JP2000302560A - Cast refractory containing zirconia in high content - Google Patents
Cast refractory containing zirconia in high contentInfo
- Publication number
- JP2000302560A JP2000302560A JP11114765A JP11476599A JP2000302560A JP 2000302560 A JP2000302560 A JP 2000302560A JP 11114765 A JP11114765 A JP 11114765A JP 11476599 A JP11476599 A JP 11476599A JP 2000302560 A JP2000302560 A JP 2000302560A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- content
- glass
- cast refractory
- high zirconia
- 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
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000005187 foaming Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000011819 refractory material Substances 0.000 claims description 12
- 239000006060 molten glass Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 27
- 230000035939 shock Effects 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 229910011255 B2O3 Inorganic materials 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はガラス溶融炉に適し
た高ジルコニア鋳造耐火物に関し、特に熱衝撃に対して
安定であり、溶融ガラスに対する発泡性が低い高ジルコ
ニア鋳造耐火物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high zirconia cast refractory suitable for a glass melting furnace, and more particularly to a high zirconia cast refractory which is stable against thermal shock and has a low foaming property for molten glass.
【０００２】[0002]
【従来の技術】鋳造耐火物は、原料を溶融し、溶融物を
所定形状の鋳型に流し込み、これを徐々に冷却して製造
される。従って、焼成耐火物とは、組織、製法とも異な
る耐火物として知られている。2. Description of the Related Art Cast refractories are produced by melting a raw material, pouring the molten product into a mold having a predetermined shape, and gradually cooling the molten product. Therefore, the fired refractory is known as a refractory having a different structure and a different production method.
【０００３】このような鋳造耐火物の中で、ジルコニア
を多く含む高ジルコニア鋳造耐火物は、ジルコニアの結
晶と僅かのガラス相からなり、溶融ガラスに対する耐食
性に、極めて優れており、ガラス溶融炉に広く用いられ
ている。[0003] Among such cast refractories, high zirconia cast refractories containing a large amount of zirconia are composed of zirconia crystals and a small amount of glass phase, and are extremely excellent in corrosion resistance to molten glass. Widely used.
【０００４】しかしながら、高ジルコニア鋳造耐火物
は、熱衝撃に弱く、ガラスに泡を発生させる欠点があっ
た。[0004] However, high zirconia cast refractories are susceptible to thermal shock and have the disadvantage of generating bubbles in the glass.
【０００５】このため、これまでにも種々の改良がなさ
れた。例えば、特公平４−４２７１号公報では、原料中
に含まれるＦｅやＣｕなどを少なくすることによって、
発泡性を改善した高ジルコニア鋳造耐火物が提案されて
いる。また、特開平６−１８３８３２号公報では、Ｍｇ
Ｏを加えることによって、熱衝撃性及び発泡性を改善し
ている。For this reason, various improvements have been made so far. For example, Japanese Patent Publication No. 4-4271 discloses that by reducing Fe, Cu, and the like contained in a raw material,
High zirconia cast refractories with improved foamability have been proposed. In Japanese Patent Application Laid-Open No. 6-183832, Mg
By adding O, the thermal shock resistance and the foaming property are improved.
【０００６】[0006]
【発明が解決しようとする課題】ジルコニアは、溶融し
た際に、酸素が理論値より少ない不飽和酸化物になりや
すく、強い還元性の組成になる。また、高ジルコニア鋳
造耐火物の中には、不純物として含まれるＦｅ、Ｃｕや
Ｃｒなどが還元されて金属として存在している。これら
の理由により、高ジルコニア鋳造耐火物は、溶融ガラス
に泡を発生しやすい。When zirconia is melted, oxygen tends to become an unsaturated oxide containing less oxygen than the theoretical value, resulting in a strong reducing composition. Further, in the high zirconia cast refractories, Fe, Cu, Cr, etc., which are contained as impurities, are reduced and exist as metals. For these reasons, high zirconia cast refractories are prone to bubbles in the molten glass.
