JPH0354159A - Production of sintered body of ceramics - Google Patents

Production of sintered body of ceramics

Info

Publication number
JPH0354159A
JPH0354159A JP1188533A JP18853389A JPH0354159A JP H0354159 A JPH0354159 A JP H0354159A JP 1188533 A JP1188533 A JP 1188533A JP 18853389 A JP18853389 A JP 18853389A JP H0354159 A JPH0354159 A JP H0354159A
Authority
JP
Japan
Prior art keywords
powder
sintered body
sintering
ceramic
raw material
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
Application number
JP1188533A
Other languages
Japanese (ja)
Other versions
JP2632218B2 (en
Inventor
Mitsuo Kuwabara
光雄 桑原
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.)
Honda Motor Co Ltd
Original Assignee
Honda Motor 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 Honda Motor Co Ltd filed Critical Honda Motor Co Ltd
Priority to JP1188533A priority Critical patent/JP2632218B2/en
Priority to GB8928030A priority patent/GB2239028B/en
Priority to BE8901334A priority patent/BE1003553A5/en
Priority to FR898916669A priority patent/FR2655978B1/fr
Priority to DE3941516A priority patent/DE3941516C2/en
Priority to CA002005686A priority patent/CA2005686C/en
Publication of JPH0354159A publication Critical patent/JPH0354159A/en
Application granted granted Critical
Publication of JP2632218B2 publication Critical patent/JP2632218B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F3/26—Impregnating
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/573—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F01L3/22—Valve-seats not provided for in preceding subgroups of this group; Fixing of valve-seats
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Abstract

PURPOSE:To obtain a high-quality sintered body of ceramics by using ceramic powder blended with a Li compound and sintering auxiliary powder as raw materials and producing a sintered body. CONSTITUTION:In production of sintered body of ceramics using ceramic powder and sintering auxiliary powder to form a glass phase in a sintering process of the ceramic powder as raw material powder, the raw material powder is blended with <=0.005wt.%-<3wt.% calculated as oxide of a Li compound. By adding a given amount of the Li compound to the raw material powder, sintering temperature is dropped, plastic fluidity of glass phase and volume diffusion at neck between the mutual ceramic powder are improved so that sintering properties and density can be made better. Furthermore, a temperature range to reduce viscosity of glass phase is more extremely widened than a case of addition of an oxide of Na, K, etc., and plastic deformation like that of ZrO2-Al2O3-based ceramics is observed so that toughness of sintered body of ceramics can be improved.

Description

【発明の詳細な説明】 Ａ．発明の目的 （１）産業上の利用分野 本発明はセラミック焼結体の製造方法、特に、原料粉末
として、セラミック粉末と、そのセラごック粉末の焼結
過程でガラス相を形或する焼結助剤粉末とを用いるセラ
果ツク焼結体の製造方法に関する． （２）従来の技術 従来、セラごツタ焼結体の物性値のばらつきを解消し、
また信頼性を向上させるために、前記原料粉末の高純度
化および微細化といった手段が採用されている。[Detailed Description of the Invention] A. Object of the Invention (1) Industrial Field of Application The present invention relates to a method for producing a ceramic sintered body, and in particular, to a method for producing a ceramic sintered body, in particular, a method for producing a ceramic sintered body, in which ceramic powder is used as a raw material powder, and a glass phase is formed during the sintering process of the ceramic powder. This article relates to a method for manufacturing ceramic sintered bodies using binder powder. (2) Conventional technology Conventionally, variations in the physical properties of Ceragotsuta sintered bodies have been eliminated,
Furthermore, in order to improve reliability, measures such as increasing the purity and making the raw material powder finer are adopted.

（３）発明が解決しようとする課題 しかしながら前記手段を採用すると、原料粉末のコスト
の上昇に伴いセラ５ツク焼結体の製造コストが高くなり
、また作業環境を悪化し、その上原料粉末の分散混合が
難しく取扱い性が悪い、といった種々の問題を生じる。(3) Problems to be Solved by the Invention However, if the above means is adopted, the manufacturing cost of the ceramic sintered body increases due to the increase in the cost of the raw material powder, and the working environment deteriorates. This causes various problems such as difficulty in dispersive mixing and poor handling.

