JPH10297970A - Production of silicon carbide-based sintered compact - Google Patents

Production of silicon carbide-based sintered compact

Info

Publication number
JPH10297970A
JPH10297970A JP9111048A JP11104897A JPH10297970A JP H10297970 A JPH10297970 A JP H10297970A JP 9111048 A JP9111048 A JP 9111048A JP 11104897 A JP11104897 A JP 11104897A JP H10297970 A JPH10297970 A JP H10297970A
Authority
JP
Japan
Prior art keywords
slurry
silicon carbide
water
polyalkylene polyamine
sintered body
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.)
Pending
Application number
JP9111048A
Other languages
Japanese (ja)
Inventor
Tadashi Matsumoto
匡史 松本
Akihiko Kumaki
明彦 熊木
Masahito Matsubara
雅人 松原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SEKIYU SANGYO KASSEIKA CENTER
Idemitsu Kosan Co Ltd
Taiheiyo Cement Corp
Japan Petroleum Energy Center JPEC
Original Assignee
SEKIYU SANGYO KASSEIKA CENTER
Petroleum Energy Center PEC
Chichibu Onoda Cement Corp
Idemitsu Kosan Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SEKIYU SANGYO KASSEIKA CENTER, Petroleum Energy Center PEC, Chichibu Onoda Cement Corp, Idemitsu Kosan Co Ltd filed Critical SEKIYU SANGYO KASSEIKA CENTER
Priority to JP9111048A priority Critical patent/JPH10297970A/en
Publication of JPH10297970A publication Critical patent/JPH10297970A/en
Pending legal-status Critical Current

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  • Ceramic Products (AREA)
  • Producing Shaped Articles From Materials (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a crack-free, high-density sintered compact by casting or pressure molding of a slurry comprising carbon powder coated with N- polyoxyalkylene polyalkylene polyamine, silicon carbide and water followed by conducting a sintering. SOLUTION: This sintered compact is obtained by the above-mentioned process; wherein, the amount of an N-polyoxyalkylene polyalkylene polyamine applied to carbon powder is pref. 0.01-0.1 mg/m<2> ; preferable composition of an slurry is as follows: 100 pts.wt. of water, 2-16 pts.wt. of the carbon powder coated with the N-polyoxyalkylene polyalkylene polyamine, and 200-400 pts.wt. of silicon carbide powder. Preferably, the slurry also contain 0.2-1.5 pts.wt. based on 100 pts.wt. of the water, of at least one kind selected from boron, boron carbide and dispersant(s) which is at least one kind selected from respective carbides, nitrides, carbonitrides and borides of group 4A, 5A and 6A metals, aluminum oxide and zirconium oxide.

Description

【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、鋳込み成形又は加
圧成形による高密度の炭化珪素質焼結体の製造方法に関
する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-density silicon carbide sintered body by casting or pressure molding.

【0002】[0002]

【従来の技術】セラミックスの鋳込み成形には泥漿が用
いられるが、この泥漿には、セラミックス原料や焼結助
剤などの固型分と水の他に、分散剤で代表される成形助
剤が含まれる。鋳込み成形に適した泥漿を作製するに
は、一般には成形助剤により泥漿性状を正確に調整する
必要がある。すなわち、均一な性状の焼結体を得るため
には泥漿が十分な分散性を示すことが必要とされ、成形
工程時間の短縮化や成形体形状寸法の安定性を確保する
上では泥漿中の固型分含有量が高いもの(着肉速度が速
く、成形収縮率が小さい)、すなわち泥漿濃度(固型分
含有率)が高い方が有利である。更に、造形性を忠実に
再現するには泥漿が高い流動性を有すること、すなわち
できるだけ低い粘性を示すことが望ましい。
2. Description of the Related Art Slurry is used in the casting of ceramics. In addition to water and solid components such as ceramic raw materials and sintering aids, water, as well as molding aids represented by dispersants, are used in the slurry. included. In order to produce a slurry suitable for casting, it is generally necessary to precisely control the properties of the slurry by a molding aid. That is, in order to obtain a sintered body having uniform properties, it is necessary for the slurry to exhibit sufficient dispersibility, and in order to shorten the molding process time and to ensure the stability of the shape and dimensions of the formed body, It is advantageous that the solid content is high (the inking rate is high and the molding shrinkage is small), that is, the slurry concentration (solid content) is high. Furthermore, in order to faithfully reproduce the molding properties, it is desirable that the slurry has a high fluidity, that is, exhibits a viscosity as low as possible.

【0003】また、セラミックスの加圧成形には顆粒が
用いられるが、成形型枠への充填性や成形体密度を高め
るためには均一な嵩密度で空隙率の低い球形顆粒を用い
るのが好ましく、成形体の密度分布を始めとする性状の
均一性を確保する上でも良い。このような顆粒の製造に
あたっては水を溶媒(分散媒)とする固型分含有量が高
い泥漿から造粒すると有利である。水系溶媒は、有機系
溶媒よりも作業上扱い易く、安価であり、溶媒除去処理
も容易で、使用溶媒回収設備等も不要となる。また高固
型分濃度泥漿とすることで造粒時の乾燥を短時間で行う
ことができ、同一重量の顆粒製造に対し、より少量の泥
漿量で済むため、製造設備の縮小化や製造コストの低減
をはかることができる。
[0003] Granules are used for pressure molding of ceramics, but spherical granules having a uniform bulk density and a low porosity are preferably used in order to enhance the filling property of the molding frame and the density of the molded body. It is also possible to secure uniformity of properties including the density distribution of the molded body. In producing such granules, it is advantageous to granulate from a slurry having a high solid content using water as a solvent (dispersion medium). Aqueous solvents are easier to handle in operation than organic solvents, are inexpensive, can be easily removed, and require no solvent recovery equipment. In addition, the use of a high-solids-concentration slurry allows for drying during granulation in a short period of time, and a smaller amount of slurry is required for the production of granules of the same weight. Can be reduced.