【０００７】この対策として、高ジルコニア鋳造耐火物
を製造する際に、極力酸化状態を維持して原料を溶融し
たり、溶融物に酸素を吹き込んで酸化させていた。しか
し、これらの方法では、溶融ガラスの発泡を抑制するに
は、不十分であった。As a countermeasure, when producing a high zirconia cast refractory, a raw material is melted while maintaining an oxidized state as much as possible, or oxygen is blown into the molten material to oxidize it. However, these methods were insufficient to suppress the foaming of the molten glass.
【０００８】また、特公平４−４２７１号公報の方法で
は、原料の価格が高く、製品が高価なものになる。In the method disclosed in Japanese Patent Publication No. 4-4271, the cost of raw materials is high and the product is expensive.
【０００９】さらに、特開平６−１８３８３２号公報の
方法では、アルミノシリケートガラスなどのアルカリ金
属酸化物の少ないガラスには有効であるが、ＴＶブラウ
ン管パネル用ガラス、ＰＤＰ（プラズマディスプレイ）
ガラスなどアルカリ金属酸化物を多く合むガラスには、
効果が得られない。Furthermore, the method disclosed in Japanese Patent Application Laid-Open No. 6-183832 is effective for glass containing a small amount of alkali metal oxide such as aluminosilicate glass, but it is effective for glass for TV cathode-ray tube panels and PDP (plasma display).
For glass containing a large amount of alkali metal oxides such as glass,
No effect.
【００１０】このため、実際には、ガラス溶融炉の築炉
が終了し、熱上げの際に、炉の空焚きをして、ジルコニ
アを飽和酸化物とし、Ｆｅ、ＣｕやＣｒなどの金属を酸
化物にした後に、ガラス原料を投入することが多く行わ
れている。[0010] Therefore, in practice, the furnace of the glass melting furnace is completed, and when heating is performed, the furnace is emptied to convert zirconia into a saturated oxide and to remove metals such as Fe, Cu and Cr. After being converted to an oxide, a glass raw material is often charged.
【００１１】この様な従来技術の問題点に鑑み、本発明
は、十分な耐熱衝撃性と、各種溶融ガラスに対し低い発
泡性を有する高ジルコニア鋳造耐火物を提供することを
目的とする。In view of such problems of the prior art, an object of the present invention is to provide a high zirconia cast refractory having sufficient thermal shock resistance and low foaming properties for various molten glasses.
【００１２】[0012]
【課題を解決するための手段】本発明の解決手段は、前
掲の請求項１〜３に記載の高ジルコニア鋳造耐火物であ
る。The solution of the present invention is a high zirconia cast refractory according to the first to third aspects of the present invention.
【００１３】[0013]
【発明の実施の形態】本発明は、Ｆｅ2Ｏ3、ＣｕＯ及び
Ｃｒ2Ｏ3の合計含有量を０．２（好ましくは０．１５）
重量％以下とし、Ｂ2Ｏ3を０．０５〜０．３（好ましく
は０．０５〜０．１５）重量％とし、Ｐ2Ｏ5を実質的に
ゼロ％にする点に大きな特徴を有する。BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, the total content of Fe 2 O 3 , CuO and Cr 2 O 3 is 0.2 (preferably 0.15).
And wt% or less, the B 2 O 3 and 0.05 to 0.3 (preferably 0.05 to 0.15)% by weight, has a great feature in that to substantially zero% of P 2 O 5 .
【００１４】まず、本発明の前掲となる成分を説明す
る。First, the above-mentioned components of the present invention will be described.
【００１５】ＺｒＯ2の含有量は、８６〜９６重量％、
好ましくは８８〜９５重量％であ る。ＺｒＯ2が９６
重量％よりも多過ぎると、製作の際に亀裂を発生し、８
６重量％よりも少な過ぎると、耐食性が劣る。The content of ZrO 2 is 86 to 96% by weight,
Preferably it is 88 to 95% by weight. 96 ZrO 2
If the content is too high, cracks will occur during production, and
If the amount is less than 6% by weight, the corrosion resistance is poor.
