JPH05279115A - Dense sintered compact of chromium oxide and its production - Google Patents
Dense sintered compact of chromium oxide and its productionInfo
- Publication number
- JPH05279115A JPH05279115A JP10190892A JP10190892A JPH05279115A JP H05279115 A JPH05279115 A JP H05279115A JP 10190892 A JP10190892 A JP 10190892A JP 10190892 A JP10190892 A JP 10190892A JP H05279115 A JPH05279115 A JP H05279115A
- Authority
- JP
- Japan
- Prior art keywords
- chromium oxide
- powder
- sintered body
- present
- weight
- 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
Links
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910000423 chromium oxide Inorganic materials 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000843 powder Substances 0.000 claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000010304 firing Methods 0.000 claims description 14
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000001513 hot isostatic pressing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 13
- 229910052719 titanium Inorganic materials 0.000 abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 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
- 238000002156 mixing Methods 0.000 abstract 1
- 230000003068 static effect Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 19
- 230000000996 additive effect Effects 0.000 description 13
- 230000002159 abnormal effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005452 bending Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000009694 cold isostatic pressing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、緻密質酸化クロム焼結
体及びその製造方法に関し、特に、ガラス溶融用部材や
金属溶融用部材などに利用することができる高強度の緻
密質酸化クロム焼結体及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dense chromium oxide sintered body and a method for producing the same, and particularly to a high-strength dense chromium oxide sintered body which can be used as a glass melting member, a metal melting member, or the like. The present invention relates to a bound body and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】酸化クロムは、溶融ガラスやスラグに対
する耐食性に優れており、従来より耐火物として利用さ
れている。しかし、酸化クロムは、クロム元素の価数が
焼成時雰囲気により、２+，３+，４+ ，５+，６+と変化
するものであり、極めて焼結し難い物質であり、しか
も、焼成中1000℃付近より異常粒子成長の発生がみられ
ることから、従来技術では、以下に詳記するとおり、所
望する酸化クロムの緻密質焼結体を得ることができなか
った。2. Description of the Related Art Chromium oxide is excellent in corrosion resistance against molten glass and slag, and has been conventionally used as a refractory material. However, chromium oxide is a substance in which the valence of the chromium element changes to 2 + , 3 + , 4 + , 5 + , 6 + depending on the atmosphere during firing, and is a substance that is extremely difficult to sinter. Since abnormal grain growth occurs around 1000 ° C. in the middle, it was not possible to obtain a desired dense sintered body of chromium oxide by the conventional technique, as described in detail below.
【０００３】最近、酸化クロムの高付加化を目的とし、
緻密な酸化クロム焼結体を製造する方法が提案されてい
る。例えば、(1) P.D.Ownby等は、Ｐｏ2（酸素分圧）を
制御した雰囲気中で酸化クロム成形体を焼成し、これに
より高純度緻密質焼結体を得ることが提案されており
（JACS,55,433〜436P,1972参照）、また、(2) 酸化クロ
ム成形体を炭素粉末中に埋め込んで焼成することによ
り、高純度緻密質焼結体を得ることが提案されている
（特公昭63−387号公報参照）。Recently, for the purpose of increasing the addition of chromium oxide,
A method for producing a dense chromium oxide sintered body has been proposed. For example, (1) PDOwnby and the like have been proposed to fire a chromium oxide compact in an atmosphere in which Po 2 (oxygen partial pressure) is controlled to obtain a high-purity dense sintered compact (JACS, 55,433 to 436P, 1972), and (2) it is proposed to obtain a high-purity dense sintered body by embedding a chromium oxide compact in carbon powder and firing it (Japanese Patent Publication No. 63-387). (See the official gazette).
