JPH03109271A - Sheet for sintering - Google Patents
Sheet for sinteringInfo
- Publication number
- JPH03109271A JPH03109271A JP1247055A JP24705589A JPH03109271A JP H03109271 A JPH03109271 A JP H03109271A JP 1247055 A JP1247055 A JP 1247055A JP 24705589 A JP24705589 A JP 24705589A JP H03109271 A JPH03109271 A JP H03109271A
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- powder
- carbon
- fired
- sintering
- 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 abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 9
- 239000004917 carbon fiber Substances 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 229910017083 AlN Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910003465 moissanite Inorganic materials 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 241000981595 Zoysia japonica Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
Landscapes
- Furnace Charging Or Discharging (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はコバルト含有量の多い超硬合金のような被焼成
物を真空中又は非酸化性雰囲気中で焼成する際に使用さ
れる焼成用シートに関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is a method for firing a material to be fired, such as a cemented carbide with a high cobalt content, in a vacuum or in a non-oxidizing atmosphere. It concerns the seat.
（従来の技術）
従来、超硬合金等の被焼成物を真空中又は非酸化性雰囲
気中で焼成する場合には、被焼成物とそれを載置するカ
ーボン製のセッターとの間の融着を防止するために、敷
粉と称されるＡｌｚＯｓ粉体のような高融点セラミック
ス粉体をセッター上に散布していたが、この作業は人手
によるため散布の不均一から被焼成物にうねりやピンホ
ール等の欠点を生じやすく、またコスト高となる問題が
あった。(Prior art) Conventionally, when firing an object to be fired such as cemented carbide in a vacuum or in a non-oxidizing atmosphere, fusion between the object to be fired and a carbon setter on which it is placed has occurred. In order to prevent this, a high melting point ceramic powder such as AlzOs powder, called "shiba powder", was sprinkled on the setter, but since this work was done manually, uneven scattering caused undulations and undulations on the fired object. There is a problem that defects such as pinholes are likely to occur and the cost is high.
そこで、本発明者等は有機フィルムの表面に高融点のセ
ラミックス粉体を有機性バインダーにより保持させてコ
ーティング層を形成した焼成用シートを先に発明し、特
願昭６２−１５６８７９号（特開昭６３−３１９１４５
号）として既に提案済みである。Therefore, the present inventors first invented a sheet for firing in which a coating layer was formed by holding high melting point ceramic powder on the surface of an organic film with an organic binder, and published Japanese Patent Application No. 62-156879 (Japanese Unexamined Patent Publication No. 156879). Showa 63-319145
It has already been proposed as (No.).
ところがこの発明においては、シートの製造時あるいは
取扱い時にフィルム上から敷粉が脱落して作業環境を悪
化させることがあり、またシートの表面と裏面の形態の
相違から湾曲や焼成時におけるシートの熱収縮を発生さ
せることがあり、更には焼成時にセッターに付着してい
るＣｏが被焼成物中へ侵入して焼成品の特性に変化を招
く場合がある等の欠点があることが判明した。However, in this invention, when the sheet is manufactured or handled, bedding powder may fall off from the film, worsening the working environment, and due to the difference in the shape of the front and back surfaces of the sheet, the sheet may be bent or heated during baking. It has been found that there are drawbacks such as shrinkage may occur, and furthermore, Co adhering to the setter during firing may enter the fired product and cause changes in the properties of the fired product.
（発明が解決しようとする課題）
本発明は上記したような従来の問題点を解決して、製造
時あるいは取扱い中における敷粉の脱落を防止して作業
環境の良化を図ることができ、またシートの湾曲や熱収
縮もなく取扱いが容易であるうえ、焼成時における被焼
成物中へのＣＯの侵入をなくすることができる超硬合金
の焼成に適した焼成用シートを提供するために完成され
たものである。(Problems to be Solved by the Invention) The present invention solves the conventional problems as described above, and can improve the working environment by preventing the falling of bedding powder during manufacturing or handling. In addition, to provide a firing sheet suitable for firing cemented carbide, which is easy to handle without curving or thermal shrinkage of the sheet, and can prevent CO from entering the object to be fired during firing. It is complete.
