JP2619051B2 - Zirconia refractory and method for producing the same - Google Patents
Zirconia refractory and method for producing the sameInfo
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- JP2619051B2 JP2619051B2 JP1074618A JP7461889A JP2619051B2 JP 2619051 B2 JP2619051 B2 JP 2619051B2 JP 1074618 A JP1074618 A JP 1074618A JP 7461889 A JP7461889 A JP 7461889A JP 2619051 B2 JP2619051 B2 JP 2619051B2
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- zirconia
- solid solution
- raw material
- stabilizing component
- refractory
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Description
【発明の詳細な説明】 ［発明の目的］ （産業上の利用分野） 本発明は例えば匣鉢，敷板等の窯道具に使用されるジ
ルコニア耐火物及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a zirconia refractory used for kiln tools such as saggers and floorboards, and a method for producing the same.
（従来の技術） ジルコニア（ZrO2）耐火物は、酸化雰囲気で高い耐火
度を有し、耐腐食性にも優れる等の特徴を備えており、
近年では、例えばセラミックコンデンサ焼成用の匣鉢，
敷板等の窯道具として使用されている。(Conventional technology) Zirconia (ZrO 2 ) refractories have features such as high fire resistance in an oxidizing atmosphere and excellent corrosion resistance.
In recent years, for example, saggers for firing ceramic capacitors,
Used as a kiln tool for flooring.
ところで、ジルコニアは、周知のように1000℃付近の
相転移温度にて大きな体積変化は生ずる。このため、耐
火物原料としては、一般に、ジルコニアにカルシア（Ca
O）やマグネシア（MgO）を固溶させて等軸晶構造とした
安定化ジルコニアとして供されている。As is well known, zirconia undergoes a large volume change at a phase transition temperature near 1000 ° C. Therefore, as a refractory raw material, generally, zirconia is added to calcia (Ca
O) and magnesia (MgO) are provided as stabilized zirconia in a solid solution with an equiaxed crystal structure.
ジルコニア耐火物例えば匣鉢は、一般に、上記したよ
うな安定化ジルコニアの原料粉体に有機バインダー等を
添加した上で混練し、これを所要の匣鉢形状に加圧成形
し、乾燥後1500〜1700℃で構成することにより製造され
る。この場合、安定化ジルコニアの原料は、安定化率が
80％程度のものが一般的に使用されている。Zirconia refractories such as saggers are generally kneaded after adding an organic binder or the like to the raw material powder of stabilized zirconia as described above, press-molding this into a required sagger shape, and drying after 1500 to Manufactured by configuring at 1700 ° C. In this case, the stabilized zirconia raw material has a stabilization rate of
About 80% of them are commonly used.
（発明が解決しようとする課題） ところで、上記のようなジルコニア耐火物は、安定化
されているものの、使用するに伴いカルシウムやマグネ
シウム等の固溶安定化成分が離脱する脱固溶現象が進行
して安定化率が次第に低下し、繰返し使用によりやはり
僅かずつではあるが体積変化が生じてしまう。(Problems to be Solved by the Invention) By the way, although the zirconia refractory as described above is stabilized, a solid solution stabilizing component such as calcium or magnesium is released as the solid refractory is used. As a result, the stabilization rate gradually decreases, and a repeated use repeatedly causes a slight change in volume.
これに対し、近年自動化が進む例えば電子工業用の焼
成炉においては、窯詰め作業等も自動で行なわれるよう
になってきており、この自動化に伴い匣鉢等の窯道具の
寸法にも高い精度が要求されている。このため、従来の
安定化率80％程度のジルコニア耐火物（匣鉢）では、上
述のような体積変化により耐用回数が少なくなってしま
う問題点が生じている。On the other hand, for example, firing furnaces for the electronics industry, which have been increasingly automated in recent years, are also being used to automatically perform kiln filling work, etc., and with this automation, the dimensions of kiln tools such as saggers are also highly accurate. Is required. For this reason, in the conventional zirconia refractory (sagger) having a stabilization rate of about 80%, there is a problem that the number of times of use is reduced due to the above-mentioned volume change.
