JPH10101439A - Alumina-zirconia-silica-based melt-cast refractory - Google Patents

Alumina-zirconia-silica-based melt-cast refractory

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Publication number
JPH10101439A
JPH10101439A JP8261040A JP26104096A JPH10101439A JP H10101439 A JPH10101439 A JP H10101439A JP 8261040 A JP8261040 A JP 8261040A JP 26104096 A JP26104096 A JP 26104096A JP H10101439 A JPH10101439 A JP H10101439A
Authority
JP
Japan
Prior art keywords
glass
refractory
zirconia
alumina
silica
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
JP8261040A
Other languages
Japanese (ja)
Other versions
JP3904264B2 (en
Inventor
Toshihiro Ishino
利弘 石野
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.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
Publication date
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Priority to JP26104096A priority Critical patent/JP3904264B2/en
Publication of JPH10101439A publication Critical patent/JPH10101439A/en
Application granted granted Critical
Publication of JP3904264B2 publication Critical patent/JP3904264B2/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
    • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a refractory free from oozing of glass at a high temperature or hardly causing oozing of glass at a high temperature and suitable for glass melting kiln and free from crack by containing prescribed six chemical components as chemical components of specific alumina-zirconia-silica-based melt-cast refractory. SOLUTION: This alumina-ziroconia-silica-based melt-cast refractory contains corundum crystal, butyrate crystal, and matrix glass as basic structures and contains 20-59wt.% ZrO2 , 35-70wt.% Al2 O3 , 5-12wt.% SiO2 , 0.1-0.8wt.% (Na2 O+K2 O), 0.05-0.5wt.% B2 O5 and 0.05-0.5wt.% B2 O3 on the basis of oxide as chemical components. The refractory contains 25-32wt.% Zn and 55-67wt.% Al2 O3 as one of preferable manners. The refractory is obtained by mixing ZrO2 raw material such as desilicated zirconia or zirconia sand with Al2 O3 raw material such as Bayer alumina, SiO2 raw material such as silica sand and raw materials such as P2 O5 , B2 O3 , Na2 O and K2 O in a prescribed amount, melting the resultant batch mixture, injecting the melt into a mold and annealing the melt. The melting is carried out while keeping oxidation state by a long arc method.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、アルミナ、ジルコ
ニアとマトリックスガラス相からなる溶融耐火物で、特
に高温でのマトリックスガラスの滲出の少ない溶融耐火
物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molten refractory comprising alumina, zirconia, and a matrix glass phase, and more particularly to a molten refractory with less leaching of matrix glass at high temperatures.

【０００２】[0002]

【従来の技術】溶融耐火物は、所定配合の耐火物原料を
電気炉にて完全に溶融した湯を所定形状の鋳型に流し込
み保温しながら常温まで冷却、再固化により通常得られ
るものであって、焼成、不焼成の結合耐火物とは組織、
製法とも全く異なる、耐食性の高い耐火物として広く知
られている。2. Description of the Related Art Molten refractories are usually obtained by pouring molten metal in which a refractory raw material of a predetermined composition is completely melted in an electric furnace into a mold having a predetermined shape, cooling to room temperature while keeping the temperature, and re-solidifying. , Fired, unfired bonded refractory and tissue,
It is widely known as a refractory with high corrosion resistance, which is completely different from the production method.

【０００３】本発明により得られる溶融耐火物は、この
ように一般的には電気炉で溶融した耐火原料を所望形状
に鋳込んで造られるものであるため、以下溶融鋳造耐火
物として説明するが、溶融後炉内でそのまま固化したも
の、又は粉砕して結合耐火物の骨材としても有用なもの
である。[0003] The molten refractory obtained by the present invention is generally produced by casting a refractory raw material melted in an electric furnace into a desired shape, and will be described below as a molten cast refractory. It is also useful as an aggregate of a refractory which is solidified as it is in a furnace after melting, or is pulverized to be bonded.

【０００４】このような溶融鋳造耐火物中で、アルミナ
・ジルコニア・シリカ質溶融鋳造耐火物は、一般に、Ａ
ＺＳ耐火物という名称で呼ばれ、ガラス溶解用耐火物と
して広く用いられている。[0004] Among such fused cast refractories, alumina-zirconia-siliceous fused cast refractories generally include A
It is called ZS refractory and is widely used as a glass melting refractory.