【００１６】ＳｉＯ2の含有量は、３〜１０重量％、好
ましくは３〜８．５重量％である。ＳｉＯ2はガラス相
を形成するための必須成分である。３重量％よりも少な
い と、ガラス相を形成できない。１０重量％よりも多
いと、耐食性が劣ると共に、高温荷重下でのガラス相の
滲出が増加する。The content of SiO 2 is 3 to 10% by weight, preferably 3 to 8.5% by weight. SiO 2 is an essential component for forming a glass phase. If it is less than 3% by weight, a glass phase cannot be formed. If the content is more than 10% by weight, corrosion resistance is deteriorated, and exudation of the glass phase under a high temperature load increases.
【００１７】Ａｌ2Ｏ3の含有量は、０．５〜２．０重量
％、好ましくは０．８〜１．５重量％である。Ａｌ2Ｏ3
は溶融物を流れ易くする。０．５重量％よりも少ない場
合は、この働きが小さい。２．０重量％よりも多い場合
は、安定したガラス相が得られない。The content of Al 2 O 3 is 0.5 to 2.0% by weight, preferably 0.8 to 1.5% by weight. Al 2 O 3
Facilitates the flow of the melt. When the amount is less than 0.5% by weight, this function is small. If it is more than 2.0% by weight, a stable glass phase cannot be obtained.
【００１８】Ｎａ2Ｏの含有量は、０．０５〜３重量
％、好ましくは０．０５〜２重量％である。Ｎａ2Ｏ
は、鋳造耐火物の酸化を促進して、発泡を抑制する働き
がある。しかし、３．０重量％よりも多すぎると、ガラ
ス相の膨張係数が大きくなって、鋳造物に亀裂を生じ
る。The content of Na 2 O is 0.05 to 3% by weight, preferably 0.05 to 2 % by weight. Na 2 O
Has the function of promoting oxidation of the cast refractory and suppressing foaming. However, if the content is more than 3.0% by weight, the expansion coefficient of the glass phase increases, and the casting is cracked.
【００１９】本発明は、前述のような成分の組み合わせ
を前提として改良を加えて、Ｂ2Ｏ3の含有量と、Ｆｅ2
Ｏ3、ＣｕＯ及びＣｒ2Ｏ3の合計と、Ｐ2Ｏ5の含有量と
をうまく組み合わせて、従来の技術からは推測できない
顕著な作用効果を奏することを可能としたものである。According to the present invention, the content of B 2 O 3 and the content of Fe 2
By combining the total of O 3 , CuO, and Cr 2 O 3 with the content of P 2 O 5 , it is possible to achieve a remarkable effect that cannot be estimated from the prior art.
【００２０】この点について、以下説明する。This will be described below.
【００２１】Ｆｅ2Ｏ3、ＣｕＯ及びＣｒ2Ｏ3の合計の含
有量は、０．２重量％以下である。好ましくは、０．１
５重量％以下である。特にＣｒ2Ｏ3の含有量は０．０５
重量％以下が好ましい。これらの酸化物は、酸化還元な
どの雰囲気によって容易にイオン価数が変わり、酸素を
放出したり、取り込んだりすることから、ジルコニア不
飽和酸化物の酸化を抑制する。特に、Ｃｒ元素は、この
性質が顕著である。さらに、Ｂ2Ｏ3が共存すると、この
性質は一層顕著となる。この理由により、Ｆｅ 2Ｏ3とＣ
ｕＯとＣｒ2Ｏ3の合計量は、０．２重量％以下とするの
が良い。FeTwoOThree, CuO and CrTwoOThreeIncluding the sum of
The weight is at most 0.2% by weight. Preferably, 0.1
5% by weight or less. Especially CrTwoOThreeContent is 0.05
% By weight or less is preferred. These oxides are redox
The ionic valence changes easily depending on which atmosphere
Zirconia
Suppresses oxidation of saturated oxides. In particular, the Cr element
The properties are remarkable. Further, BTwoOThreeCoexist, this
The properties become more pronounced. For this reason, Fe TwoOThreeAnd C
uO and CrTwoOThreeThe total amount of
Is good.