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記(1)、(2)
の方法で得られた焼結体では、焼結体組織の制御手段
（特に、異常粒成長抑制手段）がなされておらず、その
ため、機械的特性上満足するものではなく、所望の機械
的特性、耐食性等を備えた高付加価値を有する酸化クロ
ムの緻密質焼結体が得られていない。また、上記(2)に
よる方法で得られた焼結体では、上記した問題点以外
に、更に、その焼結体表面（炭素粉末との接触面）に反
応層（変質層）が生成しており、緻密質酸化クロム焼結
体としては不適当である。[Problems to be Solved by the Invention] However, the above (1) and (2)
The sintered body obtained by the above method does not have a means for controlling the structure of the sintered body (in particular, an abnormal grain growth suppressing means), and therefore, the mechanical characteristics are not satisfactory, and the desired mechanical characteristics are not satisfied. However, a dense sintered body of chromium oxide having high added value, such as corrosion resistance, has not been obtained. Further, in the sintered body obtained by the method according to (2) above, in addition to the above-mentioned problems, a reaction layer (altered layer) is further formed on the surface of the sintered body (contact surface with carbon powder). Therefore, it is unsuitable as a dense chromium oxide sintered body.
【０００５】最近、このような問題点、欠点を解消する
手段として、酸化クロムに種々の添加物を加えることが
試みられている。例えば、 酸化クロムに0.1〜90重量％の炭化クロムを添加した
もの（特開昭61−215253号公報）、 Ｔｉ、Ｚｒ、Ｈｆの酸化物、窒化物、炭化物又はＣ
ｒの窒化物、炭化物もしくはこれらの相互固溶体の中の
少なくとも１種の金属化合物を5〜50重量％添加したも
の（特開昭62−21755号公報）、 酸化ハフニウム、酸化ジルコニウム固溶酸化ハフニ
ウム、酸化イットリウム及び希土類元素酸化物から選ば
れる１種以上のものを1〜40重量％添加したもの（特開
昭62−70258号公報）、 などが提案されている。Recently, as a means for solving such problems and drawbacks, it has been attempted to add various additives to chromium oxide. For example, chromium oxide to which 0.1 to 90% by weight of chromium carbide is added (JP-A-61-215253), Ti, Zr, Hf oxides, nitrides, carbides or C
A nitride containing 5 to 50% by weight of at least one metal compound among the nitrides, carbides or mutual solid solutions thereof (Japanese Patent Laid-Open No. 62-21755), hafnium oxide, zirconium oxide solid solution hafnium oxide, It has been proposed to add 1 to 40% by weight of at least one selected from yttrium oxide and rare earth element oxides (JP-A-62-70258).
【０００６】しかしながら、上記〜では、上述した
ところから理解できるように、多量の添加物が加えられ
ている。従って、上記〜により得られた焼結体は、
酸化クロム本来の特性が失われており、このような手段
でも所望する緻密質焼結体を得ることができない。However, in the above items, a large amount of additives are added, as can be understood from the above. Therefore, the sintered body obtained by the above ~
The original properties of chromium oxide are lost, and the desired dense sintered body cannot be obtained by such means.
【０００７】本発明は、以上のような問題点を解消する
緻密質酸化クロム焼結体及びその製造方法を提供するこ
とを目的とする。詳細には、本発明は、従来の酸化クロ
ム焼結体よりも更に優れた機械的特性、耐食性等を備え
た高付加価値を有する緻密質酸化クロム焼結体及びその
製造方法を提供することを目的とする。An object of the present invention is to provide a dense chromium oxide sintered body and a method for producing the same, which solves the above problems. More specifically, the present invention provides a dense chromium oxide sintered body having high added value with mechanical properties, corrosion resistance, etc., which are superior to those of conventional chromium oxide sintered bodies, and a method for producing the same. To aim.
【０００８】[0008]
【課題を解決するための手段】そして、本発明は、Ｍ
ｇ、Ａｌ、Ｃａ、Ｔｉ又は希土類元素酸化物より選ばれ
た少なくとも１種以上の酸化物を特定量添加し、これを
焼成することを特徴とし、これにより上記目的とする緻
密質酸化クロム焼結体を提供するものである。The present invention is based on M
g, Al, Ca, Ti, or at least one oxide selected from rare earth element oxides in a specific amount is added, and the mixture is fired. It provides the body.