【０００５】ＡＺＳ溶融鋳造耐火物は、約８０〜８５％
（重量％、特記ないかぎり以下同じ）の結晶相とその結
晶間隙を埋めている１５〜２０％のマトリックスガラス
相からなる。結晶相は、コランダム結晶とバデライト結
晶とからなる。その組成は、市販されているもので、概
ね、ＺｒＯ2 を２８〜４１％、ＳｉＯ2 を１２〜１６
％、Ａｌ2 Ｏ3 を４５〜５２％、Ｎａ2 Ｏを１〜１．９
％程度含んでいる。[0005] AZS molten cast refractories are about 80-85%
(% By weight, the same applies hereinafter unless otherwise specified) and a 15-20% matrix glass phase filling the crystal gap. The crystal phase is composed of corundum crystals and badderite crystals. Its composition, those commercially available, generally, the ZrO 2 28 to 41%, a SiO 2 12 to 16
%, The Al 2 O 3 45 to 52%, a Na 2 O 1 to 1.9
It contains about%.

【０００６】ＺｒＯ2 は、よく知られているように、昇
温時１１５０℃付近に、降温時８５０℃付近に、単斜晶
と正方晶の相転移による変態膨張があり、異常な収縮、
膨張を示す。このマトリックスガラス相は、結晶間のク
ッションのような役割を果たし、ＡＺＳ耐火物を製造す
る際のジルコニアの正方晶から単斜晶の転移による変態
膨張による応力を吸収することにより、鋳塊を亀裂なく
製造するための重要な役割を果たす。As is well known, ZrO 2 undergoes transformation expansion due to a monoclinic and tetragonal phase transition near 1150 ° C. when the temperature rises and around 850 ° C. when the temperature falls, resulting in abnormal shrinkage,
Indicates swelling. The matrix glass phase acts as a cushion between the crystals, and absorbs the stress caused by the transformation expansion due to the cubic to monoclinic transition of zirconia in the production of AZS refractories, thereby cracking the ingot. Plays an important role in manufacturing without.

【０００７】しかし、このマトリックスガラス相は、使
用時に１４００℃以上の温度になると、耐火物の外に滲
み出す（ガラス滲出と呼ばれる）現象を示す。このガラ
ス滲出現象は、高温で、マトリックスガラス相の粘性が
低下し流動性を帯びるとともに、ＡＺＳ溶融鋳造耐火物
から高温で放出されるガスの力でもって押し出されるた
めであろうと考えられている。However, this matrix glass phase shows a phenomenon of oozing out of the refractory (called glass oozing) when the temperature becomes 1400 ° C. or more during use. It is believed that this glass leaching phenomenon is attributable to the fact that the viscosity of the matrix glass phase decreases at a high temperature and becomes fluid, and at the same time, is extruded by the force of gas released from the AZS molten cast refractory at a high temperature.

【０００８】この表面に滲出したガラスの組成は、アル
ミナ及びジルコニアに富んだ高粘性のガラスであるた
め、ガラス窯に使用した際、母ガラスに混入するとキャ
ットスクラッチやグラスノットやコードなどの母ガラス
の品質を大いに損なうガラス欠点になる。[0008] The composition of the glass leached on the surface is a high-viscosity glass rich in alumina and zirconia. Therefore, when used in a glass kiln, if mixed with the mother glass, the mother glass such as cat scratches, glass knots, cords, etc. Is a glass defect that greatly impairs the quality of the glass.

【０００９】このため、従来よりガラス滲出のないＡＺ
Ｓ溶融鋳造耐火物の開発を目指して、種々の取り組みが
なされ、種々の方法が提案されている。例えば、特公平
５−７３５０ではＦｅ2 Ｏ3 やＴｉＯ2 などの含有する
不純物の量を４００ｐｐｍ以下に制限することにより、
ガラス滲出の少ないＡＺＳ耐火物を提案している。しか
し、Ｆｅ2 Ｏ3 やＴｉＯ2 などの含有する不純物の量を
４００ｐｐｍ以下に制限することは、その原料価格が非
常に高くなることやマトリックスガラス相の量が非常に
多い場合や含有するアルカリが非常に多い場合、マトリ
ックスガラス相の粘性が非常に低下するために、高温に
加熱するとガラス滲出が生じる恐れがあり、期待される
効果が得られないと考えられる。For this reason, AZ which does not exude glass is conventionally used.
Various approaches have been made and various methods have been proposed with the aim of developing S-fused refractories. For example, in Japanese Patent Publication No. 5-7350, the amount of impurities such as Fe 2 O 3 and TiO 2 is limited to 400 ppm or less.
An AZS refractory with less glass leaching is proposed. However, limiting the amount of impurities such as Fe 2 O 3 and TiO 2 to 400 ppm or less means that the raw material price becomes extremely high, the amount of matrix glass phase is extremely large, If the amount is very large, the viscosity of the matrix glass phase is extremely reduced, so that heating to a high temperature may cause leaching of the glass, and the expected effect cannot be obtained.