【００２２】Ｂ2Ｏ3の含有量は、０．０５〜０．３重量
％である。好ましくは、０．０５〜０．１５重量％であ
る。Ｂ2Ｏ3はガラス相の膨張係数を小さくし、昇温時の
剥離を防止し、製品に引き裂け亀裂が生じるのを防止す
るなどの重要な役割を持っている。０．０５重量％より
も少ないと、この働きがない。しかし、０．３重量％よ
りも多過ぎると、ガラス相の粘性が高くなり、酸化を抑
制して、発泡を促進させる。この性質は、Ｆｅ2Ｏ3、Ｃ
ｕＯ及びＣｒ2Ｏ3らと共存すると、一層顕著となる。The content of B 2 O 3 is 0.05 to 0.3% by weight. Preferably, it is 0.05 to 0.15% by weight. B 2 O 3 has an important role of reducing the expansion coefficient of the glass phase, preventing peeling at the time of temperature rise, and preventing the product from tearing and cracking. If it is less than 0.05% by weight, this function does not work. However, if the content is more than 0.3% by weight, the viscosity of the glass phase becomes high, suppressing oxidation and promoting foaming. This property is based on Fe 2 O 3 , C
When it coexists with uO and Cr 2 O 3 , it becomes more remarkable.
【００２３】Ｐ2Ｏ5は、実質的に含有しない。Ｐ2Ｏ5は
ガラス相を軟らかくし亀裂のない鋳造物を得るには有効
である。しかし、蒸発し易く、使用に際してガラス相の
組成が変化して、鋳造物が破損することがある。P 2 O 5 is substantially not contained. P 2 O 5 is effective in softening the glass phase and obtaining a casting without cracks. However, it tends to evaporate, the composition of the glass phase changes during use, and the casting may be damaged.
【００２４】これらの酸化物の他に、Ｋ2Ｏ及び、Ｃａ
ＯやＢａＯのアルカリ土類酸化物 は、亀裂を防止する
ためには有効であるが、ガラス相の粘性を上げたり、そ
のイオン半径の大きさによって、酸化を妨げるため、添
加しない方が良い。また、ＺｎＯは、ガラス相の粘性を
下げる働きがある。しかし、添加すると、多量の初期発
泡を引き起こす。In addition to these oxides, K 2 O and Ca
Alkaline earth oxides such as O and BaO are effective for preventing cracking, but should not be added because they increase the viscosity of the glass phase or hinder oxidation depending on the size of the ionic radius. ZnO also has the function of lowering the viscosity of the glass phase. However, the addition causes a large amount of initial foaming.
【００２５】[0025]
【実施例】各実施例１〜１９の高ジルコニア鋳造耐火物
は、次のようにして製造した。EXAMPLES The high zirconia cast refractories of Examples 1 to 19 were produced as follows.
【００２６】ジルコンサンドを脱珪して得られたジルコ
ニア原料に、ＳｉＯ2、Ａｌ2Ｏ3、Ｎａ2Ｏ、Ｂ2Ｏ3、そ
の他の粉末原料を所定の割合で加え、これらを混合した
後、アーク電気炉で溶融し、用意した鋳型に鋳造し、
アルミナ粉末の中に埋没して室温まで徐冷した。[0026] SiO 2 , Al 2 O 3 , Na 2 O, B 2 O 3 , and other powdered raw materials are added to the zirconia raw material obtained by desiliconizing the zircon sand at a predetermined ratio, and after mixing these, , Melted in an electric arc furnace, cast into a prepared mold,
It was embedded in alumina powder and gradually cooled to room temperature.
【００２７】鋳型は黒鉛製で製品部分の内寸法が１００
×３００×３５０ｍｍで、その上部に内寸法が１４０×
２３５×３５０ｍｍの押し湯部分を一体に接続したもの
である。The mold is made of graphite and the inner size of the product part is 100
× 300 × 350mm, 140 × inside dimensions
A 235 × 350 mm feeder is integrally connected.
【００２８】徐冷後、製品部分を押し湯部分から切り離
して試験に使用した。得られた試験耐火物はいずれも外
観上亀裂はなかった。After gradual cooling, the product part was separated from the hot water part and used for the test. All of the test refractories obtained had no cracks in appearance.
【００２９】[0029]
【表１】 [Table 1]
【表２】 表１及び表２は、実施例１〜１９の高ジルコニア鋳造耐
火物に含まれる化学成分(単位は重量％、但しＣｒ2Ｏ3
のみはｐｐｍ）及び特性を示す。[Table 2] Tables 1 and 2 show the chemical components contained in the high zirconia cast refractories of Examples 1 to 19 (units are% by weight, but Cr 2 O 3).