【0004】鋳込み成形又は加圧成形による炭化珪素質
セラミックスの製造は、原料固型分として、炭化珪素粉
末の他、焼結助剤、成形助剤、また複合焼結体を作製す
る場合は更に他の高融点セラミックス原料成分などを加
え、これに水などを分散媒として混合してなる泥漿を、
鋳込み成形に於いては石膏或いは多孔質樹脂製の鋳込み
型に入れて吸水後脱型することにより成形体を作製し、
また加圧成形に於いては該泥漿を噴霧乾燥等で造粒して
得た顆粒を硬質金型等の成形型枠に充填し加圧すること
により成形体を作製し、成形体を焼結する。ここで、泥
漿は高い固型分濃度の泥漿とするのが前述の如く望まし
いが、固型分濃度を高めるにつれ、粘性が上昇し、流動
性及び分散性の何れもが低下する傾向にある。その結
果、泥漿の不均一化が生じ易い。ここで、焼結助剤とし
て水等の分散媒に対して濡れ性の悪い物質、とりわけ水
に対する濡れ性が著しく悪い炭素を焼結助剤として含む
ような場合は、分散が著しく困難となり、高濃度の泥漿
が得難いものとなる。
In the production of silicon carbide ceramics by casting or pressure molding, in addition to silicon carbide powder as a raw material solid component, a sintering aid, a molding aid, and a composite sintered body are further produced. A slurry formed by adding other high-melting-point ceramic material components and the like and mixing water and the like as a dispersion medium,
In the cast molding, put in a casting mold made of gypsum or porous resin, absorb water and remove the mold to produce a molded body,
In the press molding, granules obtained by granulating the slurry by spray drying or the like are filled in a molding frame such as a hard mold and pressed to produce a molded body, and the molded body is sintered. . Here, as described above, it is desirable that the slurry has a high solid component concentration. However, as the solid component concentration is increased, the viscosity tends to increase, and both fluidity and dispersibility tend to decrease. As a result, the slurry is likely to be non-uniform. Here, when a substance having poor wettability with respect to a dispersion medium such as water as a sintering aid, particularly carbon having extremely poor wettability with water is included as a sintering aid, dispersion becomes extremely difficult, and It becomes difficult to obtain a concentration of slurry.

【0005】一方、焼結助剤の中ではカーボンブラック
などの微粉炭素には、炭化珪素表面に発生し易い酸化層
の抑制に効果があり、また硼素又は炭化硼素は焼結性の
向上、すなわち高緻密化及び易焼結化に顕著な効果があ
ることが知られている。しかるに炭素粉末の水に対する
分散性は甚だ悪く、この分散性を改善する上で従来下記
のような成形助剤の使用、或いは前処理が行われてき
た。すなわち、(1)スチレン・アクリル酸共重合体を
分散剤として用いる(特開平1−231269号公
報)、(2)ジエチルアミンとポリカルボン酸を含有し
た溶液を解膠剤として用いる(特開昭62−16725
4号公報)、(3)フミン酸又はその塩をカーボン粉末
表面に付着させる処理を行い、珪酸ソーダを分散剤とし
て使用する(特開平5−319931号公報)等であ
る。
On the other hand, among the sintering aids, fine carbon powder such as carbon black has an effect of suppressing an oxide layer which easily occurs on the surface of silicon carbide, and boron or boron carbide improves sinterability, that is, It is known that there is a remarkable effect on high densification and easy sintering. However, the dispersibility of carbon powder in water is extremely poor, and in order to improve this dispersibility, the following molding aids or pretreatments have conventionally been used. That is, (1) a styrene-acrylic acid copolymer is used as a dispersant (JP-A-1-231269), and (2) a solution containing diethylamine and polycarboxylic acid is used as a deflocculant (Japanese Patent Laid-Open No. Sho 62). -16725
No. 4) and (3) a treatment of attaching humic acid or a salt thereof to the surface of a carbon powder, and using sodium silicate as a dispersant (Japanese Patent Application Laid-Open No. Hei 5-319931).

【0006】しかしながら、(1)のスチレン・アクリ
ル酸共重合体は、炭素粉末量に対し少なくとも15重量
%以上の添加量としない限り分散し難く、また分解温度
が比較的高いので焼成条件の調整が容易でない。(2)
のジエチルアミンとポリカルボン酸を含有した溶液は、
高い固型分濃度の泥漿とすると分散性が低下し、粘性の
上昇が見られる。(3)は、比較的高い固型分濃度でも
泥漿の分散性は確保できるもののフミン酸又はその塩を
大量に使用しないと十分な分散効果が得難く、とりわけ
比較的肉厚な焼結体を作製すると大量に含まれる成形助
剤の加熱分解と離脱に伴い焼結体に亀裂が入り易いとい
う欠点があった。
However, the styrene / acrylic acid copolymer (1) is difficult to disperse unless it is added in an amount of at least 15% by weight or more based on the amount of carbon powder, and the decomposition temperature is relatively high. Is not easy. (2)
The solution containing diethylamine and polycarboxylic acid is
When the slurry has a high solid content, the dispersibility decreases and the viscosity increases. In (3), although the dispersibility of the slurry can be ensured even at a relatively high solid content, it is difficult to obtain a sufficient dispersing effect unless a large amount of humic acid or a salt thereof is used. There is a drawback in that the sintered body is liable to crack due to the thermal decomposition and detachment of a large amount of the forming aid when manufactured.

【0007】[0007]

【発明が解決しようとする課題】従って本発明は、炭素
粉末を焼結助剤として用い、鋳込み成形又は加圧成形に
より、亀裂の無い、高密度の炭化珪素質セラミックス焼
結体を製造する方法を提供することを目的とする。
Accordingly, the present invention provides a method for producing a crack-free, high-density silicon carbide-based ceramics sintered body by casting or pressure molding using carbon powder as a sintering aid. The purpose is to provide.

【0008】[0008]

【課題を解決するための手段】本発明者等は前記目的を
達成する為、検討を重ねた結果、炭化珪素質セラミック
スの製造方法において炭素粉末を焼結助剤として含む泥
漿作製の際、予めN−ポリオキシアルキレンポリアルキ
レンポリアミンで被覆した炭素粉末を用いれば、例えば
70%以上の固型分高濃度とした場合でも分散性に富む
泥漿が容易に得られ、これを鋳込み成形又は顆粒を経由
した加圧成形した成形体を焼結することで、亀裂のない
高緻密な炭化珪素質焼結体を容易に製造できることを見
出し、本発明を完成するに至った。
Means for Solving the Problems The inventors of the present invention have conducted various studies in order to achieve the above object. As a result, in producing a slurry containing carbon powder as a sintering aid in a method for producing silicon carbide ceramics, When carbon powder coated with N-polyoxyalkylene polyalkylene polyamine is used, a slurry having a high dispersibility can be easily obtained even at a high solid content of, for example, 70% or more. It has been found that by sintering the compact formed by pressure molding, it is possible to easily produce a high-density silicon carbide sintered compact without cracks, and completed the present invention.

