JP2942061B2 - Alumina-zirconia electroformed refractories - Google Patents
Alumina-zirconia electroformed refractoriesInfo
- Publication number
- JP2942061B2 JP2942061B2 JP4150023A JP15002392A JP2942061B2 JP 2942061 B2 JP2942061 B2 JP 2942061B2 JP 4150023 A JP4150023 A JP 4150023A JP 15002392 A JP15002392 A JP 15002392A JP 2942061 B2 JP2942061 B2 JP 2942061B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- zirconia
- refractories
- refractory
- electroformed
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】この発明は特に耐スポール性に優
れたアルミナ−ジルコニア質電鋳耐火物に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alumina-zirconia electroformed refractory having particularly excellent spall resistance.
【０００２】[0002]
【従来の技術】従来のガラス溶解炉に使用されているア
ルミナまたはジルコニア質電鋳耐火物としては、高アル
ミナ質、アルミナ・ジルコニア・シリカ質（以下ＡＺＳ
耐火物と言う）、高ジルコニア質がある。2. Description of the Related Art Alumina or zirconia electroformed refractories used in conventional glass melting furnaces include high alumina, alumina-zirconia-silica (hereinafter AZS).
Refractory), high zirconia.
【０００３】高アルミナ質の電鋳耐火物は、ガラスに対
して侵蝕抵抗が大きく、またガラスに泡、コード等の欠
陥を生じさせない特徴を持ち、アルカリ蒸気に対しても
安定で、荷重下でも変形することがない。[0003] High-alumina electroformed refractories have high corrosion resistance to glass, do not cause defects such as bubbles and cords in glass, are stable against alkali vapor, and can be used under load. No deformation.
【０００４】ＡＺＳ耐火物は、例えば特開昭６２−６５
９８１号公報に開示されているように、ジルコニアを多
量に含んでいて、溶融ガラスに対して耐蝕性が大きい。AZS refractories are disclosed in, for example, Japanese Patent Application Laid-Open No. 62-65.
As disclosed in JP-A-981, it contains a large amount of zirconia and has high corrosion resistance to molten glass.
【０００５】さらに、最近ではジルコニアを９０％以上
含む高ジルコニア質の電鋳耐火物が特開平３−２８１７
５号公報に提案されており、その使用も増加しつつあ
る。ジルコニアを多量に含有している電鋳耐火物は溶融
ガラスや飛散した生バッチに対して非常に耐蝕性が大き
く、溶融ガラスと直接接触する部分での使用に於いて耐
蝕性の点で十分満足のできるものである。Further, recently, a high zirconia electroformed refractory containing 90% or more of zirconia has been disclosed in JP-A-3-2817.
No. 5 and its use is increasing. Electroformed refractories containing a large amount of zirconia have very high corrosion resistance to molten glass and scattered raw batches, and are fully satisfactory in terms of corrosion resistance when used in direct contact with molten glass It can be.
【０００６】[0006]
【発明が解決しようとする課題】しかし、従来の電鋳耐
火物には以下のような欠点があった。すなわち、高アル
ミナ質電鋳耐火物は耐スポール性に劣り、温度条件の厳
しい場所、例えばガラス溶解炉の上部構造に使用するに
は不都合であった。ＡＺＳ耐火物は使用中に耐火物表面
からガラス状のものが流れ落ち、それが溶融ガラスに欠
陥を生じる原因となっていた。高ジルコニア質電鋳耐火
物はその緻密さやジルコニアの結晶変態により耐スポー
ル性に劣るため使用温度や使用場所が極端に制限されて
いた。However, conventional electrocast refractories have the following disadvantages. That is, the high-alumina electroformed refractory is inferior in spall resistance and is inconvenient for use in a place where temperature conditions are severe, for example, an upper structure of a glass melting furnace. During use, the AZS refractory caused a glassy material to flow off the surface of the refractory, which caused defects in the molten glass. Since the high zirconia electroformed refractory is inferior in spall resistance due to its denseness and crystal transformation of zirconia, the use temperature and place of use have been extremely limited.
【０００７】本発明の目的は、このようなアルミナまた
はジルコニア質電鋳耐火物の欠点を解消するものであ
り、Ａｌ2 Ｏ3 の含有量を８０％以上に維持させて、比
重および気孔率を大きく変化させることなく、溶融ガラ
スやアルカリ蒸気に対して高い耐蝕性を保持し、さらに
溶融ガラスに接した時に発生する泡を低く抑え、かつ耐
スポール性の高いアルミナ−ジルコニア質電鋳耐火物を
提供することである。An object of the present invention is to eliminate such disadvantages of the alumina or zirconia electroformed refractories, and to maintain the Al 2 O 3 content at 80% or more to reduce the specific gravity and the porosity. Without significantly changing, it retains high corrosion resistance to molten glass and alkali vapor, suppresses bubbles generated when it comes in contact with molten glass, and has high spall resistance alumina-zirconia electroformed refractories. To provide.