【００１０】また、ガラス滲出の機構から考えて、含有
するマトリックスガラス相の量を減らすことは、その解
決策の一つと考えられるが、マトリックスガラス相は亀
裂防止に重要な役割を担っているために、単純にその量
を減少させると、亀裂が生じ、煉瓦としての機能がなく
なる。In view of the mechanism of glass leaching, reducing the amount of the matrix glass phase contained is considered as one of the solutions. However, the matrix glass phase plays an important role in preventing cracks. If the amount is simply reduced, cracks are formed and the function as a brick is lost.

【００１１】さらに、マトリックスガラス自身の粘性を
高めることも考えられ、粘性を上げるためにＮａ2 Ｏ含
有量を低減させることも考えられるが、吉木文平著「耐
火物工学」に示されているように、Ｎａ2 Ｏ含有量を低
減させると、含有したＳｉＯ2 がＡｌ2 Ｏ3 と反応して
ムライトを生成し、マトリックスガラス相が著しく低減
するとともに、ムライトが生成すると亀裂などの発生の
原因になり、耐火物本来の機能を果たさなくなる。この
ため、単純に、Ｎａ2 Ｏを低減させることだけでは、解
決にならない。Further, it is conceivable to increase the viscosity of the matrix glass itself, and it is also conceivable to reduce the Na 2 O content in order to increase the viscosity. As shown in “Refractory Engineering” by Bunki Yoshiki. Meanwhile, when the Na 2 O content is reduced, the contained SiO 2 reacts with Al 2 O 3 to generate mullite, and the matrix glass phase is significantly reduced, and when mullite is generated, cracks and the like may occur. The refractory does not fulfill its original function. Therefore, simply reducing Na 2 O does not solve the problem.

【００１２】特公昭４２−１５６０３では、アルカリ金
属酸化物を含有しない系で、Ｐ2 Ｏ5 、Ｂ2 Ｏ3 、Ｖ2
Ｏ5 などを含有させることにより、鋳塊を亀裂なく製造
できることが示されているが、Ｖ2 Ｏ5 は母ガラスに混
入すると着色の原因になり、きわめて好ましくない。ま
た、Ｐ2 Ｏ5 、Ｂ2 Ｏ3 については、アルカリ金属酸化
物が０．６５％以下の範囲においては、鋳塊を亀裂なく
製造するには、Ｐ2 Ｏ5 、Ｂ2 Ｏ3 を１．５％以上の多
量に含有させている。このような多量のＰ2 Ｏ5 、Ｂ2
Ｏ3 の含有は、マトリックスガラスの粘性を極端に下
げ、その当時は問題にされていなかったガラス滲出を生
じさせる。Japanese Patent Publication No. 42-15603 discloses a system containing no alkali metal oxide and containing P 2 O 5 , B 2 O 3 , V 2
By containing such O 5, but the ingot has been shown to be able to manufacture without cracking, V 2 O 5 is cause coloration mixed in the mother glass, extremely undesirable. As for P 2 O 5 and B 2 O 3 , in order to produce an ingot without cracking when the alkali metal oxide content is 0.65% or less, P 2 O 5 and B 2 O 3 must be 1%. It is contained in a large amount of 0.5% or more. Such a large amount of P 2 O 5 , B 2
The inclusion of O 3 drastically reduces the viscosity of the matrix glass, causing glass bleeding which was not at the time.

【００１３】また、Ｐ2 Ｏ5 、Ｂ2 Ｏ3 の含有量の少な
い場合には、アルカリ金属酸化物を１％以上含有させて
おり、このような組成物では、前述と同様にマトリック
スガラス相の粘性が低くなるためにガラス成分の滲出量
が多くなり、特に高温でのガラス窯用としての使用には
適さない。このように、ガラス粘性を大きく左右する非
常に重要なアルカリ金属酸化物と他の成分との関係につ
いて、充分に解明されていない。When the content of P 2 O 5 and B 2 O 3 is low, the content of the alkali metal oxide is 1% or more. Because of the low viscosity, the amount of leaching of the glass component increases, and it is not particularly suitable for use in glass kilns at high temperatures. As described above, the relationship between a very important alkali metal oxide which greatly affects the viscosity of glass and other components has not been sufficiently elucidated.

【００１４】[0014]

【発明が解決しようとする課題】本発明は、従来のＡＺ
Ｓ溶融鋳造耐火物が有する高温でのガラス滲出がない又
は少ない、ガラス溶融窯用に適した亀裂のないＡＺＳ溶
融鋳造耐火物を提供しようとするものである。SUMMARY OF THE INVENTION The present invention relates to a conventional AZ
An object of the present invention is to provide a crack-free AZS molten cast refractory suitable for use in a glass melting furnace, which has no or little glass leaching at a high temperature of the S molten cast refractory.