本発明は前記に鑑み、従来の前記手段に代え、原料粉末
としては通常の純度および粒度をもつものを用い、且つ
焼結助剤に本来の機能を発揮させて、高品質なセラ稟ツ
タ焼結体を得ることのできる前記製造方法を提供するこ
とを目的とする．Ｂ．発明の構威 （１）課題を解決するための手段 本発明は、原料粉末として、セラミック粉末と、そのセ
ラくツク粉末の焼結過程でガラス相を形戒する焼結助剤
粉末とを用いるセラ稟ツク焼結体の製造方法において、
前記原料粉末に、酸化物換算値にて、Ｏ．　Ｏ　Ｏ　５
重量％以上、３重量％未満のＬｉ化合物を添加すること
を特徴とする．（２）作　用 セラごツタ粉末の焼結過程では、焼結助剤粉末が焼結温
度にてガラス相を形成し、このガラス相を介してセラミ
ック粉末相互が焼結する。この場合、焼結支配因子とし
ては、ガラス相の塑性流動およびセラ〔ツタ粉末相互間
のネックにおける体積拡散を挙げることができ、これら
は、焼結温度および原料粉末組成により左右されるもの
である。In view of the above, the present invention has been developed to produce high quality Ceramic Tsuta sintering by using raw material powder with normal purity and particle size and by allowing the sintering aid to perform its original function, in place of the conventional means described above. The object of the present invention is to provide the above-mentioned manufacturing method that can obtain solid bodies. B. Structure of the Invention (1) Means for Solving the Problems The present invention uses a ceramic powder as a raw material powder and a sintering aid powder that forms a glass phase during the sintering process of the ceramic powder. In the method for manufacturing a ceramic sintered body,
The raw material powder has an oxide content of O. O O 5
It is characterized by adding a Li compound of at least 3% by weight and less than 3% by weight. (2) Function In the sintering process of Ceragotsuta powder, the sintering aid powder forms a glass phase at the sintering temperature, and the ceramic powders are sintered together through this glass phase. In this case, the controlling factors for sintering include the plastic flow of the glass phase and the volumetric diffusion at the neck between the cera powders, which are influenced by the sintering temperature and the raw material powder composition. .

そこで、焼結温度を上昇させることにより、塑性流動お
よび体積拡散を改善することが考えられるが、このよう
な手法を採用すると、局部的な粗大粒の生戒および粗大
気孔の生戒を惹起するおそれがある。Therefore, it may be possible to improve plastic flow and volumetric diffusion by increasing the sintering temperature, but if such a method is adopted, it may cause the formation of local coarse grains and coarse pores. There is a risk.

一方、原料粉末組戒に関し、焼結温度を一定にして、Ｎ
ａ，Ｋ，Ｒｂ，Ｃｓといったアルカリ金属の酸化物また
はアルカリ土類金属を原料粉末に添加して塑性流動等を
改善することが考えられるが、これらの化合物質はセラ
ミック焼結体の耐熱性、耐食性の劣化を招くおそれがあ
る。On the other hand, regarding raw material powder assembly, the sintering temperature was kept constant and N
It may be possible to add oxides of alkali metals or alkaline earth metals such as a, K, Rb, and Cs to the raw powder to improve plastic flow, etc., but these compounds can improve the heat resistance of ceramic sintered bodies, This may lead to deterioration of corrosion resistance.

本発明によれば、原料粉末に、前記特定量のＬｉ化合物
を添加することによって、焼結温度を低下させ、またガ
ラス相の塑性流動およびセラくツク粉末相互間のネック
における体積拡散を改善して、焼結性および密度を向上
させることができる。According to the present invention, by adding the specific amount of Li compound to the raw material powder, the sintering temperature is lowered, and the plastic flow of the glass phase and the volume diffusion at the neck between the ceramic powders are improved. As a result, sinterability and density can be improved.

しかも、ガラス相の粘性を低下させるための温度幅は、
Ｎａ，Ｋ等の酸化物等を添加した場合に比べて、極めて
広くなり、ＺｒＯｚ−Ａｌ２０ｓ系セラくツクスのよう
な塑性変形が観測され、したがってセラミック焼結体の
靭性を向上させることができる． また、前記Ｌｉ化合物の添加により、異常粒戒長を抑制
して物性値のばらつきを解消し、その上信頼性を向上さ
せることが可能となる。Moreover, the temperature range for reducing the viscosity of the glass phase is
Compared to the case where oxides such as Na, K, etc. are added, the plastic deformation becomes much wider and plastic deformation similar to that of ZrOz-Al20s ceramics is observed, and therefore the toughness of the ceramic sintered body can be improved. Furthermore, the addition of the Li compound makes it possible to suppress abnormal grain lengths, eliminate variations in physical property values, and improve reliability.

なお、Ｌｉ化合物の添加量が、酸化物換算値にて、Ｏ．
　Ｏ　Ｏ　５重量％未満では、偏析を生して部分的な密
度差を招くだけでなく、粗大気孔を生成してセラミック
焼結体の物性が低下する。一方、前記添加量が３重量％
以上では、異常低温焼結を惹起してセラミック焼結体の
強度、耐熱性および耐食性の低下を招来する。Note that the amount of the Li compound added is O.
If O 2 O is less than 5% by weight, it not only causes segregation and local density differences, but also generates coarse pores and deteriorates the physical properties of the ceramic sintered body. On the other hand, the amount added is 3% by weight.
The above causes abnormally low temperature sintering, resulting in a decrease in the strength, heat resistance, and corrosion resistance of the ceramic sintered body.