【０００８】[0008]
【課題を解決するための手段】この目的を達成するため
に種々の研究を重ねた結果、本発明者らは高アルミナ質
電鋳耐火物の鉱物構成について、発泡の原因と考えられ
るガラス相の構成成分を低くし、しかも熱衝撃時の応力
を緩和すると考えられるＺｒＯ2 を混在させることによ
って、比重および気孔率を大きく変化させることなく、
溶融ガラスやアルカリ蒸気に対して高い耐蝕性を保持
し、さらに溶融ガラスに接した時に発生する泡を低く抑
えて耐スポール性の高いアルミナ−ジルコニア質鋳造耐
火物が製造できることを見出した。As a result of various studies to achieve this object, the present inventors found that the mineral composition of the high-alumina electroformed refractory has a glass phase which is considered to be a cause of foaming. By lowering the components and mixing ZrO 2, which is considered to relieve the stress at the time of thermal shock, without significantly changing the specific gravity and the porosity,
It has been found that an alumina-zirconia cast refractory having high spall resistance can be produced while maintaining high corrosion resistance to molten glass and alkali vapor, and suppressing bubbles generated when the molten glass comes into contact with molten glass.
【０００９】本発明の要旨は重量％でＡｌ2 Ｏ3 が８０
〜９４％、ＺｒＯ2 が１．５〜１５％、その他の成分が
２．７〜６．４％である電鋳耐火物である。さらにその
他の成分としてＳｉＯ2 を０．６〜１．２％、Ｎａ2 Ｏ
を２〜５％、ＣａＯを０．１〜０．２％それぞれ含む電
鋳耐火物が好ましい。The gist of the present invention is that Al 2 O 3 is 80% by weight.
To 94% ZrO 2 is 1.5 to 15%, the other component is a refractory electroforming is 2.7 to 6.4%. Further, as other components, 0.6 to 1.2% of SiO 2 and Na 2 O
Is preferably 2 to 5% and 0.1 to 0.2% of CaO.
【００１０】各組成の範囲についてその理由を述べる。The reason for each composition range will be described.
【００１１】ＺｒＯ2 が１．５％未満だと、ＺｒＯ2 の
効果が不十分であり、１５％を越えると、耐スポール性
と発泡性に劣る。When the content of ZrO 2 is less than 1.5%, the effect of ZrO 2 is insufficient, and when it exceeds 15%, the spall resistance and the foaming property are poor.
【００１２】さらに、ＳｉＯ2 が０．６〜１．２％、Ｎ
ａ2 Ｏが２〜５％、ＣａＯが０．１〜０．２％であるの
が好ましいが、これらは大部分がガラス相の構成成分で
あり、多いと発泡が多くなりやすく、少ないと製品にク
ラック、コーナースポール等の欠陥が生じやすくなる。Furthermore, 0.6-1.2% of SiO 2 , N
It is preferable that a 2 O is 2 to 5% and CaO is 0.1 to 0.2%, but these are mostly constituent components of the glass phase. Defects, such as cracks and corner spalls, are likely to occur.
【００１３】[0013]
【作用】前記構成により、本発明の耐火物は、比重およ
び気孔率を大きく変化させることなく、溶融ガラスに対
して低発泡性を維持しながら従来の高アルミナ質電鋳耐
火物に比べて耐蝕性を増加させ、さらには高アルミナ質
電鋳耐火物はもちろん、ＡＺＳ耐火物や高ジルコニア質
電鋳耐火物と比べても極めて優れた耐スポール性を奏す
る。With the above construction, the refractory of the present invention has a lower corrosion resistance than the conventional high-alumina electroformed refractory while maintaining a low foaming property with respect to the molten glass without largely changing the specific gravity and the porosity. In addition, it exhibits extremely excellent spall resistance as compared with AZS refractories and high zirconia electroformed refractories, as well as high alumina electroformed refractories.
【００１４】これらの配合組成の電鋳耐火物がいかなる
機構でこのように優れた耐スポール性を発現するかにつ
いて、その詳細は不明であるが、組成中のジルコニア粒
子が一部アルミナと共晶をつくり、ジルコニア自身の変
態による膨脹収縮がコランダムの膨脹を相殺することに
より結果的に耐火物全体の膨脹を小さくしていると思わ
れる。The mechanism by which the electroformed refractory having such a composition exhibits such excellent spall resistance is unknown, but the zirconia particles in the composition are partially eutectic with alumina. It is believed that the expansion and contraction due to zirconia's own transformation offset the expansion of corundum, thereby reducing the expansion of the entire refractory.