Only ppm) and properties.
【００３０】表１で化学成分の割合を表す欄の記号
「−」は、０．０５重量％未満を示し、実質的に含まな
いことを意味している。In Table 1, the symbol "-" in the column representing the ratio of chemical components indicates less than 0.05% by weight, meaning that it is substantially not contained.
【００３１】発泡性は次の方法で試験した。各耐火物の
表面から２５ｍｍ以上内部の３箇所から直径５０ｍｍ、
厚さ１５ｍｍの大きさの試験片を切り出し、この試験片
の上に、内径３５ｍｍ、厚さ１５ｍｍのアルミナ質のリ
ングを乗せて、その中央に各種ガラス約１０ｇを乗せて
昇温し、１３５０℃で１６時間保持した。冷却後、試験
片の中央部分１５×１５ｍｍのガラスに残った泡を数え
て、この数をｃｍ2当たりに換算して、発泡性を評価し
た。The foamability was tested by the following method. 50 mm in diameter from three places inside at least 25 mm from the surface of each refractory,
A test piece having a thickness of 15 mm was cut out, an alumina ring having an inner diameter of 35 mm and a thickness of 15 mm was placed on the test piece, and about 10 g of various kinds of glass was placed at the center thereof, and the temperature was raised to 1350 ° C. For 16 hours. After cooling, the number of bubbles remaining in the glass of 15 × 15 mm in the central portion of the test piece was counted, and this number was converted into cm 2 to evaluate the foamability.
【００３２】耐熱衝撃性は次の方法で試験した。各耐火
物から１００×３００×３００ｍｍの大きさの引け巣の
ない試験片を切り出し、試験片の３００×３００ｍｍの
面を電気抵抗発熱体を用いて加熱した。昇温速度は１０
０℃／時間で１５００℃まで昇温し、１５００℃で２時
間保持した。発生した亀裂及び剥離(試験片の表面が貝
殻状に割れて剥がれること）を観察した。The thermal shock resistance was tested by the following method. A test specimen without shrinkage cavities having a size of 100 × 300 × 300 mm was cut out from each refractory, and a 300 × 300 mm surface of the test specimen was heated using an electric resistance heating element. Heating rate is 10
The temperature was raised to 1500 ° C. at 0 ° C./hour, and kept at 1500 ° C. for 2 hours. The generated cracks and peeling (the surface of the test piece was broken into shells and peeled) were observed.
【００３３】次に比較試験を行った。各比較例１〜１１
について実施例１〜１９と同じ手順で試験耐火物を作
り、同様の試験を行った。Next, a comparative test was performed. Comparative Examples 1 to 11
, Test refractories were prepared in the same procedure as in Examples 1 to 19, and the same tests were performed.
【００３４】表３及び表４は比較例の化学成分及び特性
を示す。Tables 3 and 4 show the chemical components and properties of the comparative examples.
【００３５】[0035]
【表３】 [Table 3]
【表４】 [Table 4]
【００３６】[0036]
【発明の効果】本発明の高ジルコニア鋳造耐火物は、前
述の試験結果からも明らかなように、熱衝撃に対して安
定であり、亀裂及び剥離が発生しない。The high zirconia cast refractory of the present invention is stable against thermal shock and does not cause cracking or peeling, as is clear from the above test results.
【００３７】さらに、本発明の高ジルコニア鋳造耐火物
は、Ｆｅ2Ｏ3とＣｕＯとＣｒ2Ｏ3の合計量及びＢ2Ｏ3の
量並びにＰ2Ｏ5の含有量を限定することにより、次のよ
うな効果を得ることができる。すなわち、アルミノシリ
ケートガラスのみでなく、ソーダライムガラス、硼珪酸
ガラス、ＴＶブラウン管パネル用ガラス、ＰＤＰガラス
（鉛ガラスを含む）、ＬＣＤ（液晶ディスプレイ）ガラ
スなどの種々の溶融ガラスに対して、泡の発生が１０個
／ｃｍ2以下であり、極めて少ない。Further, the high zirconia cast refractory of the present invention is characterized by limiting the total amount of Fe 2 O 3 , CuO and Cr 2 O 3 , the amount of B 2 O 3 and the content of P 2 O 5 , The following effects can be obtained. That is, not only aluminosilicate glass but also various molten glasses such as soda lime glass, borosilicate glass, glass for TV cathode ray tube, PDP glass (including lead glass), LCD (liquid crystal display) glass, etc. The occurrence is 10 / cm 2 or less, which is extremely low.