（３）実施例 原料粉末において、セラミック粉末としては、Ａ　１１
　０３　、Ｓ　Ｉ　Ｏ＠　、Ｚ　ｒ　Ｏ！等の酸化物粉
末、Ｓ　ｉｓ　Ｎａ　、ＴｉＮ，ＺｒＮ．．ＢＮ等の窒
化物粉末、Ｓ　ｉＣ，Ｔｉｃ，ＭｏＣ等の炭化物粉末等
が単独で、または混合粉末として用いられる。(3) In the example raw material powder, the ceramic powder was A 11
03 , S I O @ , Z r O! oxide powders such as S is Na, TiN, ZrN. ．． Nitride powder such as BN, carbide powder such as SiC, Tic, MoC, etc. can be used alone or as a mixed powder.

焼結助剤粉末は、ガラス相を形成してセラミック粉末の
焼結性を向上させる機能を有し、この種焼結助剤粉末と
しては、ＡＩ２ｔ　Ｏｓ　、Ｙｚ○，、ＭｇＯＳＴｉＯ
ｚ　、Ｓ　ｉｏｚ　、ＺｒＯｔ　．．ＣｅＯｚ　、Ｌａ
ｗ　Ｏｓ　、Ｓ　ｉｓ　Ｎａ　、ＴｉＮ，ＡＩＮ，Ｔｉ
Ｃ等の粉末が単独で、または混合粉末として用いられる
。The sintering aid powder has the function of forming a glass phase to improve the sinterability of the ceramic powder. Examples of this type of sintering aid powder include AI2tOs, Yz○, and MgOSTiO.
z, Sioz, ZrOt. ．． CeOz, La
w Os , S is Na , TiN, AIN, Ti
Powders such as C are used alone or as a mixed powder.

原料粉末におけるセラミック粉末と焼結助剤粉末との配
合割合は次の通りである。The mixing ratio of ceramic powder and sintering aid powder in the raw material powder is as follows.

セラミック粉末　　　　　７５〜９９．７重景％焼結助
剤粉末　　　　　０．３〜２５重量％前記のような配合
割合を採用する理由は、焼結助剤粉末の添加量が０．３
重量％未満では、緻密なセラミック焼結体を得ることが
難しくなり、一方、２５重量％を上回ると、セラくツク
ス本来の特性を損うからである。Ceramic powder: 75 to 99.7% by weight Sintering aid powder: 0.3 to 25% by weight The reason for adopting the above blending ratio is that the amount of sintering aid powder added is 0.3% by weight.
If it is less than 25% by weight, it will be difficult to obtain a dense ceramic sintered body, while if it exceeds 25% by weight, the original properties of ceramics will be impaired.

Ｌｉ化合物としては、Ｌｉの酸化物、水酸化物、炭酸塩
等が該当し、これらは粉末の状態で用いられる。またＣ
Ｈ，ＣＯＯＬ　ｉ等の液体も使用可能である。Examples of Li compounds include Li oxides, hydroxides, and carbonates, which are used in powder form. Also C
Liquids such as H and COOL i can also be used.

このＬｉ化合物の添加量は、酸化物換算値にて、０．　
０　０　５重量％以上、３重量％未満であるが、好まし
くは上限値は１重量％である。その理由は、セラミック
焼結体における１２００゜Ｃ以上の高温特性の劣化およ
び耐薬品性の低下が懸念されるからである。The amount of this Li compound added is 0.
0 0 5% by weight or more and less than 3% by weight, but preferably the upper limit is 1% by weight. The reason for this is that there are concerns about deterioration of the high temperature properties of the ceramic sintered body at temperatures above 1200°C and a decrease in chemical resistance.

このＬｉ化合物の添加に伴い、その添加量に応じてセラ
ミック粉末の使用量が減じられる。With the addition of this Li compound, the amount of ceramic powder used is reduced in accordance with the amount added.

セラミック粉末としてＳｉｓＮｎ粉末を用い、また焼結
助剤粉末としてＡ／！．Ｃｈ粉末を用い、さらにＬｉ化
合物としてＬｉｚＣＯｚを用いた場合、Ｌｉｚｃｃｈは
、焼結過程において約６２０゜Ｃで分解して酸化吻Ｌｉ
ｚＯを生成する。そのＬｉ，Ｏは、ＳｉｚＮ４粉末表面
の酸化物層およびＡＩｌｚＯｘと反応して、例えば、Ｌ
ｊ４ＳｉＯ．、Ｌｊｚ　ＳｉＣｈ　、ＬｉＡｉＶ．Ｏｔ
　，Ｌｉ！Ａｌ１。SisNn powder was used as the ceramic powder, and A/! was used as the sintering aid powder. ．． When Ch powder is used and LizCOz is used as a Li compound, Lizcch decomposes at about 620°C during the sintering process and becomes oxidized Li.
Generate zO. The Li, O reacts with the oxide layer on the surface of the SizN4 powder and AIlzOx, and for example, L
j4SiO. , Ljz SiCh, LiAiV. Ot
,Li! Al1.