【０００９】即ち、本発明は、「酸化クロム粉末とＭ
ｇ、Ａｌ、Ｃａ、Ｔｉ又は希土類酸化物より選ばれた少
なくとも１種以上の酸化物粉末0.1重量％以上1.0重量％
未満との混合粉末を焼成してなることを特徴とする緻密
質酸化クロム焼結体。」及び「(1) 酸化クロム粉末にＭ
ｇ、Ａｌ、Ｃａ、Ｔｉ又は希土類酸化物より選ばれた少
なくとも１種以上の酸化物粉末0.1重量％以上1.0重量％
未満を混合し、該混合粉末を非酸化雰囲気中で1550℃〜
1700℃の温度範囲で焼成すること、又は、(2) この焼結
体を更に熱間静水圧処理を施すこと、を特徴とする緻密
質酸化クロム焼結体の製造方法。」を要旨とするもので
ある。That is, the present invention provides "chromium oxide powder and M
0.1% by weight or more and 1.0% by weight or more of at least one oxide powder selected from g, Al, Ca, Ti or rare earth oxides
A dense chromium oxide sintered body, which is obtained by firing a mixed powder of And "(1) M in chromium oxide powder
0.1% by weight or more and 1.0% by weight or more of at least one oxide powder selected from g, Al, Ca, Ti or rare earth oxides
Less than 1550 ° C. in a non-oxidizing atmosphere.
A method for producing a dense chromium oxide sintered body, which comprises firing in a temperature range of 1700 ° C., or (2) further subjecting this sintered body to hot isostatic pressing. Is the gist.
【００１０】[0010]
【作用】本発明における特徴の１つである「Ｍｇ、Ａ
ｌ、Ｃａ、Ｔｉ及び／又は希土類の各酸化物からなる添
加物粉末」の作用について、以下詳細に説明する。酸化
クロム粉末に加えられる上記添加物は、いずれも焼成
中、酸化クロム粒子の異常粒成長を抑制し、酸化クロム
焼結体の緻密化を促進する作用を奏する。[Function] One of the features of the present invention is "Mg, A
The effect of the "additive powder consisting of oxides of 1, Ca, Ti and / or rare earths" will be described in detail below. All of the above-mentioned additives added to the chromium oxide powder have the effect of suppressing abnormal grain growth of the chromium oxide particles during firing and promoting the densification of the chromium oxide sintered body.
【００１１】この異常粒成長抑制機構としては、焼成中
酸化クロム粒子とＭｇ、Ａｌ、Ｃａ、Ｔｉ、希土類元素
の各酸化物とが反応し、化合物を生成する。そして、こ
の生成した化合物は、酸化クロム間に存在し、これによ
り酸化クロム粒子の異常粒成長が抑制する作用が生ず
る。その結果として、酸化クロム結晶の粒子径が均一な
緻密質焼結体が得られる。例えば、ＭｇＯを添加した場
合、酸化クロム粒子間にスピネル組成物が生成し、これ
が異常粒子成長抑制及び緻密化効果をもたらすものであ
る。As a mechanism for suppressing abnormal grain growth, chromium oxide particles react with each oxide of Mg, Al, Ca, Ti and rare earth elements during firing to form a compound. The produced compound is present between the chromium oxides, which causes an effect of suppressing abnormal grain growth of the chromium oxide particles. As a result, a dense sintered body in which the particle diameter of the chromium oxide crystal is uniform can be obtained. For example, when MgO is added, a spinel composition is formed between the chromium oxide particles, which brings about an effect of suppressing abnormal particle growth and a densification effect.
【００１２】ただし、ここで重要なことは、酸化クロム
粒子間に生成する化合物が非連続的に酸化クロム粒子間
に存在することであり、これが連続的に存在すれば、上
記作用効果が生ぜず、酸化クロム粒子間の焼結性を阻害
することになる。このため、本発明では、後記するとお
り、この種添加物粉末の添加量が重要な要因となるもの
である。However, what is important here is that the compound formed between the chromium oxide particles is discontinuously present between the chromium oxide particles, and if it is continuously present, the above-mentioned action and effect will not occur. , Which impairs the sinterability between the chromium oxide particles. Therefore, in the present invention, as will be described later, the addition amount of the seed additive powder is an important factor.
【００１３】次に、本発明を詳細に説明すると、本発明
で用いる酸化クロム粉末としては、例えばＣｒＯ、Ｃｒ
2Ｏ3、ＣｒＯ2等の粉末を使用することができる。これ
ら酸化クロム粉末のうち、特に限定するものではない
が、高温における安定性からＣｒ2Ｏ3を主体とする酸化
クロム粉末を使用するのが好ましい。Next, the present invention will be described in detail. Examples of the chromium oxide powder used in the present invention include CrO and Cr.