この欠点を解消するには、予め安定化率の高い安定化
ジルコニアを使用して匣鉢を製造することが考えられる
が、このような高安定化率の安定化ジルコニア原料は極
めて高価であり、製造コストが大きく上昇する問題があ
る。In order to solve this drawback, it is conceivable to manufacture a sagger using a stabilized zirconia having a high stabilization rate in advance, but a stabilized zirconia raw material having such a high stabilization rate is extremely expensive, There is a problem that the manufacturing cost increases significantly.
本発明は上記事情に鑑みてなされたもので、その目的
は、一般的な安定化ジルコニア原料を使用して高い安定
化率の製品を安価に製造することのできるジルコニア耐
火物及びその製造方法を提供するにある。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a zirconia refractory capable of inexpensively producing a product having a high stabilization rate using a general stabilized zirconia raw material and a method for producing the same. To offer.
［発明の構成］ （課題を解決するための手段） 本発明の第１のジルコニア耐火物の製造方法は、安定
化ジルコニアの原料粉体にジルコニアに対する固溶安定
化成分を添加して焼成するようにしたところに特徴を有
する。[Constitution of the Invention] (Means for Solving the Problems) In the first method for producing a zirconia refractory of the present invention, a solid solution stabilizing component for zirconia is added to raw material powder of stabilized zirconia and calcined. It has the characteristic in the place where
また、本発明の第２のジルコニア耐火物は、安定化ジ
ルコニアの原料粉体を所要形状に成形して焼成し、この
焼成品にジルコニアに対する固溶安定化成分を添加した
状態としたところに特徴を有する。Further, the second zirconia refractory of the present invention is characterized in that a raw material powder of stabilized zirconia is formed into a required shape and fired, and the fired product is added with a solid solution stabilizing component for zirconia. Having.
さらに、本発明の第３のジルコニア耐火物の製造方法
は、安定化ジルコニアの原料粉体を所要形状に成形して
焼成した焼成品に、ジルコニアに対する固溶安定化成分
を添加し、これをジルコニアに対する固溶可能温度まで
上昇させたところに特徴を有する。Further, the third method for producing a zirconia refractory of the present invention comprises the steps of: adding a solid solution stabilizing component to zirconia to a fired product obtained by shaping a raw material powder of stabilized zirconia into a required shape and firing; This is characterized in that the temperature is raised to a temperature at which solid solution is possible.
（作用） 本発明者等は、種々の実験，研究の結果、安定化ジル
コニア原料にジルコニアに対する固溶安定化成分を添加
して焼成することにより、固溶安定化成分がジルコニア
に固溶し、より高い安定化率の焼成製品が得られること
を知見し、本発明を完成させるに至った。なお、固溶安
定化成分を添加した未焼成成形体の作り方としては、原
料粉体調合の段階で固溶安定化成分を粉末状態もしく
は、水などの溶媒に溶解した状態や懸濁させた状態で添
加し、これを混練・成形する方法の他に、安定化ジルコ
ニアの原料粉体を混練・成形した後、固溶安定化成分を
溶液状態や懸濁液状態で含浸等の方法で添加することも
可能であるが、成形後の含浸によって添加する場合に
は、含浸中に未焼成成形品が壊れやすいので、あらかじ
め添加し成形する方が望ましい。(Action) As a result of various experiments and studies, the present inventors have found that a solid solution stabilizing component is dissolved in zirconia by adding a solid solution stabilizing component to zirconia to a stabilized zirconia raw material and firing. The inventors have found that a fired product with a higher stabilization rate can be obtained, and have completed the present invention. The green body to which the solid-solution stabilizing component is added may be prepared in a powdery state, a state of being dissolved in a solvent such as water, or a state of being suspended in a raw material powder preparation stage. In addition to the method of kneading and molding this, after kneading and molding the raw material powder of stabilized zirconia, the solid solution stabilizing component is added by a method such as impregnation in a solution state or a suspension state. Although it is also possible to add it by impregnation after molding, it is preferable to add and mold in advance because the green molded article is easily broken during the impregnation.