【0009】すなわち、本発明は、N−ポリオキシアル
キレンポリアルキレンポリアミンで被覆された炭素粉末
と、炭化珪素と、水とを含有する泥漿を鋳込み成形し、
得られた成形体を焼結することを特徴とする炭化珪素質
焼結体の製造方法を提供するものである。
[0009] That is, the present invention is to cast and mold a slurry containing carbon powder coated with N-polyoxyalkylene polyalkylene polyamine, silicon carbide and water,
An object of the present invention is to provide a method for producing a silicon carbide-based sintered body, characterized by sintering the obtained molded body.

【0010】また、本発明はN−ポリオキシアルキレン
ポリアルキレンポリアミンで被覆された炭素粉末と、炭
化珪素と、水とを含有する泥漿を造粒し、得られた造粒
物を加圧成形し、次いで得られた成形体を焼結すること
を特徴とする炭化珪素質焼結体の製造方法を提供するも
のである。
[0010] The present invention also provides a method of granulating a slurry containing carbon powder coated with N-polyoxyalkylene polyalkylene polyamine, silicon carbide and water, and subjecting the obtained granules to pressure molding. And a method for producing a silicon carbide-based sintered body, characterized by sintering the obtained molded body.

【0011】[0011]

【発明の実施の形態】本発明で用いる固型分原料として
の炭化珪素は、粉末状のものであればα型又はβ型結晶
の何れの炭化珪素であっても良い。
BEST MODE FOR CARRYING OUT THE INVENTION Silicon carbide as a solid material used in the present invention may be any of α-type and β-type crystals as long as it is in powder form.

【0012】本発明においては、焼結助剤として用いる
炭素粉末がN−ポリオキシアルキレンポリアルキレンポ
リアミンで被覆されている点に特徴があり、この化合物
で被覆された炭素粉末は水に対する分散性が飛躍的に向
上する。ここで、N−ポリオキシアルキレンポリアルキ
レンポリアミンとしては、ポリアルキレンポリアミンに
アルキレンオキシドが付加した化合物が挙げられる。ポ
リアルキレンポリアミンとしては、エチレンジアミン、
ジエチレントリアミン、トリエチレンテトラミン、テト
ラエチレンペンタミン、ペンタエチレンヘキサミン、プ
ロピレンジアミン、ブチレンジアミン等が挙げられ、こ
れに付加するアルキレンオキシドとしてはエチレンオキ
シド、プロピレンオキシド、ブチレンオキシド、スチレ
ンオキシド等が挙げられる。これらのアルキレンオキシ
ドは1種が付加しても2種以上が付加していてもよい。
これらアルキレンオキシドの付加モル数は1〜300が
好ましい。
The present invention is characterized in that the carbon powder used as a sintering aid is coated with N-polyoxyalkylene polyalkylene polyamine, and the carbon powder coated with this compound has a dispersibility in water. Improve dramatically. Here, as the N-polyoxyalkylene polyalkylene polyamine, a compound obtained by adding an alkylene oxide to a polyalkylene polyamine is exemplified. As polyalkylene polyamine, ethylenediamine,
Examples thereof include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, and butylenediamine, and alkylene oxides added thereto include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. One of these alkylene oxides may be added, or two or more thereof may be added.
The addition mole number of these alkylene oxides is preferably from 1 to 300.

【0013】炭素粉末としては、一般に市販されている
ものを用いることができ、数nm〜数μm程度の炭素粉末
が好ましい。
As the carbon powder, a commercially available carbon powder can be used, and a carbon powder of several nm to several μm is preferable.

【0014】炭素粉末表面をN−ポリオキシアルキレン
ポリアルキレンポリアミンで覆う方法としては、特に限
定されないが、比較的簡単な方法として、例えば水10
0重量部に対し、炭素粉末約4重量部とN−ポリオキシ
アルキレンポリアルキレンポリアミン約0.1重量部を
ボールミル等で混合し、該混合物を大気中約75〜95
℃で乾燥させることによってN−ポリオキシアルキレン
ポリアルキレンポリアミンが約0.04mg/m2 程度被
覆された粉末を容易に得ることができる。このような方
法で作製した被覆炭素粉末は、多少の被覆ムラ等を生じ
ることがあるものの、実用上は均一に被覆されたものと
比べ、殆ど遜色ない水系分散媒への分散性を示す。ま
た、N−ポリオキシアルキレンポリアルキレンポリアミ
ンの炭素粉末への被覆量としては0.01〜0.1mg/
2 が好ましい。被覆量が少なすぎると被覆が剥がれ易
くなり、また過剰に被覆しても分散効果の更なる向上は
望めず、また加熱時の分解離脱分を増すだけとなる。
尚、予め炭素粉末をN−ポリオキシアルキレンポリアル
キレンポリアミンで被覆せずに、炭素粉末や炭化珪素粉
末その他の成分と同時にN−ポリオキシアルキレンポリ
アルキレンポリアミンを水に添加しても、予め覆った場
合と比較し、分散性がかなり劣る。同程度の分散性を得
るにはかなり大量のN−ポリオキシアルキレンポリアル
キレンポリアミンが必要となり、その場合固型分濃度の
低下や成形体焼結時の亀裂発生が著しく生じ易くなるの
で好ましくない。
The method for covering the surface of the carbon powder with N-polyoxyalkylene polyalkylene polyamine is not particularly limited, but as a relatively simple method, for example, water 10
0 parts by weight, about 4 parts by weight of carbon powder and about 0.1 parts by weight of N-polyoxyalkylene polyalkylene polyamine are mixed by a ball mill or the like, and the mixture is air-mixed for about 75 to 95
By drying at about ° C, a powder coated with about 0.04 mg / m 2 of N-polyoxyalkylene polyalkylene polyamine can be easily obtained. Although the coated carbon powder produced by such a method may cause some coating unevenness or the like, it has practically the same dispersibility in an aqueous dispersion medium as compared with a uniformly coated one. Further, the coating amount of the N-polyoxyalkylene polyalkylene polyamine on the carbon powder is 0.01 to 0.1 mg /
m 2 is preferred. If the coating amount is too small, the coating tends to peel off, and even if the coating is excessive, further improvement of the dispersing effect cannot be expected, and the amount of decomposition and detachment during heating only increases.
Incidentally, without previously coating the carbon powder with the N-polyoxyalkylene polyalkylene polyamine, even if the N-polyoxyalkylene polyalkylene polyamine was added to water simultaneously with the carbon powder, the silicon carbide powder and other components, the carbon powder was covered in advance. Dispersibility is considerably inferior to the case. In order to obtain the same degree of dispersibility, a considerably large amount of N-polyoxyalkylene polyalkylene polyamine is required. In such a case, the solid component concentration is lowered and cracks are liable to occur during sintering of the molded product.