Powders such as 2 O 3 and CrO 2 can be used. Of these chromium oxide powders, although not particularly limited, it is preferable to use a chromium oxide powder mainly containing Cr 2 O 3 because of its stability at high temperatures.
【００１４】本発明は、前記したとおり、酸化クロム粉
末に対する添加物として、Ｍｇ、Ａｌ、Ｃａ、Ｔｉ、希
土類の各酸化物の単独又は併用して使用することを特徴
の１つとするものである。この種添加物を例示すれば、
ＭｇＯ、Ａｌ2Ｏ3、ＣａＯ、ＴｉＯ2、Ｙ2Ｏ3等を挙げ
ることができる。また、本発明において、酸化クロム粉
末に上記添加物を単独で使用することができるが、２種
以上の添加物を配合した場合（上記各酸化物の併用の場
合）、より高強度の緻密質酸化クロム焼結体が得られる
ので、より好ましい（後記表２試料No.6〜10参照）。As described above, the present invention is characterized by using Mg, Al, Ca, Ti, or a rare earth oxide alone or in combination as an additive to the chromium oxide powder. .. An example of this kind of additive is:
Examples thereof include MgO, Al 2 O 3 , CaO, TiO 2 , and Y 2 O 3 . Further, in the present invention, the above additives can be used alone in the chromium oxide powder, but when two or more additives are blended (when the above oxides are used in combination), a higher strength and compactness are obtained. It is more preferable because a chromium oxide sintered body can be obtained (see sample Nos. 6 to 10 in Table 2 below).
【００１５】その添加量は、本発明において、併用の場
合をも含めて0.1重量％以上1.0重量％未満の範囲が好ま
しい。添加物粉末の添加量として、1.0重量％以上の場
合、生成する化合物が酸化クロム粒子の周りに連続的に
存在するようになり、前記した異常粒成長抑制作用が生
じ難く、酸化クロム粒子間の焼結性を阻害するようにな
るので、好ましくない。また、酸化クロム粒界に低融点
組成物が多量に形成するため、焼結体の高温特性及び耐
食性の点でも好ましくない。In the present invention, the addition amount is preferably in the range of 0.1% by weight or more and less than 1.0% by weight including the case of combined use. When the amount of the additive powder added is 1.0% by weight or more, the compound to be produced will be continuously present around the chromium oxide particles, and the above-mentioned abnormal grain growth suppressing action is unlikely to occur. It becomes unfavorable because it impairs sinterability. Further, since a large amount of the low melting point composition is formed at the chromium oxide grain boundaries, it is not preferable in terms of high temperature characteristics and corrosion resistance of the sintered body.
【００１６】一方、添加物粉末が0.1重量％未満では、
酸化クロム粒子の異常粒成長の抑制作用が生じ難く、緻
密な組織になり難いので、同じく好ましくない。したが
って、本発明において、この添加物の添加範囲は、0.1
重量％以上1.0重量％未満が好ましく、この点も本発明
の特徴に１つとするものである。On the other hand, if the additive powder is less than 0.1% by weight,
The effect of suppressing the abnormal grain growth of chromium oxide particles is unlikely to occur, and it is difficult to form a dense structure, which is also not preferable. Therefore, in the present invention, the addition range of this additive is 0.1
The content is preferably not less than 1.0% by weight and less than 1.0% by weight, which is one of the features of the present invention.
【００１７】本発明において、酸化クロム焼結体を製造
するための出発原料として使用する酸化クロム及び添加
物の各粉末は、2μｍ以下のできるだけ微細な粉末を用
いるのが好ましい。この理由は、2μｍ以下の出発原料
を用いることにより、緻密な焼結体になり易いためであ
る。特に、本発明においては、限定するものではない
が、水熱法、アルコキシドの加水分解法又は中和共沈法
等によって得られる1μｍ以下の粉末を用いることが好
ましい。In the present invention, each powder of chromium oxide and an additive used as a starting material for producing a chromium oxide sintered body is preferably as fine as 2 μm or less. The reason for this is that a dense sintered body is likely to be formed by using a starting material of 2 μm or less. In the present invention, although not particularly limited, it is preferable to use a powder of 1 μm or less obtained by a hydrothermal method, an alkoxide hydrolysis method, a neutralization coprecipitation method, or the like.