【００１５】[0015]

【課題を解決するための手段】本発明は、これらの点に
鑑み、ＡＺＳ溶融鋳造耐火物の高温でのガラス滲出を低
減させるために、ガラス滲出が生じる主原因であるマト
リックスガラス量を低減させるにあたり、ＡＺＳ溶融鋳
造耐火物の製造時に亀裂が発生せず、溶融ガラスに対す
る耐食性や砂利を発生させたり溶融ガラス素地を着色さ
せるような耐素地汚染抵抗性を大きく損なうことなく、
そのマトリックスガラス相の主たる組成を検討すること
により、高温時のガラス滲出がない又は少ない、ガラス
溶融窯用に適したＡＺＳ溶融鋳造耐火物を亀裂なく製造
することに成功したものである。SUMMARY OF THE INVENTION In view of the above, the present invention reduces the amount of matrix glass, which is a main cause of glass leaching, in order to reduce the leaching of AZS molten cast refractories at high temperatures. In the production of AZS molten cast refractories, cracks do not occur at the time of production, without greatly impairing the corrosion resistance to the molten glass and the resistance to soil contamination such as generating gravel or coloring the molten glass substrate,
By examining the main composition of the matrix glass phase, the inventors succeeded in producing an AZS molten cast refractory having no or little glass leaching at high temperature and suitable for a glass melting furnace without cracking.

【００１６】すなわち本発明は、コランダム結晶、バデ
ライト結晶及びマトリックスガラスを基本組織とするア
ルミナ・ジルコニア・シリカ質溶融耐火物であって、化
学成分として、酸化物を基準とする重量％で、 ＺｒＯ2 ２０〜５９％、 Ａｌ2 Ｏ3 ３５〜７０％、 ＳｉＯ2 ５〜１２％、 Ｎａ2 Ｏ＋Ｋ2 Ｏ ０．１〜０．８％、 Ｐ2 Ｏ5 ０．０５〜０．５％、 Ｂ2 Ｏ3 ０．０５〜０．５％、 を含有することを特徴とするアルミナ・ジルコニア・シ
リカ質溶融耐火物を提供する。That is, the present invention relates to an alumina-zirconia-silica fused refractory having a basic structure of corundum crystal, baddelite crystal and matrix glass, wherein ZrO 2 is used as a chemical component in a weight% based on oxide. 20~59%, Al 2 O 3 35~70 %, SiO 2 5~12%, Na 2 O + K 2 O 0.1~0.8%, P 2 O 5 0.05~0.5%, B 2 O 3 0.05 to 0.5%, to provide an alumina-zirconia-silica fusion refractory characterized by containing.

【００１７】本発明耐火物の好ましい態様の１つは、化
学成分として、酸化物を基準とする重量％で、ＺｒＯ2
を２５〜３２％、Ａｌ2 Ｏ3 を５５〜６７％含む。本発
明の他の好ましい態様の１つは、化学成分として、酸化
物を基準とする重量％で、Ｎａ2 ＯとＫ2 Ｏのいずれを
も０．１〜０．５％かつ合量で０．６％以下含む。One of the preferred embodiments of the refractory of the present invention is that, as a chemical component, ZrO 2 is contained in a weight% based on the oxide.
The 25 to 32%, including Al 2 O 3 55~67%. One other preferred embodiment of the present invention, as chemical components, in weight percent based on the oxides, 0.1 to 0.5% and the total amount any of Na 2 O and K 2 O 0 0.6% or less.

【００１８】本発明耐火物は、後述する理由により厳密
な化学分析値により制御されることが必要であり、耐火
物の組織としては、バデライトとコランダムの結晶粒界
をＰ2 Ｏ5 、Ｂ2 Ｏ3 、Ｎａ2 Ｏ、Ｋ2 Ｏを重要な成分
とした、少量であるが軟らかいマトリックスガラス成分
が充填された緻密かつ均質な組織からなる。本発明耐火
物のより好ましい組成範囲は表１のとおりである。It is necessary that the refractory of the present invention be controlled by strict chemical analysis values for the reasons described below. The refractory has a structure in which the grain boundaries of badderite and corundum are composed of P 2 O 5 and B 2. It consists of a dense and homogeneous structure filled with a small but soft matrix glass component containing O 3 , Na 2 O and K 2 O as important components. The more preferable composition range of the refractory of the present invention is as shown in Table 1.

