in the coating film method, thereby making it possible to sinter products economically and stably in quality. It is to provide a setter for sintering a sintered alloy.
[0007]
[Means for Solving the Problems]
The present inventors have studied the material of the coating film used for the setter for sintering of a hard sintered alloy, and it is difficult for a thermodynamically stable oxide to react with a hard sintered alloy during sintering. Of the oxides, lanthanum rare earth metal oxides are optimal, and hard sintered alloys using setters coated with lanthanum rare earth metal oxides have no welding, deformation, or material defects, This knowledge has been obtained and the present invention has been completed.
[0008]
That is, the setter for sintering a hard sintered alloy according to the present invention is characterized in that a coating film containing a lanthanum rare earth metal oxide as a main component is formed on the surface of a carbonaceous material.
[0009]
The lanthanum rare earth metals are the element symbols La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, but the coating in the setter for sintering of the present invention The film is made of a lanthanum rare earth metal oxide. Specifically, the film is mainly composed of at least one of lanthanum rare earth metal oxides, and in addition to these, magnesium oxide, calcium oxide, aluminum oxide, yttrium oxide. A stable oxide such as zirconium oxide may be added. The lanthanum rare earth oxide is preferably 90% by weight or more, and the amount of the stable oxide added is preferably 10% by weight or less. Among oxides of lanthanum rare earth metals, it is more preferable that at least one of erbium oxide, ytterbium oxide, holmium oxide, dysprosium oxide, terbium oxide, and gadolinium oxide and no other oxide is added, Among them, it is even more preferable that at least one of erbium oxide, ytterbium oxide, dysprosium oxide, and gadolinium oxide is not added.
[0010]
The coating film according to the present invention has a thickness of less than 0.01 mm, and the hard sintered alloy easily reacts with and adheres to the base material. The service life is short. Since the bond gold easily reacts and welds with the base material, 0.01 mm to 1 mm is preferable. Further, when the porosity exceeds 30%, the liquid phase metal permeates into the film during sintering, and reaction and welding are likely to occur.
[0011]
Further, the coating film may be provided with an intermediate layer made of a refractory metal such as W or Mo or another oxide such as Al 2 O 3 , ZrO 2 , or Y 2 O 3 between the substrate and the element. May be composed of multilayer films of different lanthanum rare earth metal oxides.
[0012]
The hard sintered alloy in the present invention is mainly composed of carbides, nitrides, and iron group metals of Group 4a, 5a, and 6a elements of the periodic table, and specifically, cemented carbides of various compositions or A cermet can be mentioned.
[0013]
The base material in the setter for sintering of the present invention is made of a carbonaceous material, and specific examples include graphite or carbonaceous carbon material.
[0014]
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, and a firing method of coating powder and alkoxide film. Among them, the plasma spraying method is preferable because a dense and excellent adhesion film can be formed even with a high melting point lanthanum rare earth metal oxide.
[0015]
[Action]
The setter for sintering of the hard sintered alloy of the present invention has a function in which 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 that occurs during sintering. The lanthanum rare earth metal oxide constituting the coating film has an effect of improving the setter life by exhibiting excellent welding resistance.
[0016]
[Example 1]
By forming a coating film on a flat plate surface of a carbonaceous material having a porosity of 5% by a plasma spraying method using a granular calcined powder of the compounds shown in Table 1, products 1 to 6 of the present invention. And the setter for sintering of comparative products 1-6 was produced. Table 1 also shows the measurement results of the thickness and porosity of the obtained coating film. The plasma spraying conditions were gas: nitrogen + hydrogen, current: 500 A, voltage: 70 V, etc., and the film thickness was adjusted by the spraying time.
[0017]
[Table 1]
[Example 2]
Using the setters for sintering of the present invention products 1 to 6 and comparative products 1 to 6 obtained in Example 1, pressed powder compacts of cemented carbide and cermet chips of the following materials and shapes are obtained. The setter and the chip reacted and welded, and the number of times until they became unusable was determined. The results are shown in Table 2.
Cemented carbide (A) Composition (% by weight): 88WC-2TiC-4TaC-6Co, shape: ISO SNMA120408
Cemented carbide (B) Composition (% by weight): 80WC-20Co, shape: about 50 × 50 × 10 mm
Cermet (C) Composition (% by weight): 55TiCN-15WC-10TaC-5Mo 2 C-7Co-8Ni, shape: SNMA120408 of ISO
[0019]
[Table 2]
【The invention's effect】
As described above, the setter for sintering a hard sintered alloy according to the present invention has a coating film formed on the surface of a carbonaceous material that reacts and welds the hard cemented carbide and the carbonaceous material that occur during sintering. To prevent. Since the lanthanum rare earth metal oxide constituting the coating film exhibits excellent welding resistance, it exhibits the effect of improving the setter life.
Claims (1)
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 JP2003082402A (en) | 2003-03-19 |
| JP3865363B2 true JP3865363B2 (en) | 2007-01-10 |
Family
ID=19099963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001275024A Expired - Lifetime JP3865363B2 (en) | 2001-09-11 | 2001-09-11 | Setter for sintering hard sintered alloys |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3865363B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200420431A (en) | 2002-11-20 | 2004-10-16 | Shinetsu Chemical Co | Heat resistant coated member, making method, and treatment using the same |
| JP3962354B2 (en) * | 2003-05-01 | 2007-08-22 | 日立ツール株式会社 | Coated graphite tray |
| JP2004332012A (en) * | 2003-05-01 | 2004-11-25 | Shin Etsu Chem Co Ltd | Heat-resistant holder and heat-treating/sintering method |
| JP4605436B2 (en) * | 2004-03-26 | 2011-01-05 | Ｔｄｋ株式会社 | Sintered magnet sintering jig and method of manufacturing sintered magnet |
| JP5995809B2 (en) * | 2013-09-13 | 2016-09-21 | 三井金属鉱業株式会社 | Baking jig and method for manufacturing the baking jig |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073794A (en) * | 2001-06-18 | 2003-03-12 | Shin Etsu Chem Co Ltd | Heat-resistant coated member |
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2001
- 2001-09-11 JP JP2001275024A patent/JP3865363B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JP2003082402A (en) | 2003-03-19 |
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