【００１８】これら出発原料を用いて前記した添加量範
囲で配合し、水又はアセトン、ヘキサン、アルコ−ルな
どの有機溶媒を加えて湿式混合粉砕し、次に、この原料
粉末混合物を冷間静水圧成形（ＣＩＰ成形）又は一軸成
形した後、焼成する。焼成条件としては、真空中又はア
ルゴン等の非酸化雰囲気中で1550℃〜1700℃の温度範囲
で焼成することができる。These starting materials are blended in the above-mentioned addition amount range, water or an organic solvent such as acetone, hexane, alcohol or the like is added and wet mixed and pulverized. After hydroforming (CIP molding) or uniaxial molding, firing is performed. As a firing condition, firing can be performed in a temperature range of 1550 ° C. to 1700 ° C. in a vacuum or a non-oxidizing atmosphere such as argon.
【００１９】また、本発明において、上記一次焼成した
焼結体に対して更に熱間静水圧（ＨＩＰ）処理をするこ
とができる。このＨＩＰ処理を行うことにより、より一
層緻密な、より一層強度の高い焼結体が得られるので、
より好ましい（後記表３試料No.16〜18参照）。Further, in the present invention, the hydrostatic pressure (HIP) treatment can be further applied to the above-mentioned primary-fired sintered body. By performing this HIP treatment, a more compact sintered body having higher strength can be obtained.
It is more preferable (see sample Nos. 16 to 18 in Table 3 below).
【００２０】[0020]
【実施例】以下、本発明の実施例１（表２中の試料No.1
〜10）及び実施例２（表３中の試料No.16〜18）を比較
例（表２中の試料No.11〜15）と共に挙げ、本発明をよ
り詳細に説明する。EXAMPLE Hereinafter, Example 1 of the present invention (Sample No. 1 in Table 2)
~ 10) and Example 2 (Sample Nos. 16 to 18 in Table 3) together with Comparative Examples (Sample Nos. 11 to 15 in Table 2), the present invention will be described in more detail.
【００２１】（実施例１）表１に示す平均粒径、純度を
有する市販原料を使用し、表２に示す組成でボ−ルミル
にて湿式混合（溶媒：水）した後、1000ｋｇｆ／ｃｍ2
の圧力下で冷間静水圧成形（ＣＩＰ成形）を行い、成形
体を作製した。この成形体を表２に示す焼成条件（焼成
温度1550〜1700℃、Ａｒ雰囲気）で２時間焼成し、酸化
クロム焼結体を得た。Example 1 Commercially available raw materials having the average particle size and purity shown in Table 1 were used, and the composition shown in Table 2 was wet-mixed with a ball mill (solvent: water) and then 1000 kgf / cm 2
Cold isostatic pressing (CIP molding) was performed under the pressure of 1 to prepare a molded body. This compact was fired for 2 hours under the firing conditions shown in Table 2 (firing temperature 1550 to 1700 ° C, Ar atmosphere) to obtain a chromium oxide sintered body.
【００２２】得られた各酸化クロム焼結体の相対密度
（酸化クロムの理論密度5.21に対する％）を測定し、そ
の測定結果を表２に示した。また、各酸化クロム焼結体
の曲げ強度を測定し、その結果を同じく表２に示した。
なお、この曲げ強度は、JISR 1601に準じて3×4×40ｍ
ｍの試料を作成し、スパン30ｍｍで測定した値である。The relative density (% of the theoretical density of chromium oxide of 5.21) of each of the obtained chromium oxide sintered bodies was measured, and the measurement results are shown in Table 2. The bending strength of each chromium oxide sintered body was measured, and the results are also shown in Table 2.
The bending strength is 3 × 4 × 40m according to JISR 1601.
It is a value obtained by making a sample of m and measuring it with a span of 30 mm.