【００１９】[0019]

【表１】 [Table 1]

【００２０】次に各成分の好ましい範囲と理由を説明す
る。ＺｒＯ2 成分はＡＺＳ溶融鋳造耐火物としては、そ
のガラス素地に対する耐食性という観点からは多い方が
よいが、本発明では、高温でのガラス滲出量を少なくす
るために、マトリックスガラス相の量が少なくなってい
るので、ＺｒＯ2 含有量が多くなると、ＺｒＯ2 の変態
膨張量とそれに伴う応力が大きくなりすぎ、マトリック
スガラス相が体積変化を吸収しきれなくなるために、鋳
塊を亀裂なく製造するのが困難になる。また、少なすぎ
るとガラス素地に対する耐食性が乏しくなる。Next, the preferred ranges and reasons for each component will be described. The ZrO 2 component, as an AZS fusion-cast refractory, is preferably large from the viewpoint of corrosion resistance to the glass substrate, but in the present invention, the amount of the matrix glass phase is reduced in order to reduce the amount of glass exudation at high temperatures. Therefore, when the ZrO 2 content increases, the transformation expansion amount of ZrO 2 and the accompanying stress become too large, and the matrix glass phase cannot absorb the volume change. Becomes difficult. On the other hand, if the amount is too small, the corrosion resistance to the glass substrate becomes poor.

【００２１】Ａｌ2 Ｏ3 成分は、ＡＺＳ溶融鋳造耐火物
の結晶構造を構成する成分中で、ＺｒＯ2 と並んで重要
な成分で、コランダム結晶を構成し、溶融ガラスに対し
てＺｒＯ2 の次に強い耐食性を示すとともに、ＺｒＯ2
のような変態膨張を示さない。その量が７０％超である
と、マトリックスガラス相の量が少なくなるとともにム
ライト生成を起こしやすくするために鋳塊を亀裂なく製
造することができなくなる。少なすぎるとマトリックス
ガラス相の量が多くなるために、従来のガラス滲出特性
と変わらなくなる。[0021] Al 2 O 3 component is a component which constitutes the crystal structure of the AZS fusion cast refractories, a critical component along with ZrO 2, constitutes corundum crystals, of ZrO 2 to the molten glass following In addition to exhibiting strong corrosion resistance, ZrO 2
Does not show the transformation expansion like If the amount is more than 70%, the amount of the matrix glass phase is reduced and the ingot cannot be produced without cracks because mullite is easily generated. If the amount is too small, the amount of the matrix glass phase increases, so that it does not differ from the conventional glass exudation characteristics.

【００２２】ＳｉＯ2 成分は、マトリックスガラス相を
構成する主成分で特性を左右する重要な成分である。５
％未満であると、マトリックスガラス相量が少なくなっ
てマトリックスガラス相がＺｒＯ2 の体積変化を吸収し
きれなくなるために、鋳塊を亀裂なくなる製造するのが
困難になる。１２％超であると、マトリックスガラス相
の量が多くなるために、従来のガラス滲出特性と変わら
なくなる。The SiO 2 component is a main component constituting the matrix glass phase and is an important component that determines the properties. 5
%, The amount of the matrix glass phase is so small that the matrix glass phase cannot absorb the volume change of ZrO 2 , so that it is difficult to manufacture the ingot without cracking. If it exceeds 12%, the amount of the matrix glass phase increases, so that it does not differ from the conventional glass exudation characteristics.

【００２３】Ｎａ2 ＯとＫ2 Ｏのアルカリ成分は、マト
リックスガラス相の温度と粘性の関係を調整する重要な
成分である。その含有量が合量で０．８％超であるとガ
ラス滲出が従来のものと変わらなくなる。Ｎａ2 ＯとＫ
2 Ｏは単独で用いてもよいが、両者を共存させることに
より、ガラス粘性を下げることなくガラス化範囲が広が
るために、従来いわれているアルカリ含有量が少ないと
ころでもムライトの生成が起こりにくくなる。このた
め、より好ましくは、Ｎａ2 ＯとＫ2 Ｏはそれぞれ０．
１〜０．５％含みかつその合量が０．６％以下であるこ
とが、そのガラス滲出特性の点から好ましい。一方、そ
の合量が、０．１％未満であると、マトリックスガラス
相の粘性が高くなりすぎると同時にムライトを生成させ
るために、鋳塊を亀裂なく製造することができない。The alkaline components of Na 2 O and K 2 O are important components for adjusting the relationship between the temperature and the viscosity of the matrix glass phase. If the total content is more than 0.8%, glass ooze will not be different from the conventional one. Na 2 O and K
Although 2 O may be used alone, the coexistence of the two allows the vitrification range to be widened without lowering the glass viscosity, so that the generation of mullite is less likely to occur even in the place where the alkali content is conventionally low. . For this reason, more preferably, each of Na 2 O and K 2 O is 0.1%.
It is preferable that it contains 1 to 0.5% and the total amount is 0.6% or less from the viewpoint of the glass exudation characteristics. On the other hand, if the total amount is less than 0.1%, the viscosity of the matrix glass phase becomes too high, and at the same time, mullite is generated, so that an ingot cannot be produced without cracks.