ＯＩｔｈ、Ｌ　ｉＡｊ２ｓ　ｔｏｎ　、Ｌ　ｉＡｆｓ　
ｉｔ　Ｏｈ等の微量の化合物を生成する。これら化合物
は、焼結温度を低下させ、また焼結助剤により形成され
たガラス層の塑性流動およびＳｊｉＮａ粉末相互間のネ
ックにおける体積拡散を改善する作用を有するものであ
る． Ｌｉ化合物の添加によって、前記のような作用が得られ
る理由は推定の域を出ないが、次のように考えられる。OIth, L iAj2s ton, L iAfs
It produces trace amounts of compounds such as it Oh. These compounds have the effect of lowering the sintering temperature and improving the plastic flow of the glass layer formed by the sintering aid and the volume diffusion at the neck between the SjiNa powders. The reason why the above effect is obtained by adding a Li compound is beyond speculation, but it is thought to be as follows.

即ち、Ｌｉのイオン半径は、６配位、０．６８人であり
、これと近似するＡ１”は６配位であってＬｉと反応し
易く、またＬｉのイオン半径は比較的小さく、結晶がコ
ンパクトであり、これらにより前記作用が得られるもの
と思われる．前記反応性は他の焼結助剤粉末についても
言えるもので、例えば、Ｔｉ’゜、Ｚｒ’゜、Ｍ，２−
はそれぞれ６配位である． 前記１，　ｉ　４　Ｓ　ｓ　Ｏ　ａ等の化合物は強度が
極めて低く、またセラごツタ焼結体の耐熱性を低下させ
るといった不具合を惹起するので、Ｌｉ化合物の添加量
の設定は重要な意義をもつ。例えば、Ｌｉ化合物Ｏ添カ
コ量が３重量％以上では、セラミ・冫ク焼結体の南熱性
は約１０００゜Ｃとなり、耐熱鋼のそれと略同程度にま
で低下する， 前記Ｌｉ化合物による、局部的な異常粒成長抑制作用は
、次の事例において確認される。That is, the ionic radius of Li is 6-coordinated and 0.68 people, and A1'', which is similar to this, is 6-coordinated and easily reacts with Li.Also, the ionic radius of Li is relatively small and the crystal is It is thought that the above effect can be obtained because of the compact size.The above reactivity also applies to other sintering aid powders, such as Ti'゜, Zr'゜, M, 2-
are each 6-coordinated. Compounds such as 1 and i 4 S s O a have extremely low strength and cause problems such as lowering the heat resistance of the ceramic sintered body, so setting the amount of Li compounds added is of great significance. Motsu. For example, when the amount of Li compound O added is 3% by weight or more, the thermal resistance of the ceramic/solid sintered body is approximately 1000°C, which is approximately the same level as that of heat-resistant steel. The abnormal grain growth inhibiting effect is confirmed in the following cases.

例えば、ＳｉｓＮｎ粉末に、焼結助剤粉末として、５重
量％のＡ４２ｚＯｓ粉末および５重量％のｙ，ｏ．粉末
を添加した原料粉末を用い、焼結温度１７５０゜Ｃにて
焼結したセラごツタ焼結体においては、直径３〜５μｍ
に戒長したＳｉ３１’Ｌａ粒間に、直径８〜１０μｍの
異常或長した粒子や粒子塊が存在するが、前記原料粉末
にＬｔ化合物を微量添加、例えばＬｉ．ＣＯ．を０．　
１重量％添加すると、前記粒子は直径０．７〜２μｍ、
長さ約５μｍ程度にその成長を抑制される． この異常粒戒長抑制作用は、Ｌｉと共にＺｒ、Ｍｇ，Ｔ
ｉ，Ｃｒ等が共存すると、一Ｎ顕著となる。For example, in SisNn powder, 5% by weight of A42zOs powder and 5% by weight of y,o. Ceragotsuta sintered bodies sintered at a sintering temperature of 1750°C using raw material powder with added powder have a diameter of 3 to 5 μm.
There are abnormally elongated particles and particle agglomerates with a diameter of 8 to 10 μm between the Si31'La grains, which have a diameter of 8 to 10 μm. C.O. 0.
When added at 1% by weight, the particles have a diameter of 0.7-2 μm;
Its growth is suppressed to a length of about 5 μm. This abnormal grain length suppressing effect is caused by Zr, Mg, and T as well as Li.
When i, Cr, etc. coexist, 1N becomes significant.