【００２３】なお、第２表には、本発明の範囲外の例を
試料No.11〜15（比較例）として合わせて記載した。即
ち、第２表中の試料No.1〜10は、本発明の範囲内であっ
て、本発明の実施例に相当し、試料No.11〜15は、本発
明の範囲外であって、比較例に相当する。In Table 2, examples outside the scope of the present invention are also shown as sample Nos. 11 to 15 (comparative examples). That is, sample Nos. 1 to 10 in Table 2 are within the scope of the present invention and correspond to Examples of the present invention, and sample Nos. 11 to 15 are outside the scope of the present invention. It corresponds to a comparative example.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】表２から明らかなように、本発明の範囲内
である試料No.1〜10では、いずれも相対密度が99％であ
り、しかも、30ｋｇｆ／ｍｍ2以上の曲げ強度を有する
緻密質酸化クロム焼結体が得られることが理解できる。
また、本発明で特定する添加物を単独で添加した試料N
o.1〜5に比して、これら添加物を併用した試料No.6〜10
では、より高強度の焼結体が得られることが理解でき
る。As is clear from Table 2, in Samples Nos. 1 to 10 which are within the scope of the present invention, the relative densities are all 99%, and the compacts having the bending strength of 30 kgf / mm 2 or more. It can be seen that a chromium oxide sintered body is obtained.
In addition, the sample N in which the additive specified in the present invention is added alone
Compared to o.1 ~ 5, sample No.6 ~ 10 using these additives together
Then, it can be understood that a higher strength sintered body can be obtained.
【００２７】これに対して、添加物を添加しない試料N
o.11及び同12では、相対密度が86％及び92％であって、
3ｋｇｆ／ｍｍ2及び7ｋｇｆ／ｍｍ2のものが得られるに
すぎなかった。また、添加物を添加し、本発明で限定す
る焼成温度範囲内の1550℃で焼成したとしても、その添
加物の添加量が本発明で限定する範囲外の10％という多
量配合した試料No.14及び同15では、相対密度、曲げ強
度とも本発明の実施例である試料No.1〜10に比して極め
て劣る酸化クロム焼結体が得られるにすぎなかった。更
に、本発明で限定する範囲外の2％配合した試料No.13で
も、上記と同様、相対密度、曲げ強度とも極めて劣るも
のが得られるにすぎなかった。On the other hand, sample N containing no additive
o.11 and 12 have relative densities of 86% and 92%,
Only 3 kgf / mm 2 and 7 kgf / mm 2 were obtained. Further, even if the additive is added and fired at 1550 ° C. within the firing temperature range limited by the present invention, the additive amount of the additive is 10% outside the range limited by the present invention in a large blended sample No. In No. 14 and No. 15, only a chromium oxide sintered body was obtained in which the relative density and bending strength were extremely inferior to those of Sample Nos. 1 to 10 which are Examples of the present invention. Further, in the case of Sample No. 13 containing 2% outside the range limited by the present invention, as in the above case, the relative density and the bending strength were very poor.
【００２８】（実施例２）実施例１で得られた本発明の
範囲内での焼結体（表２中の試料No.1〜3）について、
さらに熱間静水圧（ＨＩＰ）処理を実施した。この処理
条件は、1200ｋｇｆ／ｃｍ2の圧力でＡｒ雰囲気下、160
0℃の温度で2時間保持した。(Example 2) Regarding the sintered bodies (Sample Nos. 1 to 3 in Table 2) obtained in Example 1 and within the scope of the present invention,
Further, hot isostatic pressure (HIP) treatment was performed. The processing conditions are as follows: a pressure of 1200 kgf / cm 2 and an Ar atmosphere at 160
It was kept at a temperature of 0 ° C. for 2 hours.
【００２９】このＨＩＰ処理を行った焼結体について、
前記実施例１と同様、相対密度及び曲げ強度を測定し
た。その測定結果を試料No.16〜18として表３に示す。
この表３から明らかなように、実施例１で得られた焼結
体をさらにＨＩＰ処理することにより、より一層緻密化
し、より高強度な焼結体が得られることが理解できる。Regarding the sintered body which has been subjected to this HIP treatment,
The relative density and bending strength were measured in the same manner as in Example 1. The measurement results are shown in Table 3 as sample Nos. 16-18.
As is clear from Table 3, it can be understood that the sintered body obtained in Example 1 is further densified to obtain a sintered body having higher strength by HIPing.