【００２４】このアルカリ含有量の少ないところでのガ
ラス化範囲を広げる点において、次に述べる、Ｐ2 Ｏ
5 、Ｂ2 Ｏ3 成分が、非常に重要な役割を果たし、必須
成分である。In order to widen the vitrification range where the alkali content is low, P 2 O
5 , B 2 O 3 component plays a very important role and is an essential component.

【００２５】Ｐ2 Ｏ5 成分は、マトリックスガラス成分
として、いわゆる軟らかいガラスを形成しうるものとし
て、少量のマトリックスガラスでも亀裂なく鋳塊を製造
するのに効果があり、また、得られる鋳造物をガラス溶
融窯用の耐火物として使用してもガラスへの砂利の発生
又は着色などの恐れがない。The P 2 O 5 component, as a matrix glass component, is capable of forming a so-called soft glass, and is effective for producing an ingot without cracking even with a small amount of matrix glass. Even when used as a refractory for a glass melting furnace, there is no danger of generation of gravel on the glass or coloring.

【００２６】Ｂ2 Ｏ3 成分は、アルカリ金属酸化物の代
わりに、Ｐ2 Ｏ5 と共働して軟らかいガラスを形成しう
るものとして、少量のマトリックスガラスでも亀裂なく
鋳塊を製造するのに効果がある。The B 2 O 3 component is capable of forming a soft glass in cooperation with P 2 O 5 instead of the alkali metal oxide, so that even a small amount of matrix glass can be used to produce an ingot without cracking. effective.

【００２７】Ｐ2 Ｏ5 、Ｂ2 Ｏ3 それぞれの含有量は、
０．５％超であるとガラス粘性が軟らかくなりすぎるた
めか、ガラス滲出が従来のものと変わらなくなる。ま
た、０．０５％未満では、少量のアルカリ成分のマトリ
ックスガラス相の粘性を軟らかくできないために、鋳塊
を亀裂なく製造することができなくなる。The content of each of P 2 O 5 and B 2 O 3 is as follows:
If it exceeds 0.5%, the glass ooze will not be different from the conventional one, probably because the glass viscosity becomes too soft. On the other hand, if it is less than 0.05%, the viscosity of the matrix glass phase of a small amount of the alkali component cannot be softened, so that the ingot cannot be produced without cracks.

【００２８】その他の成分については、本発明の目的効
果を損なわない程度において若干含まれていてもよい
が、可及的に少量に制限することが望ましい。例えば、
Ｆｅ2 Ｏ3 、ＴｉＯ2 、ＣａＯ、ＭｇＯは、工業原料の
不純物として混入するもので、できる限り少ない方がよ
いが、工業的な範囲としてその合量で０．０５〜０．４
％の範囲で含有されてもその特性に影響を及ぼさない。Other components may be contained to some extent so as not to impair the effects of the present invention, but it is desirable to limit the amount to as small as possible. For example,
Fe 2 O 3 , TiO 2 , CaO and MgO are mixed as impurities of industrial raw materials, and the smaller the better, the better.
% Does not affect its properties.

【００２９】[0029]

【実施例】脱珪ジルコニアやジルコンサンドなどのＺｒ
Ｏ2 原料とバイヤーアルミナなどのＡｌ2 Ｏ3 原料と珪
砂などのＳｉＯ2 原料とＰ2 Ｏ5 、Ｂ2 Ｏ3 、Ｎａ2
Ｏ、Ｋ2 Ｏなどの原料となるものを、所定量に調整した
バッチ混合物を５００ＫＶＡ単相アーク電気炉に装入
し、溶融温度２０００℃前後で完全に溶融した。EXAMPLE Zr such as desiliconized zirconia and zircon sand
O 2 raw material, Al 2 O 3 raw material such as Bayer alumina, SiO 2 raw material such as silica sand, P 2 O 5 , B 2 O 3 , Na 2
A batch mixture prepared by adjusting raw materials such as O and K 2 O to a predetermined amount was charged into a 500 KVA single-phase electric arc furnace, and was completely melted at a melting temperature of about 2000 ° C.