セラミック焼結体に、焼結後熱処理を施すことは、その
焼結体の耐熱性、耐食性を向上させ、また高温クリープ
性を改善する上で有効である。この熱処理は、８００〜
１６００゜Ｃの再結晶温度範囲にて、１回または複数回
行い、粒界ガラス相の結晶化とＬｉの固定化を図る。Applying post-sintering heat treatment to a ceramic sintered body is effective in improving the heat resistance and corrosion resistance of the sintered body, as well as improving high-temperature creep properties. This heat treatment
This is carried out once or multiple times in a recrystallization temperature range of 1600°C to crystallize the grain boundary glass phase and fix Li.

〔実施例Ｉ〕[Example I]

表Ｉは、各種セラξソク焼結体のｍ威および焼結温度を
示す。Table I shows the strength and sintering temperature of various ceramic sintered bodies.

Ｓ　！　３　Ｎａ粉末としては、平均直径０．７μｍで
、α化率９０％以上のものが用いられた。また焼結助剤
粉末の平均直径において、Ｙ２０３粉末は０．１ｐｍ，
Ａｎ．○，粉末は０．６μｍＳＺｒＯ，粉末は０．２μ
ｍである。その他の焼結助剤扮末およびＬｉ．ＣＯ，粉
末としては試薬特級を使用した。S! 3 Na powder with an average diameter of 0.7 μm and a gelatinization rate of 90% or more was used. In addition, the average diameter of the sintering aid powder is 0.1 pm for Y203 powder,
An. ○, powder is 0.6 μm SZrO, powder is 0.2 μm
It is m. Other sintering aid powders and Li. Special reagent grade CO was used as powder.

各セラ旦ツタ焼結体Ａ，〜Ｅｚ−ｚの製造に当っては、
それに対応する原料粉末単独、または原料粉末にＬｉ化
合物を添加した混合粉末に水を加え、ボールミルにて２
４時間湿式混合した後、スリップキャスティングにて縦
１２閣、横５０ｆｆＩＩ＋、長さ１２０ＩｎＩｍの板状
或形体を威形した。In manufacturing each ceradan ivy sintered body A, ~Ez-z,
Add water to the corresponding raw material powder alone or a mixed powder of raw material powder with Li compound added, and use a ball mill for 2
After wet mixing for 4 hours, a plate-like body with 12 lengths, 50 ffII+ width, and 120 InIm length was formed by slip casting.

各成形体を十分に乾燥した後、それらに表Ｉに示す焼結
温度にて焼結処理を施し、セラミック焼結体Ａ，〜Ｅｔ
−ｔを得た。After sufficiently drying each molded body, they were subjected to sintering treatment at the sintering temperature shown in Table I, and ceramic sintered bodies A, ~Et
-t was obtained.

表■は各セラミック焼結体Ａ１＝Ｅｚ−ｚの各種物性を
示す。Table (3) shows various physical properties of each ceramic sintered body A1=Ez-z.

表 ■ 表Ｉ．■から明らかなように、本発明により得られたセ
ラミック焼結体Ａｚ　，　　Ｂ２　，　　Ｃ２　，　　
Ｄ．，Ｅｘ−＋　，　　Ｅｚ−ｚは、Ｌｉ化合物の添加
により比較例セラミック焼結体Ａ，．Ｂ．，Ｃ，，Ｄ．
Ｅ，に比べて焼結温度が５０または１００℃低く、また
密度も０．　１　〜０．　２　５　ｇ　／ｃｒｉ３程度
高く、さらに硬さおよび曲げ強さも向上している。Table ■ Table I. As is clear from (2), the ceramic sintered bodies obtained by the present invention Az, B2, C2,
D. , Ex-+ , Ez-z are different from those of comparative example ceramic sintered bodies A, . B. ,C,,D.
The sintering temperature is 50 or 100°C lower than that of E., and the density is 0. 1 ~ 0. It is about 25 g/cri3 higher, and the hardness and bending strength are also improved.

セラミック焼結体Ａｔ　，Ａ２について、鏡面研摩後、
その鏡面を光学顕微鏡にて観察したところ、セラミック
焼結体Ａ．においては、直径２５〜３０μｍの粗大気孔
と、直径約１μｍの気孔が存在するが、セラミック焼結
体Ａ２においては気孔の直径が１〜２μｍと微細であり
、またその数も極端に少ないことが判明した。Regarding the ceramic sintered body At, A2, after mirror polishing,
When the mirror surface was observed with an optical microscope, it was found that the ceramic sintered body A. In A2, there are coarse pores with a diameter of 25 to 30 μm and pores with a diameter of about 1 μm, but in ceramic sintered body A2, the diameter of the pores is as fine as 1 to 2 μm, and the number of pores is extremely small. found.