（課題を解決するための手段）
上記の課題を解決するためになされた本発明は、真空中
又は非酸化性雰囲気中で加熱されたときに熱分解し得る
有機性バインダー中に、重量％で１０〜８５％の高融点
セラミックス粉体と、１〜３０％のカーボン粉末又はカ
ーボン繊維と、１〜３５％のフェノール樹脂とを均一に
分散させたことを特徴とするものである。(Means for Solving the Problems) The present invention, which has been made to solve the above problems, contains an organic binder that can be thermally decomposed when heated in a vacuum or a non-oxidizing atmosphere. It is characterized by uniformly dispersing 10 to 85% of high melting point ceramic powder, 1 to 30% of carbon powder or carbon fiber, and 1 to 35% of phenol resin.
以下、本発明を図面とともに詳細に説明する。Hereinafter, the present invention will be explained in detail with reference to the drawings.
図面は本発明に係る滑性向上シートの断面図を示すもの
で、（１）は有機性バインダー、（２）はセラミックス
粉体、（３）はカーボン微粒子、（４）はフェノール樹
脂である。The drawing shows a cross-sectional view of the lubricity-improving sheet according to the present invention, in which (1) is an organic binder, (2) is a ceramic powder, (3) is a carbon fine particle, and (4) is a phenol resin.
を機性バインダー（１）は真空中又は非酸化性雰囲気中
で５００°Ｃ以下の温度で焼成されたときに熱分解し得
る特性を持つものであり、例えばポリビニルアルコール
、カルボキシメチルセルロースのような水溶性樹脂、ポ
リビニルブチラール、スチレンのような有機溶剤易溶性
樹脂、あるいはアクリル、酢酸ビニル、ブタジェン系の
樹脂、エマルジョン等が使用される。また、有機性バイ
ンダー（１）は後述するセラミックス粉体（２）とカー
ボン微粒子（３）等の残部を占め、それを保持するもの
であるが、重量％で１０〜５０％の範囲内とすることが
シート形成上好ましい。The mechanical binder (1) has the property of being thermally decomposed when fired at a temperature below 500°C in a vacuum or in a non-oxidizing atmosphere, such as water-soluble binders such as polyvinyl alcohol and carboxymethyl cellulose. Organic solvent easily soluble resins such as polyvinyl butyral, polyvinyl butyral, and styrene, acrylic, vinyl acetate, and butadiene resins, and emulsions are used. In addition, the organic binder (1) accounts for and holds the remainder of the ceramic powder (2) and carbon fine particles (3), which will be described later, and should be within the range of 10 to 50% by weight. This is preferable in terms of sheet formation.
高融点セラミックス粉体（２）としてはＡ１□０３、Ａ
ＩＮ ５ＺｒＯ□、ＳｉＣ等の粉体が使用され、その平
均粒度が５〜１００μｍ程度のものが好ましい。高融点
セラミックス粉体（２）は重量比で１０〜８５％含有さ
れるものである。含有率が１０％未満では焼成時におけ
る滑性を充分に発揮することが困難となり、また被焼成
物の融着を確実に防止することが困難となる。一方、含
有率が８５％より多くなると相対的に有機性バインダー
（１）の含有量が少なくなり、シート状の形態に保持す
ることが困難となる。High melting point ceramic powder (2) is A1□03, A
Powder such as IN 5ZrO□, SiC, etc. is used, and it is preferable that the average particle size thereof is about 5 to 100 μm. The high melting point ceramic powder (2) is contained in an amount of 10 to 85% by weight. If the content is less than 10%, it will be difficult to exhibit sufficient lubricity during firing, and it will also be difficult to reliably prevent fusion of the fired objects. On the other hand, when the content is more than 85%, the content of the organic binder (1) becomes relatively small, and it becomes difficult to maintain the organic binder (1) in a sheet-like form.
カーボン粉末又はカーボン繊維（３）としては、３〜２
０μｍ程度のカーボンの粉末、りん片、繊維を使用する
ことができ、特に天然のものが好ましい。このカーボン
はシートに剛性を付与して湾曲や焼成時における熱収縮
を防止するとともに、セッターに付着しているＣＯの被
焼成物中への侵入を防止するものであり、重量％で１〜
３０％含有されるものである。含有率が１％未満ではこ
れらの効果が十分得られず、逆に３０％より多くなると
被焼成物へカーボン成分が侵入する浸炭現象が発生する
おそれがあり好ましくない。As carbon powder or carbon fiber (3), 3 to 2
Carbon powder, scales, and fibers of about 0 μm can be used, and natural ones are particularly preferred. This carbon imparts rigidity to the sheet to prevent bending and heat shrinkage during firing, and also prevents CO adhering to the setter from penetrating into the object to be fired.