また、一旦焼成された安定化ジルコニア原料からなる
焼成品に、ジルコニアに対する固溶安定化成分を含浸さ
せた後再焼成すれば、固溶安定化成分がジルコニアに固
溶するから、上記同様により高い安定化率のジルコニア
耐火物となることを確認した。さらに、一旦焼成された
安定化ジルコニア原料からなる焼成品に対して上記と同
様の固溶安定化成分を増加しておけば、これを匣鉢等の
耐火物として使用する際の温度上昇により固溶安定化成
分がジルコニアに固溶するから、上記同様により高い安
定化率のジルコニア耐火物となることを確認した。従っ
て、本発明の製造方法による製品としては、安定化ジル
コニアの原料粉体を成形・焼成したものに固溶安定化成
分を添加しただけのものであっても、固溶安定化成分を
添加した後に再焼成したものであっても良く、いずれも
同様の高い安定化率のジルコニア耐火物として得られ
る。これらの場合の加熱（再焼成）温度としては、一般
に高温の方が高い安定化率が得られるが、1300〜1700℃
が好ましい。In addition, if the fired product made of the stabilized zirconia raw material once fired is impregnated with the solid solution stabilizing component for zirconia and then refired, the solid solution stabilizing component dissolves in zirconia, and thus is higher than the above. It was confirmed that the zirconia refractory had a stabilized rate. Furthermore, if a solid solution stabilizing component similar to the above is increased in a fired product made of the stabilized zirconia raw material once fired, the solid solution stabilizing component is increased due to an increase in temperature when used as a refractory such as a sagger. Since the solution stabilizing component solid-dissolves in zirconia, it was confirmed that a zirconia refractory having a higher stabilization rate was obtained in the same manner as described above. Therefore, as a product according to the production method of the present invention, a solid solution stabilizing component was added even if only a solid solution stabilizing component was added to a product obtained by molding and firing a stabilized zirconia raw material powder. It may be refired later, and all are obtained as a zirconia refractory having a similar high stabilization rate. As for the heating (re-firing) temperature in these cases, a higher temperature generally gives a higher stabilization rate, but 1300 to 1700 ° C
Is preferred.
尚、ジルコニアに対する固溶安定化成分としては、カ
ルシウム（Ca），マグネシウム（Mg），イットリウム
（Ｙ），セリウム（Ce），ジスプロシウム（Dy），エル
ビウム（Er），ネオジウム（Nd），プロセオジム（P
r），ランタン（La）等がある。また、これらの固溶安
定化成分は、それらを含む化合物の粉末やコロイド溶液
状態で原料粉体に混合したり含浸させることも可能だ
が、酢酸塩，塩化物，硫化物等の可溶性塩として用いる
ことが製造上便利である。また、本発明者等の実験によ
れば、これらのうち特に酢酸塩の水溶液が良好な効果が
得られた。The solid solution stabilizing components for zirconia include calcium (Ca), magnesium (Mg), yttrium (Y), cerium (Ce), dysprosium (Dy), erbium (Er), neodymium (Nd), and proseodymium (P
r) and lantern (La). These solid-solution stabilizing components can be mixed or impregnated with the raw material powder in the form of a powder or colloidal solution of the compound containing them, but they are used as soluble salts such as acetates, chlorides and sulfides. This is convenient for manufacturing. According to experiments by the present inventors, among these, an aqueous solution of acetate was particularly effective.
また、このような固溶安定化成分の添加方法としては
各種の方法をとり得るが、例えば真空含浸法等を採用
し、水等の溶媒に溶解又は分散させ多量に含浸させるこ
とが望ましく、安定化率もその含浸量に対応して向上す
る。Further, various methods can be used as a method for adding such a solid solution stabilizing component.For example, a vacuum impregnation method or the like is adopted, and it is preferable to dissolve or disperse in a solvent such as water and impregnate in a large amount. The conversion rate also increases in accordance with the impregnation amount.
（実施例） 以下本発明のいくつかの実施例について説明する。(Examples) Hereinafter, some examples of the present invention will be described.
（１）実施例１〜実施例８ 実施例１〜実施例８は請求項１の発明に対応し、次の
ようにしてジルコニア耐火物（この場合匣鉢）を製造し
た例を示す。(1) Embodiments 1 to 8 Embodiments 1 to 8 correspond to the invention of claim 1 and show examples in which zirconia refractories (in this case, saggers) are manufactured as follows.