前記セラミック焼結体Ａ．において、その高密度化を狙
って原料粉末の高純度化および微細化を行った場合、粗
大気孔の数を減少させることはできても、その直径を減
じられないことがあり、その結果、しばしば、強度のば
らつきが大きく、また破壊靭性値がそれ程改善されない
ことがある。The ceramic sintered body A. When the raw material powder is purified and refined with the aim of increasing its density, although it is possible to reduce the number of coarse pores, it may not be possible to reduce their diameter, and as a result, often , the strength varies widely, and the fracture toughness value may not be improved that much.

また微細な原料粉末を用いると、スリップキャス？ィン
グによる戒形が困難になる、といった不具合もある。Also, if you use fine raw material powder, slip casting? There is also a problem that it becomes difficult to perform precepts by typing.

本実施例のように、Ｌｉ化合物を添加することによって
前記問題は解消される。The above problem can be solved by adding a Li compound as in this example.

セラミック焼結体Ｅ１，Ｅｚ−＋　，Ｅ２−■は、高靭
性を狙った組威を有するが、添加或分の関係がら、ボー
ラスになり易く、したがってセラミック焼結体Ｅ，では
、直径０．５μｍ程度の気孔が均一に分散し、一部これ
らの気孔が凝集した直径２〜３μｍの比較的大きな気孔
も存在する。セラミック焼結体Ｅｚ−＋　，　　Ｅｚ−
ｘにおいては、Ｌｉ化合物の添加により気孔の数がセラ
ミック焼結体Ｅ１に比べて少なくなり、強度が大幅に向
上する。The ceramic sintered bodies E1, Ez-+, and E2-■ have a structure aiming at high toughness, but due to the amount of addition, they tend to form boluses, so the ceramic sintered body E has a diameter of 0. Pores of about 5 μm are uniformly dispersed, and there are also relatively large pores of 2 to 3 μm in diameter in which these pores are aggregated. Ceramic sintered body Ez-+, Ez-
In x, the number of pores is reduced compared to the ceramic sintered body E1 due to the addition of the Li compound, and the strength is significantly improved.

〔実施例■〕[Example ■]

表■は、各種セラミック焼結体の組成を示す。 Table ■ shows the composition of various ceramic sintered bodies.

ＳｉｓＮ４粉末、ｙ，　ｏ．ｓ　粉末、Ａｉｔｏｘ＜Ｒ
末、ＺｒＯｚ粉末、ＣｅＯｚ粉末、ＬａｚＯ：＋粉末、
ＭｇＯ粉末およびＬｉＣＯｚ粉末としては実施例Ｉと同
一のものを使用した。また平均直径において、ＴｉＮ粉
末としては１．２μｍ，Ｔｉｃ粉末としては１．２μｍ
，ＳｉＣ粉末としては０．４μｍＳＡｆｆｉＮ粉末とし
ては１．０μｍ，ＴｉＯ．粉末としては０．　１μｍの
ものをそれぞれ使用した。SisN4 powder, y, o. s powder, Aitox<R
powder, ZrOz powder, CeOz powder, LazO:+ powder,
The same MgO powder and LiCOz powder as in Example I were used. In addition, the average diameter is 1.2 μm for TiN powder and 1.2 μm for Tic powder.
, 0.4 μm for SiC powder, 1.0 μm for SAffiN powder, TiO. As a powder, it is 0. A 1 μm thick film was used.

各セラ業ノク焼結体Ｆ１〜■２を得るための、混合法、
成形法、焼結法は実施例■と同しである．焼結後、各セ
ラミック焼結体Ｆｚ　，　Ｇｔ　，　　Ｈｚ１．に、表
■に示す再結晶温度にて熱処理を施し、粒界ガラス相の
結晶化とＬｉの固定化を行った． 表■は各セラミック焼結体Ｆ，〜■２の各種物性を示す
。表中、破壊靭性値の測定は、チェブロンノッチ（Ｃｈ
ｅｖｒｏｎ　Ｎｏｔｃｈ　）法による．表 ■ 表ＩＩ［，　ＩＶから明らかなように、本発明により得
られたセラミック焼結体Ｆｚ　，　　Ｇｔ　，　　Ｈｚ
　，Ｉ　！は、Ｌｉ化合物の添加により比較例セラミッ
ク焼結体Ｆ．，Ｇ．，Ｈ，，Ｉ，に比べて焼結温度が５
０〜１５０℃低く、また密度も０．０９〜０．２１ｇ　
／　ｃｍ　”程度高く、さらに曲げ強さおよび破壊靭性
値も向上している。A mixing method for obtaining each ceramic sintered body F1 to ■2,
The molding method and sintering method are the same as in Example ①. After sintering, each ceramic sintered body Fz, Gt, Hz1. A heat treatment was performed at the recrystallization temperature shown in Table 1 to crystallize the grain boundary glass phase and fix Li. Table (2) shows various physical properties of each ceramic sintered body F, to (2). In the table, fracture toughness values are measured at Chevron notches (Ch
evron Notch) method. Table II As is clear from Table II[, IV, the ceramic sintered body Fz, Gt, Hz obtained by the present invention
,I! By adding a Li compound, the comparative ceramic sintered body F. ,G. ,H,,I, the sintering temperature is 5.
0~150℃ lower and density 0.09~0.21g
/cm”, and the bending strength and fracture toughness values are also improved.