【００１５】[0015]
【実施例】本発明の好適な実施例を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described.
【００１６】[0016]
【表１】 重量％でＡｌ2 Ｏ3 が８０〜９４％、ＺｒＯ2 が２〜１
５％、ＳｉＯ2 が０．６〜１．２％、Ｎａ2 Ｏが２〜５
％の範囲になるように表１に示すように組成を種々変化
させてアルミナ−ジルコニア質電鋳耐火物を製造した。[Table 1] Al 2 O 3 is 80 to 94% by weight%, ZrO 2 is 2-1
5%, SiO 2 is 0.6~1.2%, Na 2 O is 2-5
% Of alumina-zirconia electroformed refractories with various compositions as shown in Table 1 so as to fall within the range of%.
【００１７】溶解には上部解放式のアーク炉を用いた。
溶解後、溶解物を内寸法１００ｍｍ×２００ｍｍ×３０
０ｍｍのカーボン製鋳型に流し込み、約１分後にカーボ
ン製鋳型を取り外してアルミナ細粒中で冷却した。得ら
れた製品にはクラック、コーナースポール等の外観の欠
陥は無かった。さらに、そのようにして得られた製品に
ついて、耐スポール性、耐蝕性、発泡性等の物性試験を
行った。その結果を表２に比較例と併せて示す。For melting, an open-top type arc furnace was used.
After dissolving, the melt was sized to 100 mm x 200 mm x 30
It was poured into a 0 mm carbon mold, and after about 1 minute, the carbon mold was removed and cooled in fine alumina particles. The obtained product had no appearance defects such as cracks and corner spalls. Further, the thus obtained products were subjected to physical property tests such as spall resistance, corrosion resistance and foaming property. The results are shown in Table 2 together with Comparative Examples.
【００１８】[0018]
【表２】 次に各種物性試験の方法を示す。[Table 2] Next, methods of various physical property tests will be described.
【００１９】耐スポール性試験 各耐火物からそれぞれ２５ｍｍ×３０ｍｍ×５０ｍｍの
大きさの試験片を切り出し、この試験片を１２００℃の
炉内に入れ、３０分間保持した後、炉外に取り出し、大
気中または水中で３０分間冷却させる操作を繰り返し、
剥離が生じるまでのサイクル数をスポーリング回数とし
て耐スポール性を評価した。[0019]Spall resistance test 25mm x 30mm x 50mm from each refractory
A test piece of a size was cut out, and the test piece was heated at 1200 ° C.
Put in furnace, hold for 30 minutes, take out of furnace,
Repeat the operation of cooling in the air or water for 30 minutes,
The number of cycles until peeling occurs is defined as the number of spalling cycles.
To evaluate the spall resistance.
【００２０】耐蝕性試験 各耐火物からそれぞれ直径２０ｍｍ、長さ８０ｍｍの大
きさの試験片を切り出し、この試験片をソーダライムガ
ラスを満たした内寸法１５０ｍｍ×１２０ｍｍ×８０ｍ
ｍの東芝モノフラックス製のルツボに試験片がガラスに
浸るように設置し、１４００℃の炉内で１６８時間保持
した。加熱後、試験片を半切して侵蝕量（深さ）をノギ
スで測定して耐蝕性を評価した。 Corrosion resistance test A test piece having a diameter of 20 mm and a length of 80 mm was cut out from each refractory, and this test piece was filled with soda lime glass and had an inner size of 150 mm × 120 mm × 80 m.
The test piece was placed in a glass crucible made of TOSHIBA MONOFLUX so that the test piece was immersed in glass, and kept in a furnace at 1400 ° C. for 168 hours. After heating, the test piece was cut in half and the erosion amount (depth) was measured with a caliper to evaluate the corrosion resistance.
【００２１】発泡性試験 各耐火物からそれぞれ直径５０ｍｍ、厚さ２０ｍｍの大
きさの試験片を切り出し、試験面は平滑に研磨し、洗浄
し、乾燥する。この試験片を１２００℃の炉内に入れ、
１時間保持した後、試験片の上に内径３５ｍｍ、厚さ１
５ｍｍのアルミナ質のリングを乗せて、その中央にテス
トガラスを乗せ、２時間保持した。冷却後に、拡大鏡を
用いてガラス中に存在する泡を数えて発泡性を評価し
た。Foamability test A test piece having a diameter of 50 mm and a thickness of 20 mm is cut out from each refractory, and the test surface is polished smoothly, washed and dried. This test piece was placed in a furnace at 1200 ° C.