【0015】泥漿中における前記成分の組成は、水10
0重量部に対し、N−ポリオキシアルキレンポリアルキ
レンポリアミンで被覆された炭素粉末を2〜16重量
部、炭化珪素粉末を200〜400重量部とするのが好
ましい。このように炭化珪素粉末濃度を高くしても泥漿
の水分散性及び流動性は良好である。
The composition of the above components in the slurry is water 10
It is preferable that the carbon powder coated with N-polyoxyalkylene polyalkylene polyamine is 2 to 16 parts by weight and the silicon carbide powder is 200 to 400 parts by weight with respect to 0 parts by weight. Thus, even if the concentration of the silicon carbide powder is increased, the water dispersibility and fluidity of the slurry are good.

【0016】また、泥漿中には、更に硼素、炭化硼素及
び分散材から選ばれる1種又は2種以上を配合するのが
好ましい。ここで硼素又は炭化硼素は、焼結性の向上、
すなわち焼結体の高緻密化及び易焼結化に資するもので
あり、水100重量部に対し0.2〜1.5重量部、特
に0.6〜1.2重量部添加するのが好ましい。
Further, it is preferable that one or more selected from boron, boron carbide and a dispersant are further added to the slurry. Here, boron or boron carbide improves sinterability,
That is, it contributes to high density and easy sintering of the sintered body, and it is preferable to add 0.2 to 1.5 parts by weight, particularly 0.6 to 1.2 parts by weight, per 100 parts by weight of water. .

【0017】また分散材は、焼結体中において炭化珪素
基材中に均一に分散することにより、焼結体の靱性と強
度を向上させるためのものであり、例えば周期律表第4
A族、5A族又は6A族の金属の炭化物、窒化物、炭窒
化物又は硼化物、酸化アルミニウム、及び酸化ジルコニ
ウムから選ばれる1種又は2種以上が用いられる。かか
る分散材の配合量は、炭化珪素100重量部に対し5〜
50重量部、特に10〜40重量部とするのが好まし
い。なお、以下炭化珪素及びこれら分散材を「固型分」
と称することがある。
The dispersing material is used to improve the toughness and strength of the sintered body by uniformly dispersing in the silicon carbide base material in the sintered body.
One or more selected from the group A, group 5A or group 6A metal carbides, nitrides, carbonitrides or borides, aluminum oxide, and zirconium oxide are used. The amount of the dispersant is 5 to 100 parts by weight of silicon carbide.
It is preferably 50 parts by weight, particularly preferably 10 to 40 parts by weight. Hereinafter, silicon carbide and these dispersants are referred to as “solid components”.
It may be called.

【0018】更に、鋳込み成形を行う場合は市販の分散
剤、すなわち非酸化物セラミックスの水に対する解膠剤
と称されているものを前記固型分に対して0.1〜3.
0重量%程度添加しても良い。また加圧成形を行う場合
は市販の分散剤、すなわち非酸化物セラミックスの水に
対する分散剤と称されているものを前記固型分に対して
0.1〜4.0重量%程度添加しても良く、更にこれ以
外の成形助剤を適宜添加しても良い。
Further, in the case of casting, a commercially available dispersant, that is, a so-called peptizer for water of non-oxide ceramics, is added in an amount of 0.1 to 3.
You may add about 0 weight%. In the case of performing pressure molding, a commercially available dispersant, that is, a dispersant for non-oxide ceramics in water is added in an amount of about 0.1 to 4.0% by weight based on the solid component. And other molding aids may be added as appropriate.

【0019】泥漿は、上記成分を例えばボールミルなど
で混合して作製する。なお、泥漿のpHはアルカリ側とな
ることが望ましく、必要に応じ、例えばアンモニア水、
モノエタノールアミン、市販のpH調整剤などを加えてpH
調整を行うことができる。
The slurry is prepared by mixing the above components with, for example, a ball mill. The pH of the slurry is desirably on the alkaline side, and if necessary, for example, ammonia water,
Add monoethanolamine, commercially available pH adjuster, etc.
Adjustments can be made.

【0020】鋳込み成形を行う場合は、前記鋳込み成形
用に調整した泥漿を所望形状の石膏製或いは多孔質樹脂
製の鋳型に流し込んで、鋳込み成形を行う。鋳型に吸水
させ、概ね保形されたのを見計らって、成形体を鋳込み
型から脱型し、室温〜約50℃で乾燥した後、焼結を行
う。焼結時の装置として例えば雰囲気調整可能な電気炉
等を用い、焼結は、非酸化性雰囲気、望ましくはアルゴ
ンなどの不活性ガス雰囲気又は真空中で、焼結温度19
00〜2200℃とするのが好ましい。焼結後は炉内で
室温近傍まで自然放冷することによって炭化珪素質焼結
体を得ることができる。尚、分散材を含む炭化珪素複合
焼結体を作製する場合は、前記操作で一旦作製した焼結
体をアルゴンなどの不活性ガスを圧媒としたHIP処理
を施すことによって、より高緻密で機械的性状が極めて
強固な焼結体を得ることができる。
When casting is performed, the slurry adjusted for the casting is poured into a plaster or porous resin mold having a desired shape, and the casting is performed. After allowing the mold to absorb water and seeing that the shape has been substantially retained, the molded body is released from the casting mold, dried at room temperature to about 50 ° C., and then sintered. As an apparatus for sintering, for example, an electric furnace whose atmosphere can be adjusted is used, and sintering is performed in a non-oxidizing atmosphere, preferably an inert gas atmosphere such as argon or a vacuum, at a sintering temperature of
The temperature is preferably from 00 to 2200 ° C. After the sintering, the silicon carbide-based sintered body can be obtained by naturally cooling to near room temperature in a furnace. In the case of producing a silicon carbide composite sintered body containing a dispersing material, the sintered body once produced in the above operation is subjected to HIP treatment using an inert gas such as argon as a pressure medium, so that the sintered body becomes denser. A sintered body having extremely strong mechanical properties can be obtained.