各セラミック焼結体Ｆ，〜Ｉ１の組或は、焼結時、Ａｊ
！，Ｔｉ等の金属を析出し、この析出金属により高靭性
化が図られるが、その反面不均一組織となり易い、とい
った不具合がある．例えば、Ｔ　ｉ　Ｏ　ｚ粉末を添加
したセラくツク焼結体Ｇ１においては、Ｔｉｅ．の拡散
またはＴｉＯ１への窒素等の拡散が遅く、また凝集し易
いため、均一組織を有する焼結体を得ることは非常に難
しい．これに対し、セラミック焼結体Ｇｔにおいては、
Ｌｉ化合物の添加によって、焼結性が改善され、組織の
均一化が図られている。When each ceramic sintered body F, ~I1 is assembled or sintered, Aj
! , Ti, and other metals are precipitated, and high toughness is achieved by the precipitated metals, but on the other hand, there is a problem that a non-uniform structure tends to be formed. For example, in the ceramic sintered body G1 to which T i O z powder is added, Tie. It is very difficult to obtain a sintered body with a uniform structure because the diffusion of TiO2 or nitrogen into TiO1 is slow and tends to aggregate. On the other hand, in the ceramic sintered body Gt,
By adding the Li compound, sinterability is improved and the structure is made more uniform.

Ｃ．発明の効果 本発明によれば、特定量のＬｉ化合物を添加することに
よって焼結助剤に本来の機能を発揮させて、焼結性が良
好で、均一組織を有し、また高強度、且つ高靭性なセラ
ミック焼結体を得ることができる． 特 許 出 廓 人 本田技研工業株式会社C. Effects of the Invention According to the present invention, by adding a specific amount of Li compound, the sintering aid is made to exhibit its original function, resulting in good sinterability, a uniform structure, high strength, and A highly tough ceramic sintered body can be obtained. Patent distributor Honda Motor Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] 原料粉末として、セラミック粉末と、そのセラミック粉
末の焼結過程でガラス相を形成する焼結助剤粉末とを用
いるセラミック焼結体の製造方法において、前記原料粉
末に、酸化物換算値にて、０．００５重量％以上、３重
量％未満のＬｉ化合物を添加することを特徴とするセラ
ミック焼結体の製造方法。In a method for producing a ceramic sintered body using a ceramic powder as a raw material powder and a sintering aid powder that forms a glass phase during the sintering process of the ceramic powder, the raw material powder contains: A method for producing a ceramic sintered body, characterized in that 0.005% by weight or more and less than 3% by weight of a Li compound is added.
JP1188533A 1989-07-20 1989-07-20 Manufacturing method of ceramic sintered body Expired - Fee Related JP2632218B2 (en)

Priority Applications (6)

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JP1188533A JP2632218B2 (en) 1989-07-20 1989-07-20 Manufacturing method of ceramic sintered body
GB8928030A GB2239028B (en) 1989-07-20 1989-12-12 Method of manufacturing a sintered ceramic article
BE8901334A BE1003553A5 (en) 1989-07-20 1989-12-14 Ceramic sintered article and method of making such article.
FR898916669A FR2655978B1 (en) 1989-07-20 1989-12-15
DE3941516A DE3941516C2 (en) 1989-07-20 1989-12-15 Method for producing a sintered ceramic article
CA002005686A CA2005686C (en) 1989-07-20 1989-12-15 Sintered ceramic article and method of manufacturing the same

Applications Claiming Priority (3)

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JP1188533A JP2632218B2 (en) 1989-07-20 1989-07-20 Manufacturing method of ceramic sintered body
GB8928030A GB2239028B (en) 1989-07-20 1989-12-12 Method of manufacturing a sintered ceramic article
CA002005686A CA2005686C (en) 1989-07-20 1989-12-15 Sintered ceramic article and method of manufacturing the same

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JP (1) JP2632218B2 (en)
BE (1) BE1003553A5 (en)
CA (1) CA2005686C (en)
DE (1) DE3941516C2 (en)
FR (1) FR2655978B1 (en)
GB (1) GB2239028B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304242A (en) * 2013-06-13 2013-09-18 景德镇陶瓷学院 Method for adding ceramic sintering auxiliary
JP2015093813A (en) * 2013-11-13 2015-05-18 東ソー株式会社 Zirconia powder