It contains 30%. When the content is less than 1%, these effects cannot be sufficiently obtained, and on the other hand, when it is more than 30%, there is a risk that a carburization phenomenon in which carbon components enter the object to be fired may occur, which is not preferable.
更に前記の高融点セラミックス粉体（２）及びカーボン
に加え、超硬合金の磁気特性の安定剤としての１〜３０
重量％のフェノール樹脂が添加される。Furthermore, in addition to the above-mentioned high melting point ceramic powder (2) and carbon, 1 to 30 as a stabilizer for the magnetic properties of the cemented carbide.
% by weight of phenolic resin is added.
１％未満では効果がなく、３０％を越えると相対的に他
の成分が減少してシート化が困難となる。If it is less than 1%, there is no effect, and if it exceeds 30%, other components will be relatively reduced, making it difficult to form a sheet.
このほか、シートとしての可塑性を向上させるためのポ
リエチレングリコール等の可塑剤を混入させることもで
きる。In addition, a plasticizer such as polyethylene glycol may be mixed in to improve the plasticity of the sheet.
（作用）
このように構成されたものは、超硬合金等を例えば１０
−”ｔｏｒｒの真空中で例えば１３５０°Ｃ程度の温度
で焼成する場合に被焼成物とセッターとの間や複数段積
層した各被焼成物の相互間に挟んで使用されるものであ
ることは従来のものと同様である。(Function) The device configured in this way is made of cemented carbide, etc.
- When firing at a temperature of, for example, 1350°C in a vacuum of 1.5 torr, it is used between the object to be fired and the setter, or between the objects to be fired stacked in multiple stages. It is the same as the conventional one.
しかし本発明のものは、セラミックス粉体（２）が有機
性バインダー（１）中に均一に分散混入された形態であ
るので、セラミックス粉体（２）の脱落による作業環境
の悪化、およびシートの湾曲が確実に防止されることと
なる。また焼成時においては有機性バインダー（１）の
みが熱分解し、カーボン粉末又はカーボン繊維（３）に
よって熱収縮が防止されつつセラミックス粉体（２）が
層状に残留し、滑性の付与と融着防止の作用を奏するこ
ととなる。さらに本発明によれば、前記のカーボン微粒
子（３）の存在によってセッターに付着しているＣｏの
被焼成物への侵入も完全に防止することができるうえ、
フェノール樹脂により焼成された超硬合金の磁気特性の
安定を図ることができる。However, in the case of the present invention, the ceramic powder (2) is uniformly dispersed and mixed into the organic binder (1), so the working environment is deteriorated due to the ceramic powder (2) falling off, and the sheet is damaged. Curving will be reliably prevented. Furthermore, during firing, only the organic binder (1) is thermally decomposed, and the carbon powder or carbon fiber (3) prevents heat shrinkage, while the ceramic powder (2) remains in a layered form, imparting lubricity and melting. This will have the effect of preventing wear and tear. Furthermore, according to the present invention, the presence of the carbon fine particles (3) makes it possible to completely prevent Co adhering to the setter from penetrating into the object to be fired.
The magnetic properties of the cemented carbide fired with the phenol resin can be stabilized.
以下に本発明の実施例を示す。Examples of the present invention are shown below.
（実施例）
重量％で、ポリビニルアルコール２０％、＃ １００の
ＡＩｚＯｚ ６０％、粒径３μのカーボン粉末８％、フ
ェノール樹脂１０％、可塑剤としてのポリエチレングリ
コール２％を均一に混合して、厚さ１５０ μの焼成用
シートを作成した。カーボン製のセッターの上にこの焼
成用シートを敷き、ドーナツ形状の耐摩耐衝撃用超硬合
金（外径φ３２０ ｍｍ、内径φ１゜ＯｌＩＩＩｍ、厚
み１０ｍｍ、重量１０．８ｋｇ ）を載せて水素を満た
した還元性雰囲気中で焼成した。また比較のために前記
した先願発明のシートを使用して同様に焼成した。(Example) By weight, 20% polyvinyl alcohol, 60% #100 AIzOz, 8% carbon powder with a particle size of 3μ, 10% phenolic resin, and 2% polyethylene glycol as a plasticizer were uniformly mixed and A sheet for firing with a diameter of 150 μm was prepared. This firing sheet was spread on a carbon setter, and a donut-shaped wear-resistant and impact-resistant cemented carbide (outer diameter φ320 mm, inner diameter φ1° OlIIIm, thickness 10 mm, weight 10.8 kg) was placed and filled with hydrogen. Calcined in a reducing atmosphere. Further, for comparison, the sheet of the prior invention described above was used and fired in the same manner.