【0021】加圧成形を行う場合は、前記加圧成形用に
調整した泥漿を造粒する。造粒方法は特に限定されない
が、望ましくは噴霧乾燥により行う。噴霧乾燥等によっ
て得られた造粒物を所望の形状の成形型に充填し、加圧
成形を行って成形体を作製する。焼結は、該成形体を前
記鋳込み成形の場合と同様の焼結装置を用い、概ね同様
の条件で焼結することによって炭化珪素質焼結体を得る
ことができる。なお、分散材を含む炭化珪素複合焼結体
を作製する場合はHP(熱間加圧)法やHIP(熱間等
方加圧)法などの熱間加圧焼結法を用いるとより高緻密
で機械的性状が極めて強固な焼結体を得ることができ
る。
When pressure molding is performed, the slurry prepared for the pressure molding is granulated. The granulation method is not particularly limited, but is preferably performed by spray drying. The granulated material obtained by spray drying or the like is filled in a molding die having a desired shape, and is subjected to pressure molding to produce a molded body. For sintering, a silicon carbide-based sintered body can be obtained by sintering the formed body under substantially the same conditions using the same sintering apparatus as in the case of the casting. In the case of producing a silicon carbide composite sintered body containing a dispersing material, a hot press sintering method such as a hot press (HP) method or a hot isostatic press (HIP) method is more effective. It is possible to obtain a sintered body that is dense and has extremely strong mechanical properties.

【0022】[0022]

【実施例】次に実施例を挙げて本発明を詳細に説明する
が、本発明はこれら実施例に限定されるものではない。
Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

【0023】実施例1 水250gに市販のカーボンブラック粉末(商品名:ダ
イヤブラックI,三菱化学(株)製)10gとN−ポリ
オキシアルキレンポリアルキレンポリアミン水溶液(商
品名:ディスコールN−518,第一工業製薬(株)
製)0.25gを加えて内容積2リットルのミルにてボ
ールミル混合した後、混合物を取り出し、これを80℃
の乾燥機中に24時間入れて乾燥させて被覆カーボンブ
ラック乾粉を得た。この被覆カーボンブラック乾粉8
g、平均粒径約0.7μmのβ型炭化珪素540g、水
200g、ナフタリンスルホン酸ホルマリン縮合物0.
6g、及び硼素粉末1.5gをボールミル中で混合する
ことにより泥漿を作製した。この泥漿の常温でのB型粘
度計による泥漿粘度の測定値は209mPa・sであっ
た。
Example 1 10 g of a commercially available carbon black powder (trade name: Diamond Black I, manufactured by Mitsubishi Chemical Corporation) and 250 g of an N-polyoxyalkylene polyalkylene polyamine aqueous solution (trade name: Discol N-518, 250 g of water) Daiichi Kogyo Pharmaceutical Co., Ltd.
Was mixed with a ball mill using a mill having an internal volume of 2 liters, and the mixture was taken out.
And dried in a dryer for 24 hours to obtain a coated carbon black dry powder. This coated carbon black dry powder 8
g, 540 g of β-type silicon carbide having an average particle size of about 0.7 μm, 200 g of water, and naphthalenesulfonic acid formalin condensate.
A slurry was prepared by mixing 6 g and 1.5 g of boron powder in a ball mill. The measured value of the slurry viscosity of this slurry at room temperature by a B-type viscometer was 209 mPa · s.

【0024】次いで、30×80×6mmの内形状寸法を
有する石膏型にこの泥漿を流し込み、室温で3時間静置
した後、成形物を脱型し、これを常温で約72時間乾燥
させたものを電気炉に入れ、アルゴン雰囲気下、215
0℃で15分間保持した後、炉内で自然放冷を行い焼結
体を得た。
Next, the slurry was poured into a gypsum mold having an inner shape of 30 × 80 × 6 mm, and allowed to stand at room temperature for 3 hours. Thereafter, the molded product was demolded and dried at room temperature for about 72 hours. Put the sample in an electric furnace,
After holding at 0 ° C. for 15 minutes, the mixture was naturally cooled in a furnace to obtain a sintered body.

【0025】得られた焼結体の相対密度を測定すると共
に、亀裂発生の有無を目視及び蛍光染料探傷法で調べ
た。その結果を表1に示す。
The relative density of the obtained sintered body was measured, and the presence or absence of cracks was examined visually and by a fluorescent dye flaw detection method. Table 1 shows the results.

【0026】実施例2 水250gに市販のカーボンブラック粉末(商品名:ダ
イヤブラックI,三菱化学(株)製)10gとN−ポリ
オキシアルキレンポリアルキレンポリアミン水溶液(商
品名:ディスコールN−518,第一工業製薬(株)
製)0.25gを加えて内容積2リットルのミルにてボ
ールミル混合した後、混合物を取り出し、これを80℃
の乾燥機中に24時間入れて乾燥させて被覆カーボンブ
ラック乾粉を得た。この被覆カーボンブラック乾粉9
g、平均粒径約0.7μmのβ型炭化珪素400g、平
均粒径約2μmの硼化ジルコニウム190g、水200
g、ナフタリンスルホン酸ホルマリン縮合物0.9g、
及び硼素粉末2.5gをボールミル中で混合することに
より泥漿を作製した。この泥漿の常温でのB型粘度計に
よる泥漿粘度の測定値は221mPa・sであった。
Example 2 10 g of commercially available carbon black powder (trade name: Diamond Black I, manufactured by Mitsubishi Chemical Corporation) and 250 g of an aqueous solution of N-polyoxyalkylene polyalkylene polyamine (trade name: Discol N-518, 250 g of water) were added to 250 g of water. Daiichi Kogyo Pharmaceutical Co., Ltd.
Was mixed with a ball mill using a mill having an internal volume of 2 liters, and the mixture was taken out.
And dried in a dryer for 24 hours to obtain a coated carbon black dry powder. This coated carbon black dry powder 9
g, 400 g of β-type silicon carbide having an average particle diameter of about 0.7 μm, 190 g of zirconium boride having an average particle diameter of about 2 μm, and 200 g of water.
g, naphthalenesulfonic acid formalin condensate 0.9 g,
And 2.5 g of boron powder were mixed in a ball mill to produce a slurry. The measured value of the slurry viscosity of this slurry at room temperature by a B-type viscometer was 221 mPa · s.