【００３０】この湯を内容積１３０ｍｍ×１６０ｍｍ×
３５０ｍｍの周囲をシリカ質の中空球やバイヤーアルミ
ナからなる保温材で囲まれた砂で作った鋳型に注入して
鋳造し、室温付近まで徐冷した。溶解は従来方法と同様
に、電極を湯面からあげるいわゆるロングアーク法で、
溶融途中に酸素を吹き込むなどを行い、できるだけ溶融
物の酸化状態を保つようにした。This hot water is stored in an inner volume of 130 mm × 160 mm ×
The circumference of 350 mm was cast into a mold made of sand surrounded by hollow materials made of siliceous hollow spheres and Bayer alumina, cast and cast, and gradually cooled to around room temperature. Melting is performed by the so-called long arc method in which the electrode is raised from the surface of the molten metal, as in the conventional method.
Oxygen was blown during the melting to keep the oxidized state of the melt as much as possible.

【００３１】得られた鋳造物の化学分析値（単位：重量
％）を表２〜５の上段に、諸性質を表２〜５の下段に示
した。例１〜１１は比較例、例１２〜２１は実施例であ
る。なお、得られた鋳造物はいずれもコランダム結晶、
バデライト結晶及びマトリックスガラスを基本組織とし
ていた。The chemical analysis values (unit:% by weight) of the obtained castings are shown in the upper part of Tables 2 to 5, and various properties are shown in the lower part of Tables 2 to 5. Examples 1 to 11 are Comparative Examples, and Examples 12 to 21 are Examples. The obtained castings were all corundum crystals,
Baderite crystals and matrix glass were the basic structures.

【００３２】ガラス滲出の試験は次のようにして行っ
た。直径３０ｍｍ、高さ３０ｍｍの円柱の試料をダイヤ
モンドコアドリルで切りだし、アルキメデス法にて乾燥
重量（Ｗ1 ）、水中重量（Ｗ2 ）を測定する。この試料
を電気炉にて１５００℃で１６時間保持した後、炉外に
取り出し、炉外で自然放冷する。この試料を再度、アル
キメデス法にて乾燥重量（Ｗ3 ）、水中重量（Ｗ4 ）を
測定する。このようにして得られた測定値を使い、次式
により算出したガラス滲出量（単位：体積％）を表２〜
５のＢ欄に示す。上記試験後の外観観察によるガラス滲
出の有無についても表２〜５のＡ欄に示す。また亀裂の
有無を表２〜５のＣ欄に示す。なお、Ｃ欄において
「＊」は「微細亀裂あり、ただし使用上は問題のない表
層のヘアー亀裂である」を示す。 ガラス滲出量＝｛（Ｗ3 −Ｗ4 ）／（Ｗ1 −Ｗ2 ）−
１｝×１００％The test for glass leaching was performed as follows. A cylindrical sample having a diameter of 30 mm and a height of 30 mm is cut out with a diamond core drill, and the dry weight (W 1 ) and the weight in water (W 2 ) are measured by the Archimedes method. After holding this sample at 1500 ° C. for 16 hours in an electric furnace, it is taken out of the furnace and allowed to cool naturally outside the furnace. The dry weight (W 3 ) and the underwater weight (W 4 ) of this sample are measured again by the Archimedes method. Using the measured values obtained in this way, the amount of glass leaching (unit: volume%) calculated by the following equation is shown in Tables 2 and 3.
The results are shown in column B of FIG. The presence or absence of glass exudation by appearance observation after the above test is also shown in column A of Tables 2-5. The presence or absence of cracks is shown in column C of Tables 2-5. In column C, "*" indicates "fine cracks, but hair cracks on the surface layer which have no problem in use". Glass exudation amount = ｛(W 3 −W 4 ) / (W 1 −W 2 ) −
1｝ × 100%

【００３３】[0033]

【表２】 [Table 2]

【００３４】[0034]

【表３】 [Table 3]

【００３５】[0035]

【表４】 [Table 4]

【００３６】[0036]

【表５】 [Table 5]

【００３７】[0037]

【発明の効果】このように本発明耐火物は亀裂がなく、
従来使用されているＡＺＳ溶融鋳造耐火物と比較して、
高温でのガラス滲出が少ない又は生じないために、例え
ば、ガラス窯の溶解槽の上部構造に使用した場合、高温
での滲出物が母ガラスに混入することによるグラスノッ
トなどのガラス欠点を発生させにくいので、ガラス窯用
耐火物として非常に優れる。As described above, the refractory of the present invention has no crack,
Compared to the conventionally used AZS fusion cast refractories,
Because glass exudation at high temperatures is small or not generated, for example, when used in the upper structure of a melting furnace of a glass kiln, glass exudates at high temperatures cause glass defects such as glass knots due to being mixed into the mother glass. Because it is difficult, it is very excellent as a refractory for glass kilns.