After holding for 1 hour, an inner diameter of 35 mm and a thickness of 1
A 5 mm alumina ring was placed, the test glass was placed in the center, and the ring was held for 2 hours. After cooling, the bubbles present in the glass were counted using a magnifying glass to evaluate the foamability.
【００２２】表１に示した実施例１〜２２は、いずれも
Ａｌ2 Ｏ3 が８０％以上の組成になっていて、ＺｒＯ2
が２〜１５％、ＳｉＯ2 が０．６〜１．２％、Ｎａ2 Ｏ
が２〜４．８％、ＣａＯが０．１〜０．２％である。そ
のような組成の各種電鋳耐火物を常法により製造した。
その結果、表２に示されているように、侵蝕率はＺｒＯ
2 添加量の増加とともに減少した。そして従来の高アル
ミナ質電鋳耐火物である比較例１〜３に比べても本発明
の各実施例は侵蝕率は小さく、耐蝕性の大きいことが認
められた。スポーリング回数は空冷で５４回以上、水冷
でも２８回以上であり、高い耐スポール性を示した。発
泡性は全般に小さく、特に実施例３，４，７〜１１，１
８が良好である。In each of Examples 1 to 22 shown in Table 1, Al 2 O 3 has a composition of 80% or more, and ZrO 2
But 2 to 15%, SiO 2 is 0.6~1.2%, Na 2 O
Is 2 to 4.8% and CaO is 0.1 to 0.2%. Various electroformed refractories having such compositions were produced by a conventional method.
As a result, as shown in Table 2, the erosion rate was ZrO
2 Decreased with increasing amount of addition. Further, it was confirmed that each of the examples of the present invention had a low erosion rate and a high corrosion resistance as compared with Comparative Examples 1 to 3 which were conventional high-alumina electroformed refractories. The number of times of spalling was 54 or more times in air cooling and 28 or more times in water cooling, indicating high spall resistance. Foamability is generally small, and in particular, Examples 3, 4, 7 to 11, 1
8 is good.
【００２３】比較例１，２，３，１３は表１に示されて
いるように従来の高アルミナ質およびＡＺＳ質の電鋳耐
火物である。表２に示すように、この種の電鋳耐火物の
スポーリング回数は多いものでも１０回であり、極端に
悪い。As shown in Table 1, Comparative Examples 1, 2, 3, and 13 are conventional high alumina and AZS electroformed refractories. As shown in Table 2, the number of times of spalling of this type of electroformed refractory is as high as 10 at most, which is extremely bad.
【００２４】比較例４，５は表１に示すようにＺｒＯ2
が１％であり、耐スポール性は表２に示すように不十分
である。In Comparative Examples 4 and 5, as shown in Table 1, ZrO 2
Is 1%, and the spall resistance is insufficient as shown in Table 2.
【００２５】比較例６〜１２は表１に示すようにＺｒＯ
2 が１５％を越えるものであり、表２に示すように侵蝕
率は少ないものの、耐スポール性および発泡性が不十分
である。In Comparative Examples 6 to 12, as shown in Table 1, ZrO
2 exceeds 15%, and as shown in Table 2, the erosion rate is small, but the spall resistance and the foaming property are insufficient.
【００２６】比較例１４〜１７は一般に耐スポール性が
電鋳耐火物より優れていると考えられる焼成耐火物であ
る。これらにおいてさえも耐スポール性は表２に示すよ
うに本発明の各実施例と同等またはやや優れている程度
である。言うまでもなく比較例１４〜１７の侵蝕性およ
び発泡性は著しく劣る。Comparative Examples 14 to 17 are fired refractories which are generally considered to have better spall resistance than electroformed refractories. Even in these, as shown in Table 2, the spall resistance is equivalent to or slightly superior to each embodiment of the present invention. Needless to say, the erosion and foaming properties of Comparative Examples 14 to 17 are remarkably inferior.
【００２７】[0027]
【発明の効果】以上述べたように本発明に係るアルミナ
−ジルコニア質電鋳耐火物はＺｒＯ2を１．５〜１５％
の範囲にすることにより従来品に比較して比重および気
孔率を大きく変化させることなく耐蝕性および発泡性を
保持しつつ耐スポール性を大きく高めることができた。
そしてＺｒＯ2 が５〜１０％の範囲にあるとき特に耐ス
ポール性が効果的であった。 ◆Alumina according to the present invention as described above, according to the present invention - zirconia electrocast refractories and ZrO 2 1.5 to 15%
With the above range, the spall resistance could be greatly increased while maintaining the corrosion resistance and the foaming property without largely changing the specific gravity and the porosity as compared with the conventional product.