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【発明の効果】本発明は、以上詳記したとおり、添加す
る酸化物（Ｍｇ、Ａｌ、Ｃａ、Ｔｉ又は希土類酸化物よ
り選ばれた少なくとも１種以上の酸化物）の量を0.1重
量％以上1.0重量％未満と最小限に抑えているため、高
温特性劣下のない機械的特性を有する緻密質酸化クロム
焼結体が得られる効果が生ずる。そして、本発明によ
り、ガラス溶融用部材、金属用部材等の利用分野におい
て好適に利用することができる緻密質酸化クロム焼結体
を提供することができる。INDUSTRIAL APPLICABILITY As described in detail above, the present invention provides that the amount of added oxide (at least one oxide selected from Mg, Al, Ca, Ti or rare earth oxides) is 0.1% by weight or more. Since the amount is minimized to less than 1.0% by weight, there is an effect that a dense chromium oxide sintered body having mechanical characteristics without deterioration in high temperature characteristics can be obtained. Further, according to the present invention, it is possible to provide a dense chromium oxide sintered body which can be suitably used in a field of use such as a glass melting member and a metal member.
Claims (3)
ｉ又は希土類酸化物より選ばれた少なくとも１種以上の
酸化物粉末0.1重量％以上1.0重量％未満との混合粉末を
焼成してなることを特徴とする緻密質酸化クロム焼結
体。1. A chromium oxide powder and Mg, Al, Ca, T
A dense chromium oxide sintered body obtained by firing a mixed powder of at least one oxide powder selected from i or rare earth oxides and 0.1% by weight or more and less than 1.0% by weight.
ｉ又は希土類酸化物より選ばれた少なくとも１種以上の
酸化物粉末0.1重量％以上1.0重量％未満を混合し、該混
合粉末を非酸化雰囲気中で1550℃〜1700℃の温度範囲で
焼成することを特徴とする緻密質酸化クロム焼結体の製
造方法。2. A chromium oxide powder containing Mg, Al, Ca, T
i or a mixture of at least one oxide powder of at least one selected from rare earth oxides in an amount of 0.1% by weight or more and less than 1.0% by weight and firing the mixed powder in a temperature range of 1550 ° C to 1700 ° C in a non-oxidizing atmosphere. And a method for producing a dense chromium oxide sintered body.
ｉ又は希土類酸化物より選ばれた少なくとも１種以上の
酸化物粉末0.1重量％以上1.0重量％未満を混合し、該混
合粉末を非酸化雰囲気中で1550℃〜1700℃の温度範囲で
焼成し、更に熱間静水圧処理を施すことを特徴とする緻
密質酸化クロム焼結体の製造方法。3. A chromium oxide powder containing Mg, Al, Ca, T
i or at least one oxide powder selected from rare earth oxides, 0.1% by weight or more and less than 1.0% by weight is mixed, and the mixed powder is fired in a temperature range of 1550 ° C. to 1700 ° C. in a non-oxidizing atmosphere, A method for producing a dense chromium oxide sintered body, which further comprises hot isostatic pressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10190892A JPH05279115A (en) | 1992-03-27 | 1992-03-27 | Dense sintered compact of chromium oxide and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10190892A JPH05279115A (en) | 1992-03-27 | 1992-03-27 | Dense sintered compact of chromium oxide and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05279115A true JPH05279115A (en) | 1993-10-26 |
Family
ID=14313012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10190892A Pending JPH05279115A (en) | 1992-03-27 | 1992-03-27 | Dense sintered compact of chromium oxide and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05279115A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014511328A (en) * | 2011-02-15 | 2014-05-15 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Sintered materials based on doped chromium oxide |
| CN113636833A (en) * | 2021-09-06 | 2021-11-12 | 郑州大学 | Chromium oxide ceramic material, preparation method thereof and heat preservation device for sintering chromium oxide ceramic material |
-
1992
- 1992-03-27 JP JP10190892A patent/JPH05279115A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014511328A (en) * | 2011-02-15 | 2014-05-15 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Sintered materials based on doped chromium oxide |
| US9242885B2 (en) | 2011-02-15 | 2016-01-26 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Sintered material based on doped chromium oxide |
| CN113636833A (en) * | 2021-09-06 | 2021-11-12 | 郑州大学 | Chromium oxide ceramic material, preparation method thereof and heat preservation device for sintering chromium oxide ceramic material |
| CN113636833B (en) * | 2021-09-06 | 2023-11-24 | 郑州大学 | A chromium oxide ceramic material and its preparation method and a heat preservation device for sintering the chromium oxide ceramic material |
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