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】コランダム結晶、バデライト結晶及びマト
リックスガラスを基本組織とするアルミナ・ジルコニア
・シリカ質溶融耐火物であって、化学成分として、酸化
物を基準とする重量％で、 ＺｒＯ2 ２０〜５９％、 Ａｌ2 Ｏ3 ３５〜７０％、 ＳｉＯ2 ５〜１２％、 Ｎａ2 Ｏ＋Ｋ2 Ｏ ０．１〜０．８％、 Ｐ2 Ｏ5 ０．０５〜０．５％、 Ｂ2 Ｏ3 ０．０５〜０．５％、 を含有することを特徴とするアルミナ・ジルコニア・シ
リカ質溶融耐火物。An alumina-zirconia-silica fused refractory having a basic structure of corundum crystal, baddelite crystal and matrix glass, wherein ZrO 2 is 20 to 59% by weight as a chemical component based on an oxide. %, Al 2 O 3 35 to 70%, SiO 2 5 to 12%, Na 2 O + K 2 O 0.1 to 0.8%, P 2 O 5 0.05 to 0.5%, B 2 O 30 Alumina / zirconia / silica fused refractory, characterized by containing 0.05 to 0.5%. 【請求項２】化学成分として、酸化物を基準とする重量
％で、ＺｒＯ2 を２５〜３２％、Ａｌ2 Ｏ3 を５５〜６
８％含有する請求項１記載のアルミナ・ジルコニア・シ
リカ質溶融耐火物。As wherein chemical components, in weight percent based on the oxides, the ZrO 2 25 to 32%, the Al 2 O 3 fifty-five to six
The alumina-zirconia-silica-based fused refractory according to claim 1, which contains 8%. 【請求項３】化学成分として、酸化物を基準とする重量
％で、Ｎａ2 ＯとＫ2 Ｏをそれぞれ０．１〜０．５％か
つ合量で０．６％以下含有する請求項１又は２記載のア
ルミナ・ジルコニア・シリカ質溶融耐火物。3. The chemical composition according to claim 1, wherein Na 2 O and K 2 O are each contained in an amount of 0.1 to 0.5% and a total amount of 0.6% or less in terms of% by weight based on the oxide. Or the alumina-zirconia-silica-based fused refractory according to 2 above. 【請求項４】化学成分として、酸化物を基準とする重量
％で、Ｆｅ2 Ｏ3 ＋ＴｉＯ2 ＋ＣａＯ＋ＭｇＯを０．０
５〜０．４％含有する請求項１、２又は３記載のアルミ
ナ・ジルコニア・シリカ質溶融耐火物。As wherein chemical components, in weight percent based on the oxides, the Fe 2 O 3 + TiO 2 + CaO + MgO 0.0
4. The alumina-zirconia-silica fused refractory according to claim 1, which contains 5 to 0.4%.
JP26104096A 1996-10-01 1996-10-01 Alumina / zirconia / silica molten refractory Expired - Lifetime JP3904264B2 (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6158248A (en) * 1998-02-26 2000-12-12 Asahi Glass Company Ltd. Fused-cast-alumina-zirconia-silica refractory, methods of making it and glass melting furnace employing it
JP2007504088A (en) * 2003-09-01 2007-03-01 サン−ゴバン・サントル デゥ ルシェルシュ エ デチューデ・ウロペアン Green component for manufacturing sintered refractory products with improved bubble generation behavior
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JP2009196886A (en) * 2001-03-23 2009-09-03 Vitro Global Sa Method and system for feeding and burning pulverized fuel in glass melting furnace, and burner for use in the same
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US6158248A (en) * 1998-02-26 2000-12-12 Asahi Glass Company Ltd. Fused-cast-alumina-zirconia-silica refractory, methods of making it and glass melting furnace employing it
JP2009196886A (en) * 2001-03-23 2009-09-03 Vitro Global Sa Method and system for feeding and burning pulverized fuel in glass melting furnace, and burner for use in the same
JP2007504088A (en) * 2003-09-01 2007-03-01 サン−ゴバン・サントル デゥ ルシェルシュ エ デチューデ・ウロペアン Green component for manufacturing sintered refractory products with improved bubble generation behavior
JP2008513328A (en) * 2004-09-20 2008-05-01 サン−ゴベン・セントル・ドゥ・レシェルシェ・エ・デチュード・ユーロペアン AZS products with reduced leaching
DE112009000274T5 (en) 2008-01-30 2011-02-10 Krosakiharima Corp., Kitakyushu-shi Refractory zirconia-mullite raw material and plate-shaped brick
US8138109B2 (en) 2008-01-30 2012-03-20 Krosakiharima Corporation Zirconia-mullite refractory raw material and a plate brick
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US10000417B2 (en) 2012-08-24 2018-06-19 Refel S.P.A. Fused cast refractory material based on aluminium oxide, zirconium dioxide and silicon dioxide, and use of such a material
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