And especially spalling resistance when ZrO 2 is in the range of 5-10% was effective. ◆
───────────────────────────────────────────────────── フロントページの続き (72)発明者 遠藤 茂男 東京都中央区日本橋久松町４番４号 糸 重ビル 東芝モノフラックス株式会社内 (56)参考文献 特開 昭51−89806（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C04B 35/657 C04B 35/10 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Shigeo Endo 4-4 Nihonbashi Hisamatsucho, Chuo-ku, Tokyo Itoshige Building Toshiba Monoflux Co., Ltd. (56) References JP-A-51-89806 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) C04B 35/657 C04B 35/10
Claims (2)
ＺｒＯ2 が１．５〜１５％で、その他の成分が２．７〜
６．４％であることを特徴とするアルミナ−ジルコニア
質電鋳耐火物。1. An Al 2 O 3 content of 80-94% by weight,
ZrO 2 is 1.5 to 15%, and other components are 2.7 to
An alumina-zirconia electroformed refractory having a content of 6.4%.
６〜１．２％、Ｎａ2 Ｏが２〜５％、ＣａＯが０．１〜
０．２％であることを特徴とする請求項１に記載のアル
ミナ−ジルコニア質電鋳耐火物。2. The above-mentioned other component has a SiO 2 content of 0.1%.
6~1.2%, Na 2 O is 2 to 5%, CaO is 0.1
The alumina-zirconia electroformed refractory according to claim 1, wherein the content is 0.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4150023A JP2942061B2 (en) | 1992-05-19 | 1992-05-19 | Alumina-zirconia electroformed refractories |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4150023A JP2942061B2 (en) | 1992-05-19 | 1992-05-19 | Alumina-zirconia electroformed refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05319912A JPH05319912A (en) | 1993-12-03 |
| JP2942061B2 true JP2942061B2 (en) | 1999-08-30 |
Family
ID=15487807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4150023A Expired - Lifetime JP2942061B2 (en) | 1992-05-19 | 1992-05-19 | Alumina-zirconia electroformed refractories |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2942061B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9073773B2 (en) | 2011-03-11 | 2015-07-07 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object, glass overflow forming block, and process for glass object manufacture |
| US9174874B2 (en) | 2011-03-30 | 2015-11-03 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object, glass overflow forming block, and process of forming and using the refractory object |
| US9216928B2 (en) | 2011-04-13 | 2015-12-22 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object including beta alumina and processes of making and using the same |
| US9249043B2 (en) | 2012-01-11 | 2016-02-02 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object and process of forming a glass sheet using the refractory object |
| US11814317B2 (en) | 2015-02-24 | 2023-11-14 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory article and method of making |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5706767B2 (en) * | 2010-06-17 | 2015-04-22 | Ａｇｃセラミックス株式会社 | Thermal insulation castable powder composition and thermal insulation castable using the same |
| EP3303253B1 (en) | 2015-06-01 | 2023-08-16 | Saint-Gobain Ceramics&Plastics, Inc. | Refractory articles |
-
1992
- 1992-05-19 JP JP4150023A patent/JP2942061B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9073773B2 (en) | 2011-03-11 | 2015-07-07 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object, glass overflow forming block, and process for glass object manufacture |
| US9714185B2 (en) | 2011-03-11 | 2017-07-25 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object, glass overflow forming block, and process for glass object manufacture |
| US9174874B2 (en) | 2011-03-30 | 2015-11-03 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object, glass overflow forming block, and process of forming and using the refractory object |
| US9796630B2 (en) | 2011-03-30 | 2017-10-24 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object, glass overflow forming block, and process of forming and using the refractory object |
| US9216928B2 (en) | 2011-04-13 | 2015-12-22 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object including beta alumina and processes of making and using the same |
| US9249043B2 (en) | 2012-01-11 | 2016-02-02 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object and process of forming a glass sheet using the refractory object |
| US9902653B2 (en) | 2012-01-11 | 2018-02-27 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object and process of forming a glass sheet using the refractory object |
| US10590041B2 (en) | 2012-01-11 | 2020-03-17 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object and process of forming a glass sheet using the refractory object |
| US11814317B2 (en) | 2015-02-24 | 2023-11-14 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory article and method of making |
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| Publication number | Publication date |
|---|---|
| JPH05319912A (en) | 1993-12-03 |
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