【0027】次いで、30×80×6mmの内形状寸法を
有する石膏型にこの泥漿を流し込み、室温で3時間静置
した後、成形物を脱型し、これを常温で約72時間乾燥
させたものを電気炉に入れ、アルゴン雰囲気下、220
0℃で15分間保持した後、炉内で自然放冷を行い焼結
体を得た。
Next, the slurry was poured into a gypsum mold having an inner shape of 30 × 80 × 6 mm, and allowed to stand at room temperature for 3 hours. Thereafter, the molded product was demolded and dried at room temperature for about 72 hours. Put it in an electric furnace and place it under an argon atmosphere at 220
After holding at 0 ° C. for 15 minutes, the mixture was naturally cooled in a furnace to obtain a sintered body.

【0028】得られた焼結体の相対密度を測定すると共
に、亀裂発生の有無を目視及び蛍光染料探傷法で調べ
た。その結果も前記表1に併せて記す。
The relative density of the obtained sintered body was measured, and the presence or absence of cracks was examined visually and by a fluorescent dye flaw detection method. The results are also shown in Table 1 above.

【0029】比較例1 市販のカーボンブラック粉末(商品名:ダイヤブラック
I,三菱化学(株)製)9g、N−ポリオキシアルキレ
ンポリアルキレンポリアミン水溶液(商品名:ディスコ
ールN−518,第一工業製薬(株)製)0.2g、平
均粒径約0.7μmのβ型炭化珪素400g、平均粒径
約2μmの硼化ジルコニウム190g、水200g、ナ
フタリンスルホン酸ホルマリン縮合物0.9g、及び硼
素粉末2.5gをボールミル中に同時に入れて混合し、
泥漿を作製した。該泥漿の常温でのB型粘度計による泥
漿粘度の測定値は410mPa・sであり、カーボンブ
ラックが十分分散していない泥漿であった。
Comparative Example 1 9 g of commercially available carbon black powder (trade name: Diamond Black I, manufactured by Mitsubishi Chemical Corporation), an aqueous solution of N-polyoxyalkylene polyalkylene polyamine (trade name: Discol N-518, Daiichi Kogyo) 0.2 g, 400 g of β-type silicon carbide having an average particle size of about 0.7 μm, 190 g of zirconium boride having an average particle size of about 2 μm, 200 g of water, 0.9 g of naphthalenesulfonic acid formalin condensate, and boron 2.5 g of powder is simultaneously placed in a ball mill and mixed,
A slurry was made. The measured value of the slurry viscosity of the slurry at room temperature by a B-type viscometer was 410 mPa · s, indicating that the slurry was not sufficiently dispersed with carbon black.

【0030】実施例3 水1500gに市販のカーボンブラック粉末(商品名:
ダイヤブラックI,三菱化学(株)製)60gとN−ポ
リオキシアルキレンポリアルキレンポリアミン水溶液
(商品名:ディスコールN−518,第一工業製薬
(株)製)1.5gを加えて内容積5リットルのミルに
てボールミル混合した後、混合物を取り出し、これを8
0℃の乾燥機中に24時間入れて乾燥させて得た被覆カ
ーボンブラック乾粉を得た。この被覆カーボンブラック
乾粉31.5g、平均粒径約0.7μmのβ型炭化珪素
1400g、平均粒径約2μmの硼化ジルコニウム66
0g、水700g、分散剤としてナフタリンスルホン酸
ホルマリン縮合物3.2g、及び硼素粉末8.8gをボ
ールミル中で混合することにより泥漿を作製した。この
泥漿の常温でのB型粘度計による泥漿粘度の測定値は2
52mPa・sであった。
Example 3 A commercially available carbon black powder (trade name:
60 g of Diamond Black I (manufactured by Mitsubishi Chemical Corporation) and 1.5 g of an aqueous solution of N-polyoxyalkylene polyalkylene polyamine (trade name: Discol N-518, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) are added, and the internal volume is 5 After mixing with a ball mill in a liter mill, the mixture was taken out and mixed with 8
It was placed in a dryer at 0 ° C. for 24 hours and dried to obtain a dried carbon black powder. 31.5 g of the coated carbon black dry powder, 1400 g of β-type silicon carbide having an average particle diameter of about 0.7 μm, and zirconium boride 66 having an average particle diameter of about 2 μm
A slurry was prepared by mixing 0 g, 700 g of water, 3.2 g of formalin condensate of naphthalenesulfonic acid as a dispersant, and 8.8 g of boron powder in a ball mill. The measured value of the slurry viscosity of this slurry at room temperature by a B-type viscometer was 2
It was 52 mPa · s.

【0031】次いで、該泥漿をスプレードライヤーにて
含水率約0.3%、平均粒径43μmの顆粒を作製し、
この顆粒を50×40×10mmの内形状寸法を有する金
型に充填し、500kg/cm2 の圧力で一軸加圧成形を行
ったものを3ton/cm2 で冷間等方加圧(CIP)処理
を行い成形体を作製した。該成形体を電気炉に入れ、ア
ルゴン雰囲気下、2150℃で15分間保持した後、炉
内で自然放冷を行い焼結体を得た。
Next, granules having a water content of about 0.3% and an average particle size of 43 μm are prepared from the slurry by a spray dryer.
The granules were filled in a mold having an inner shape of 50 × 40 × 10 mm and uniaxially pressed at a pressure of 500 kg / cm 2 , and then subjected to cold isostatic pressing (CIP) at 3 ton / cm 2. A treatment was performed to produce a molded body. The molded body was placed in an electric furnace, kept at 2150 ° C. for 15 minutes in an argon atmosphere, and then naturally cooled in the furnace to obtain a sintered body.