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG71036A1 (en) * 1996-08-01 2000-03-21 Smith International Double cemented inserts
US5880382A (en) * 1996-08-01 1999-03-09 Smith International, Inc. Double cemented carbide composites
US6454027B1 (en) 2000-03-09 2002-09-24 Smith International, Inc. Polycrystalline diamond carbide composites
US7017677B2 (en) 2002-07-24 2006-03-28 Smith International, Inc. Coarse carbide substrate cutting elements and method of forming the same
US7243744B2 (en) 2003-12-02 2007-07-17 Smith International, Inc. Randomly-oriented composite constructions
US7441610B2 (en) 2005-02-25 2008-10-28 Smith International, Inc. Ultrahard composite constructions
US20210024357A1 (en) * 2018-02-13 2021-01-28 Mitsui Mining & Smelting Co., Ltd. Sintered metal carbide and heat-resistant member for silicon carbide semiconductor manufacturing device comprising same
CN112592179A (en) * 2020-11-25 2021-04-02 科益展智能装备有限公司 Gradient zirconia ceramic cutter material and preparation method thereof
CN115043655B (en) * 2022-06-18 2023-03-10 杭州新致美义齿研发有限公司 Preparation method of zirconia false tooth

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6033787A (en) * 1983-08-04 1985-02-21 Toyota Motor Corp Controller of on-vehicle television receiver
JPS60204670A (en) * 1984-03-12 1985-10-16 イー・アイ・デユポン・ド・ネモアース・アンド・コンパニー Dielectric composition
JPH02267150A (en) * 1989-04-07 1990-10-31 Harima Ceramic Co Ltd Carbon-containing refractory for iron melting

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1093280A (en) * 1955-05-03
DE865721C (en) * 1945-03-20 1953-02-05 Deutsche Edelstahlwerke Ag Porous body without or with filling of the pores with a metal
US3031340A (en) * 1957-08-12 1962-04-24 Peter R Girardot Composite ceramic-metal bodies and methods for the preparation thereof
US3925575A (en) * 1967-12-28 1975-12-09 Kaman Sciences Corp Ceramic treating process and product produced thereby
GB1325204A (en) * 1970-10-07 1973-08-01 United States Borax Chem Production of hard articles of a boron-carbon compound
FR2210803B2 (en) * 1972-12-15 1980-01-04 Siemens Ag
JPS49107308A (en) * 1973-02-13 1974-10-11
GB1536290A (en) * 1976-02-27 1978-12-20 Nat Res Dev Reaction bonded silicon nitride ceramics
JPS5832070A (en) * 1981-08-21 1983-02-24 信越化学工業株式会社 Manufacture of high density silicon carbide sintered body
JPS59182283A (en) * 1983-03-29 1984-10-17 株式会社東芝 Manufacture of electroconductive ceramic sintered body
DE3543342A1 (en) * 1985-12-07 1987-06-11 Bojak Kurt Composite material having high wear resistance and dimensional stability, and process for its manufacture
WO1988002742A1 (en) * 1986-10-17 1988-04-21 Washington Research Foundation Method for producing a surface-toughened ceramic composite
DE3724995A1 (en) * 1987-02-26 1988-09-08 Radex Heraklith Process for manufacturing a composite body and the composite body itself
DE3729126A1 (en) * 1987-09-01 1989-04-06 Mototech Motoren Umweltschutz Diesel soot-particle filter and process for the production thereof
DE3812266C1 (en) * 1988-04-13 1989-08-24 Nils Prof. Dr. 2107 Rosengarten De Claussen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6033787A (en) * 1983-08-04 1985-02-21 Toyota Motor Corp Controller of on-vehicle television receiver
JPS60204670A (en) * 1984-03-12 1985-10-16 イー・アイ・デユポン・ド・ネモアース・アンド・コンパニー Dielectric composition
JPH02267150A (en) * 1989-04-07 1990-10-31 Harima Ceramic Co Ltd Carbon-containing refractory for iron melting

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304242A (en) * 2013-06-13 2013-09-18 景德镇陶瓷学院 Method for adding ceramic sintering auxiliary
JP2015093813A (en) * 2013-11-13 2015-05-18 東ソー株式会社 Zirconia powder

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JP2632218B2 (en) 1997-07-23
DE3941516A1 (en) 1991-06-20
GB2239028A (en) 1991-06-19
GB8928030D0 (en) 1990-02-14
BE1003553A5 (en) 1992-04-21
DE3941516C2 (en) 1994-11-03
CA2005686C (en) 1996-11-05
CA2005686A1 (en) 1991-06-15
GB2239028B (en) 1994-02-23
FR2655978A1 (en) 1991-06-21
FR2655978B1 (en) 1992-08-07

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