この結果、超硬合金のへこみ量が先願発明では０．２〜
０．３ＩｎＩ１１であったのに対し２、本発明では０．
１ｍｍ以上のものは存在しなかった。また、先願発明で
は焼成された超硬合金の磁気特性値不良が１２個中に４
個、浸炭不良が３個あったのに対し、本発明の焼成用シ
ートを用いた場合にはこれらの不良はいずれも０個であ
った（Ｎ＝１２個）。As a result, the amount of dent in the cemented carbide was 0.2 to 0.2 in the prior invention.
0.3InI11, whereas in the present invention it was 0.3InI11.
There were no particles larger than 1 mm. In addition, in the prior invention, 4 out of 12 defective magnetic properties of the fired cemented carbide were found.
However, when the firing sheet of the present invention was used, there were no such defects (N=12).
なお、上記の実施例中のカーボン粉末の代わりに、直径
２０μ、長さ１．５閣のカーボン繊維を使用した場合に
も同様の結果が得られた。Note that similar results were obtained when carbon fibers having a diameter of 20 μm and a length of 1.5 μm were used instead of the carbon powder in the above examples.
（発明の効果）
以上の説明から明らかなように、本発明においては有機
性バインダー中に高融点セラミックス粉体およびカーボ
ン粉末又はカーボン繊維を混入させることによって、敷
粉の脱落を防止して作業環境の向上を図るとともに、シ
ートの湾曲および熱収縮を防止して取扱いを容易にし、
更には焼成時におけるＣｏの浸入および浸炭現象を防止
して所望の特性値を有する焼成品を得ることができるも
のである。よって、本発明は特にＣｏ含有量の多い超硬
合金の焼成に適した焼成用シートとして、産業の発展に
寄与するところは極めて大である。(Effects of the Invention) As is clear from the above explanation, in the present invention, by mixing high-melting point ceramic powder and carbon powder or carbon fiber into an organic binder, it is possible to prevent the bedding powder from falling off and improve the working environment. In addition to improving the performance of the sheet, it also prevents sheet curvature and heat shrinkage, making it easier to handle.
Furthermore, it is possible to prevent the intrusion of Co and the carburization phenomenon during firing, thereby making it possible to obtain a fired product having desired characteristic values. Therefore, the present invention greatly contributes to the development of industry as a firing sheet particularly suitable for firing cemented carbide containing a large amount of Co.
図面は本発明に係るシートの断面図である。
（１）：有機性バインダー、（２）：セラミックス粉体
（３）：カーボン粉末又はカーボン繊維、（４）： フ
ェノール樹脂。The drawing is a sectional view of a sheet according to the present invention. (1): Organic binder, (2): Ceramic powder (3): Carbon powder or carbon fiber, (4): Phenol resin.
Claims (1)
し得る有機性バインダー中に、重量％で１０〜８５％の
高融点セラミックス粉体と、１〜３０％のカーボン粉末
又はカーボン繊維と、１〜３５％のフェノール樹脂とを
均一に分散させたことを特徴とする焼成用シート。10 to 85% by weight of high melting point ceramic powder and 1 to 30% of carbon powder or carbon fiber in an organic binder that can be thermally decomposed when heated in vacuum or in a non-oxidizing atmosphere. , 1 to 35% of a phenolic resin is uniformly dispersed therein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1247055A JPH0610111B2 (en) | 1989-09-22 | 1989-09-22 | Baking sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1247055A JPH0610111B2 (en) | 1989-09-22 | 1989-09-22 | Baking sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03109271A true JPH03109271A (en) | 1991-05-09 |
| JPH0610111B2 JPH0610111B2 (en) | 1994-02-09 |
Family
ID=17157750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1247055A Expired - Lifetime JPH0610111B2 (en) | 1989-09-22 | 1989-09-22 | Baking sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610111B2 (en) |
-
1989
- 1989-09-22 JP JP1247055A patent/JPH0610111B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0610111B2 (en) | 1994-02-09 |
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