【0032】得られた焼結体の相対密度を測定すると共
に、亀裂発生の有無を目視及び蛍光染料探傷法で調べ
た。その結果も前記表1に併せて記す。
The relative density of the obtained sintered body was measured, and the presence or absence of cracks was examined visually and by a fluorescent dye flaw detection method. The results are also shown in Table 1 above.

【0033】実施例4 水1500gに市販のカーボンブラック粉末(商品名:
ダイヤブラックI,三菱化学(株)製)60gとN−ポ
リオキシアルキレンポリアルキレンポリアミン水溶液
(商品名:ディスコールN−518,第一工業製薬
(株)製)1.5gを加えて内容積5リットルのミルに
てボールミル混合した後、混合物を取り出し、これを8
0℃の乾燥機中に24時間入れて乾燥させて得た被覆カ
ーボンブラック乾粉を得た。この被覆カーボンブラック
乾粉31.5g、平均粒径約0.7μmのβ型炭化珪素
1400g、平均粒径約2μmの硼化ジルコニウム66
0g、平均粒径約0.3μmの酸化アルミニウム17
g、水700g、分散剤としてナフタリンスルホン酸ホ
ルマリン縮合物3.5g、及び硼素粉末8.0gをボー
ルミル中で混合することにより泥漿を作製した。この泥
漿の常温でのB型粘度計による泥漿粘度の測定値は35
0mPa・sであった。
Example 4 A commercially available carbon black powder (trade name:
60 g of Diamond Black I (manufactured by Mitsubishi Chemical Corporation) and 1.5 g of an aqueous solution of N-polyoxyalkylene polyalkylene polyamine (trade name: Discol N-518, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) are added, and the internal volume is 5 After mixing with a ball mill in a liter mill, the mixture was taken out and mixed with 8
It was placed in a dryer at 0 ° C. for 24 hours and dried to obtain a dried carbon black powder. 31.5 g of the coated carbon black dry powder, 1400 g of β-type silicon carbide having an average particle diameter of about 0.7 μm, and zirconium boride 66 having an average particle diameter of about 2 μm
0 g, aluminum oxide 17 having an average particle size of about 0.3 μm
g, 700 g of water, 3.5 g of a formalin condensate of naphthalenesulfonic acid as a dispersant, and 8.0 g of boron powder in a ball mill to prepare a slurry. The measured value of the slurry viscosity of this slurry at room temperature by a B-type viscometer was 35.
It was 0 mPa · s.

【0034】次いで、該泥漿をスプレードライヤーにて
含水率約0.3%、平均粒径48μmの顆粒を作製し、
この顆粒を50×40×10mmの内形状寸法を有する金
型に充填し、500kg/cm2 の圧力で一軸加圧成形を行
い成形体を作製した。該成形体を電気炉に入れ、アルゴ
ン雰囲気下、1950℃で15分間保持した後、炉内で
自然放冷を行ったものを、圧媒としてアルゴンを用い、
圧力1500kg/cm2、1800℃で30分間カプセル
フリーHIP処理をすることにより焼結体を得た。
Then, granules having a water content of about 0.3% and an average particle size of 48 μm are prepared from the slurry by a spray drier.
The granules were filled in a mold having an internal shape of 50 × 40 × 10 mm, and subjected to uniaxial pressure molding at a pressure of 500 kg / cm 2 to produce a molded body. The molded body was placed in an electric furnace, kept at 1950 ° C. for 15 minutes under an argon atmosphere, and then naturally cooled in the furnace, using argon as a pressure medium,
A sintered body was obtained by performing a capsule-free HIP treatment at a pressure of 1500 kg / cm 2 and 1800 ° C. for 30 minutes.

【0035】得られた焼結体の相対密度を測定すると共
に、亀裂発生の有無を目視及び蛍光染料探傷法で調べ
た。その結果も前記表1に併せて記す。
The relative density of the obtained sintered body was measured, and the presence or absence of cracks was examined visually and by a fluorescent dye flaw detection method. The results are also shown in Table 1 above.

【0036】比較例2 水250gに市販のカーボンブラック粉末(商品名:ダ
イヤブラックI,三菱化学(株)製)10gとフミン酸
6gを加えて内容積2リットルのミルにてボールミル混
合した後、混合物を取り出し、これを80℃の乾燥機中
に24時間入れて乾燥させて得た被覆カーボンブラック
乾粉を得た。この被覆カーボンブラック乾粉8g、平均
粒径約0.7μmのβ型炭化珪素540g、水200
g、ナフタリンスルホン酸ホルマリン縮合物0.6g、
及び硼素粉末1.5gをボールミル中で混合することに
より泥漿を作製した。この泥漿の常温でのB型粘度計に
よる泥漿粘度の測定値は269mPa・sであった。
Comparative Example 2 10 g of commercially available carbon black powder (Diablack I, manufactured by Mitsubishi Chemical Corporation) and 6 g of humic acid were added to 250 g of water, and mixed with a ball mill in a 2 liter internal volume mill. The mixture was taken out, placed in a dryer at 80 ° C. for 24 hours, and dried to obtain a coated carbon black dry powder. 8 g of this coated carbon black dry powder, 540 g of β-type silicon carbide having an average particle size of about 0.7 μm,
g, naphthalenesulfonic acid formalin condensate 0.6 g,
And 1.5 g of boron powder were mixed in a ball mill to produce a slurry. The measured value of the slurry viscosity of this slurry at room temperature by a B-type viscometer was 269 mPa · s.

【0037】次いで、30×80×6mmの内形状寸法を
有する石膏型にこの泥漿を流し込み、室温で3時間静置
した後、成形物を脱型し、これを常温で約72時間乾燥
させたものを電気炉に入れ、アルゴン雰囲気下、215
0℃で15分間保持した後、炉内で自然放冷を行い焼結
体を得た。
Next, the slurry was poured into a gypsum mold having an internal shape of 30 × 80 × 6 mm, and allowed to stand at room temperature for 3 hours. Thereafter, the molded product was demolded and dried at room temperature for about 72 hours. Put the sample in an electric furnace,
After holding at 0 ° C. for 15 minutes, the mixture was naturally cooled in a furnace to obtain a sintered body.