まず市販の安定化ジルコニア原料粉体（安定化率約80
％）に後述する固溶安定化成分を含む化合物と有機バイ
ンダーとを混合した上で混練し、これを所要形状即ち匣
鉢形状に加圧成形する。これを乾燥させた後、1600℃に
て焼成する。First, commercially available stabilized zirconia raw material powder (stabilization rate of about 80
%), A compound containing a solid solution stabilizing component, which will be described later, and an organic binder are mixed and kneaded, and the mixture is pressed into a required shape, that is, a sagger shape. After being dried, it is fired at 1600 ° C.
この場合、ジルコニアに対する固溶安定化成分を含む
化合物としては、実施例１〜４では酢酸カルシウム粉末
（Ca（CH3COO）２・H2O）、実施例5,6では酢酸マグネシ
ウム粉末（Mg（CH3COO）２・H2O）、実施例7,8では酢酸
イットリウム粉末（Ｙ（CH3COO）３・H2O）を夫々用い
ている。これらは30gを水100gに溶解し、さらにPVAを５
％添加して水溶液として、安定化ジルコニアに対する混
合割合を変化させて固溶安定化成分の添加量を変化させ
た。尚、成形体匣鉢の体積は202.3cm3、気孔率は約18〜
26％であり、酢酸カルシウム，酢酸マグネシウム及び酢
酸イットリウムの混合量は各々表1,2のようになった。In this case, as the compound containing a solid solution stabilizing component for zirconia, in Examples 1 to 4, calcium acetate powder (Ca (CH 3 COO) 2 .H 2 O), and in Examples 5 and 6, magnesium acetate powder (Mg (CH 3 COO) 2 .H 2 O), and in Examples 7 and 8, yttrium acetate powder (Y (CH 3 COO) 3 .H 2 O) was used. These dissolve 30 g in 100 g of water and add 5
% As an aqueous solution, the mixing ratio to the stabilized zirconia was changed to change the added amount of the solid solution stabilizing component. In addition, the volume of the molded sagger is 202.3 cm 3 , and the porosity is about 18 ~
It was 26%, and the mixing amounts of calcium acetate, magnesium acetate and yttrium acetate were as shown in Tables 1 and 2, respectively.
これら実施例１〜８の焼成後の安定化率及び使用（通
窯）に伴う安定化率の変化を比較例１と合わせて表1,2
に示す。比較例１は、実施例１〜８と同様の成形品を固
溶安定化成分の添加を行なわずに成形・焼成して得られ
る従来の製造方法による匣鉢である。また、表中に使用
した安定化率としては、匣鉢を1350℃の窯炉中に12分保
持後自然冷却することを５回,10回及び15回繰返した後
に測定した安定化率を夫々示している。Tables 1 and 2 show the stabilization rate after firing in Examples 1 to 8 and the change in stabilization rate due to use (through kiln) together with Comparative Example 1.
Shown in Comparative Example 1 is a sagger according to a conventional production method obtained by molding and firing the same molded product as in Examples 1 to 8 without adding a solid solution stabilizing component. The stabilization rates used in the table are the stabilization rates measured after holding the sagger in a kiln at 1350 ° C for 12 minutes and then cooling it naturally, 5 times, 10 times, and 15 times, respectively. Is shown.
この表1,2から明らかなように、固溶安定化成分の酢
酸塩を含む成形体を焼成する方法により得られた実施例
１〜８の匣鉢は、原料の安定化率（81.4％）よりも高い
安定化率となる。このように、安定化率が高まったこと
によって、実施例１〜８は従来方法で製造された比較例
１に比べて同じ通窯回数でも高い安定化率を確保するこ
とができ、言い換えるならば、脱固溶の進行により所定
のレベルに安定化率が低下するまでの期間（使用回数）
を長くすることができる。この結果、匣鉢の体積変化を
長期間に渡って小さく抑えることができて耐用回数を多
くすることができる。しかも、安定化ジルコニア原料と
しては従来と同様の一般的なものが使用されており、ま
た、製造行程としては固溶安定化成分を含んだ化合物を
原料粉体に混合する行程が増えるだけでさほど高度な技
術を必要とすることもない。As is clear from Tables 1 and 2, the saggers of Examples 1 to 8 obtained by the method of firing the molded body containing the acetate as the solid solution stabilizing component showed a stabilization rate of the raw material (81.4%). Higher stabilization rate. As described above, by increasing the stabilization rate, Examples 1 to 8 can secure a high stabilization rate even at the same number of times of passing through the kiln as compared with Comparative Example 1 manufactured by the conventional method. In other words, , The period until the stabilization rate decreases to a predetermined level due to the progress of solid solution (number of uses)
Can be lengthened. As a result, the change in volume of the sagger can be kept small over a long period of time, and the number of times of use can be increased. In addition, as the stabilized zirconia raw material, the same general ones as those used in the past are used.In addition, the production process involves adding a compound containing a solid solution-stabilizing component to the raw material powder. There is no need for advanced technology.
このように、本実施例によれば、高い安定化率のジル
コニア耐火物を安価に製造することができるものであ
る。As described above, according to the present embodiment, a zirconia refractory having a high stabilization rate can be manufactured at low cost.
（２）実施例９〜実施例18 実施例９〜18は請求項３の発明に対応し、次のように
してジルコニア耐火物（匣鉢）を製造した例を示す。(2) Embodiments 9 to 18 Embodiments 9 to 18 correspond to the invention of claim 3 and show examples in which a zirconia refractory (sagger) is manufactured as follows.
まず市販の安定化ジルコニア原料粉体（安定化率80
％）に有機バインダーを添加した上で混練し、これを匣
鉢形状に加圧成形した後1600℃にて焼成する。次に、こ
の焼成品にジルコニアに対する固溶安定化成分を含む化
合物の溶液を真空含浸法により１時間含浸させる。この
場合、実施例９〜14では、固溶安定化成分を含む化合物
として酢酸カルシウムを使用し、その含浸量を変えるた
め水溶液の濃度を変えたものを使用した。実施例15〜18
では同様にして調整した酢酸マグネシウムの水溶液を使
用した。この後、この焼成品を乾燥させ、乾燥後1450℃
及び1600℃で再焼成した。First, a commercially available stabilized zirconia raw material powder (stabilization rate 80
%), Kneaded after adding an organic binder, press-molded this into a sagger shape, and fired at 1600 ° C. Next, the fired product is impregnated with a solution of a compound containing a solid solution stabilizing component for zirconia for one hour by a vacuum impregnation method. In this case, in Examples 9 to 14, calcium acetate was used as the compound containing the solid solution stabilizing component, and the concentration of the aqueous solution was changed to change the impregnation amount. Examples 15 to 18
Then, an aqueous solution of magnesium acetate prepared in the same manner was used. Thereafter, the fired product is dried, and after drying, at 1450 ° C.
And fired again at 1600 ° C.
このようにして得られた実施例９〜18の安定化率を表
3,4に比較例２と合わせて示す。比較例２は上記の比較
例１と同様の従来の製造方法により得られた匣鉢であ
る。The stabilization rates of Examples 9 to 18 obtained in this way are shown in Table 1.
3 and 4 show the results together with Comparative Example 2. Comparative Example 2 is a sagger obtained by the same conventional manufacturing method as in Comparative Example 1 described above.
このようにして得られた匣鉢は、実施例９〜18で明ら
かなように、含浸量が多く再焼成温度が高いほど安定化
率が得られる。また脱固溶の進行によって所定レベルま
で安定化率が低下するまでの期間についても、いずれも
含浸しない場合に比べ長くできる。As is apparent from Examples 9 to 18, the sagger thus obtained has a higher stabilization rate as the impregnation amount is larger and the refiring temperature is higher. In addition, the period until the stabilization rate decreases to a predetermined level due to the progress of the solid solution can be made longer than the case where neither is impregnated.