【0038】得られた焼結体の相対密度を測定すると共
に、亀裂発生の有無を目視及び蛍光染料探傷法で調べ
た。その結果も前記表1に併せて記す。
The relative density of the obtained sintered body was measured, and the presence or absence of cracks was examined visually and by a fluorescent dye flaw detection method. The results are also shown in Table 1 above.

【0039】[0039]

【表1】 [Table 1]

【0040】[0040]

【発明の効果】表面をN−ポリオキシアルキレンポリア
ルキレンポリアミンで被覆した炭素粉末は、水に対する
濡れ性が良く、極めて良好な分散状態を示す。また、N
−ポリオキシアルキレンポリアルキレンポリアミンは、
従来の例えばフミン酸を使用する場合よりも少量の使用
で炭素の十分な分散性を付与させることができる。従っ
て焼結時に於けるこのような有機化合物の分解・離脱も
少なく、分解・離脱時に起こり易い焼結体の亀裂発生を
大幅に低減できる。従って本発明では、有機系助剤含有
量を低減させた比較的高濃度で成分分散性が良い均質な
原料泥漿を用いた鋳込み成形ができ、該成形法を経て作
製した炭化珪素質焼結体は形状面では亀裂等が無く、性
状面では均質で高緻密な焼結体を得ることができる。ま
た、同様に比較的高濃度の泥漿から顆粒を作製すること
もできることから造粒時間の短縮化と高密顆粒を得るこ
とが可能で、該顆粒を用いて加圧成形を行った高密度成
形体は、焼結後も亀裂等が無く、より高緻密な炭化珪素
質焼結体を容易に製造することができる。
The carbon powder whose surface is coated with N-polyoxyalkylene polyalkylene polyamine has good wettability with water and shows a very good dispersion state. Also, N
-Polyoxyalkylene polyalkylene polyamine,
Sufficient carbon dispersibility can be imparted by using a smaller amount than in the case of using conventional humic acid. Therefore, the decomposition and detachment of such an organic compound during sintering are small, and the cracking of the sintered body which is likely to occur at the time of decomposition and detachment can be greatly reduced. Therefore, in the present invention, it is possible to perform cast molding using a homogeneous raw material slurry having a relatively high concentration and a good component dispersibility in which the content of the organic auxiliary agent is reduced, and a silicon carbide sintered body produced through the molding method. Has no cracks or the like on the shape surface, and a homogeneous and highly dense sintered body can be obtained on the property surface. Similarly, since granules can be produced from a relatively high-concentration slurry, it is possible to shorten the granulation time and obtain high-density granules. Has no cracks and the like even after sintering, and can easily produce a denser silicon carbide sintered body.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 熊木 明彦 千葉県佐倉市大作二丁目4番2号 秩父小 野田株式会社内 (72)発明者 松原 雅人 千葉県袖ヶ浦市上泉1280番地 出光興産株 式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihiko Kumaki 2-4-2 Daisaku, Sakura City, Chiba Prefecture Inside Chichibu Onoda Co., Ltd. (72) Masato Matsubara 1280 Kamiizumi, Sodegaura City, Chiba Idemitsu Kosan Co., Ltd. In company

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】 N−ポリオキシアルキレンポリアルキレ
ンポリアミンで被覆された炭素粉末と、炭化珪素と、水
とを含有する泥漿を鋳込み成形し、得られた成形体を焼
結することを特徴とする炭化珪素質焼結体の製造方法。
1. A method comprising casting and molding a slurry containing carbon powder coated with N-polyoxyalkylene polyalkylene polyamine, silicon carbide and water, and sintering the obtained molded body. A method for producing a silicon carbide sintered body.
【請求項2】 N−ポリオキシアルキレンポリアルキレ
ンポリアミンで被覆された炭素粉末と、炭化珪素と、水
とを含有する泥漿を造粒し、得られた造粒物を加圧成形
し、次いで得られた成形体を焼結することを特徴とする
炭化珪素質焼結体の製造方法。
2. A slurry containing carbon powder coated with N-polyoxyalkylene polyalkylene polyamine, silicon carbide, and water is granulated, and the obtained granules are subjected to pressure molding, and then obtained. A method for producing a silicon carbide-based sintered body, characterized by sintering a formed compact.
【請求項3】 N−ポリオキシアルキレンポリアルキレ
ンポリアミンの被覆量が、0.01〜0.1mg/m2
ある請求項1又は2記載の製造方法。
3. The method according to claim 1, wherein the coating amount of the N-polyoxyalkylene polyalkylene polyamine is 0.01 to 0.1 mg / m 2 .
【請求項4】 泥漿が、更に硼素、炭化硼素及び分散材
から選ばれる1種又は2種以上を含有するものである請
求項1〜3のいずれか1項記載の製造方法。
4. The method according to claim 1, wherein the slurry further contains one or more selected from boron, boron carbide and a dispersant.
【請求項5】 分散材が、周期律表第4A族、5A族又
は6A族の金属の炭化物、窒化物、炭窒化物又は硼化
物、酸化アルミニウム、及び酸化ジルコニウムから選ば
れる1種又は2種以上である請求項4記載の製造方法。
5. The dispersion material is one or two selected from carbides, nitrides, carbonitrides or borides of metals belonging to Group 4A, 5A or 6A of the periodic table, aluminum oxide and zirconium oxide. The manufacturing method according to claim 4, which is the above.
JP9111048A 1997-04-28 1997-04-28 Production of silicon carbide-based sintered compact Pending JPH10297970A (en)

Priority Applications (1)

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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9111048A JPH10297970A (en) 1997-04-28 1997-04-28 Production of silicon carbide-based sintered compact

Publications (1)

Publication Number Publication Date
JPH10297970A true JPH10297970A (en) 1998-11-10

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Country Link
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100419778B1 (en) * 2001-02-16 2004-02-21 한국에너지기술연구원 Manufacturing method of silicon cabide-boron carbide composites by liquid phase reaction sintering
CN105621854A (en) * 2015-12-28 2016-06-01 滁州美业机械制造有限公司 Refrigerator center spacer and machining technique thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100419778B1 (en) * 2001-02-16 2004-02-21 한국에너지기술연구원 Manufacturing method of silicon cabide-boron carbide composites by liquid phase reaction sintering
CN105621854A (en) * 2015-12-28 2016-06-01 滁州美业机械制造有限公司 Refrigerator center spacer and machining technique thereof

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