（３）実施例19〜実施例23 この実施例は請求項２の発明に対応する。前記実施例
９〜18と同様に、市販の安定化ジルコニア原料粉体（安
定化率約80％）に有機バインダーを添加した上で混練
し、これを匣鉢形状に加圧成形した後1600℃にて焼成す
る。次に、この焼成品に夫々実施例９〜11及び15〜16と
同様な固溶安定化成分を含む各種の化合物の水溶液を用
いて真空法により１時間含浸させた。その後、この焼成
品を乾燥させた。(3) Embodiments 19 to 23 This embodiment corresponds to the second aspect of the present invention. In the same manner as in Examples 9 to 18, a commercially available stabilized zirconia raw material powder (stabilization rate: about 80%) was added with an organic binder, kneaded, and the mixture was press-molded into a sagger shape. Baking. Next, this calcined product was impregnated for 1 hour by a vacuum method using aqueous solutions of various compounds containing a solid solution stabilizing component as in Examples 9 to 11 and 15 to 16, respectively. Thereafter, the fired product was dried.
このように製造した後、匣鉢として使用して焼成温度
1350℃に設定された窯炉内に収容する。被焼成品の加熱
焼成に伴い、匣鉢自体も加熱されて固溶可能温度まで上
昇されるから、含浸された化合物中の固溶安定化成分が
ジルコニアに固溶して１回使用した後には実施例９〜18
と同様高い安定化率となった。この結果を表５に示す。After manufacturing in this way, use as sagger and firing temperature
Store in a kiln set at 1350 ° C. As the sagger itself is heated to the solid solution temperature with the heating and firing of the article to be fired, the solid solution stabilizing component in the impregnated compound becomes solid solution in zirconia and is used once. Examples 9 to 18
High stabilization rate was obtained as well. Table 5 shows the results.
従って、前記実施例９〜18と同様に脱固溶の進行によ
って所定レベルまで安定化率が低下するまでの期間を長
くすることができた。Accordingly, as in Examples 9 to 18, the period until the stabilization rate decreased to a predetermined level due to the progress of the solid solution could be lengthened.
尚、本発明は上記各実施例に限定されるものではな
く、例えば匣鉢に限らず築炉用耐火物等様々な耐火物に
適用できる等、要旨を逸脱しない範囲内で適宜変更して
実施し得る。Note that the present invention is not limited to the above embodiments, and can be applied to various refractories such as refractories for furnace construction, not limited to saggers, for example. I can do it.
［発明の効果］ 以上の説明にて明らかなように、本発明によれば、一
般的な安定化ジルコニア原料を使用して高い安定化率の
ジルコニア耐火物を安価に製造することができるという
優れた効果を奏する。 [Effects of the Invention] As is clear from the above description, according to the present invention, an excellent zirconia refractory having a high stabilization rate can be produced at low cost using a general stabilized zirconia raw material. It has the effect.
Claims (3)
に対する固溶安定化成分を添加して焼成することを特徴
とするジルコニア耐火物の製造方法。1. A method for producing a zirconia refractory, comprising adding a solid solution stabilizing component to zirconia to a raw material powder of stabilized zirconia and firing.
成形して焼成し、この焼成品にジルコニアに対する固溶
安定化成分を添加した状態としたことを特徴とするジル
コニア耐火物。2. A zirconia refractory wherein a stabilized zirconia raw material powder is formed into a required shape and fired, and the fired product is added with a solid solution stabilizing component for zirconia.
成形して焼成した焼成品に、ジルコニアに対する固溶安
定化成分を添加し、これを固溶可能温度まで上昇させた
ことを特徴とするジルコニア耐火物の製造方法、3. A zirconia solid solution-stabilizing component is added to a calcined product obtained by shaping a raw material powder of stabilized zirconia into a required shape and calcining the mixture to raise the temperature to a temperature at which solid solution is possible. Zirconia refractory manufacturing method,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1074618A JP2619051B2 (en) | 1989-03-27 | 1989-03-27 | Zirconia refractory and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1074618A JP2619051B2 (en) | 1989-03-27 | 1989-03-27 | Zirconia refractory and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02252656A JPH02252656A (en) | 1990-10-11 |
| JP2619051B2 true JP2619051B2 (en) | 1997-06-11 |
Family
ID=13552343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1074618A Expired - Lifetime JP2619051B2 (en) | 1989-03-27 | 1989-03-27 | Zirconia refractory and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2619051B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05270911A (en) * | 1992-03-25 | 1993-10-19 | Ngk Insulators Ltd | Zirconia refractory setter |
-
1989
- 1989-03-27 JP JP1074618A patent/JP2619051B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02252656A (en) | 1990-10-11 |
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