【００３８】従って、本発明の高ジルコニア鋳造耐火物
は、種々の溶融ガラスに用いることができ、しかも炉の
寿命が長くなり、欠陥のない高品質のガラスが得られ
る。Therefore, the high zirconia cast refractory of the present invention can be used for various kinds of molten glass, and the life of the furnace is prolonged, so that high quality glass free from defects can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平田 公男 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 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kimio Hirata 4-4 Nihonbashi Hisamatsucho, Chuo-ku, Tokyo Itoshige Building Toshiba Monoflux Co., Ltd.
Claims (3)
ニア鋳造耐火物において、 Ｂ2Ｏ3の含有量が０．０５〜０．３重量％であること
と、 Ｆｅ2Ｏ3とＣｕＯとＣｒ2Ｏ3の合計が０．２重量％以下
であることと、 Ｐ2Ｏ5が実質的に含まれないことを組み合わせたことを
特徴とする高ジルコニア鋳造耐火物。1. The chemical component has a ZrO 2 content of 86 to 96% by weight, a SiO 2 content of 3 to 10% by weight, and an Al 2 O 3 content of 0.5 to 2 %. A high zirconia cast refractory having a Na 2 O content of 0.05 to 3% by weight, a B 2 O 3 content of 0.05 to 0.3% by weight, A high zirconia cast refractory characterized in that the total of Fe 2 O 3 , CuO and Cr 2 O 3 is 0.2% by weight or less, and that P 2 O 5 is not substantially contained. .
ニア鋳造耐火物において、 Ｂ2Ｏ3の含有量が０．０５〜０．１５重量％であること
と、 Ｆｅ2Ｏ3とＣｕＯとＣｒ2Ｏ3の合計が０．１５重量％以
下であることと、 Ｐ2Ｏ5が実質的に含まれないことを組み合わせたことを
特徴とする高ジルコニア鋳造耐火物。2. The chemical component has a ZrO 2 content of 88 to 95% by weight, a SiO 2 content of 3 to 8.5% by weight, and an Al 2 O 3 content of 0.8 to 95% by weight. 1.5% by weight, and a high zirconia cast refractory having a Na 2 O content of 0.05 to 2 % by weight, wherein the B 2 O 3 content is 0.05 to 0.15% by weight. A combination of the following: a total of Fe 2 O 3 , CuO and Cr 2 O 3 of 0.15% by weight or less; and a substantial absence of P 2 O 5. Zirconia cast refractories.
が１０個／ｃｍ2以下であることを特徴とする請求項１
又は２に記載の高ジルコニア鋳造耐火物。3. A foaming test with a molten glass, wherein the number of foams is 10 / cm 2 or less.
Or a high zirconia cast refractory according to 2 above.
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|---|---|---|---|
| JP11476599A JP4979047B2 (en) | 1999-04-22 | 1999-04-22 | High zirconia refractories |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11476599A JP4979047B2 (en) | 1999-04-22 | 1999-04-22 | High zirconia refractories |
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|---|---|
| JP2000302560A true JP2000302560A (en) | 2000-10-31 |
| JP4979047B2 JP4979047B2 (en) | 2012-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11476599A Expired - Lifetime JP4979047B2 (en) | 1999-04-22 | 1999-04-22 | High zirconia refractories |
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|---|---|---|---|---|
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| FR2955578A1 (en) * | 2010-01-28 | 2011-07-29 | Saint Gobain Ct Recherches | REFRACTORY PRODUCT HAVING A HIGH ZIRCONY CONTENT |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01100068A (en) * | 1987-10-13 | 1989-04-18 | Asahi Glass Co Ltd | Hot melt refractory having high zirconia content |
-
1999
- 1999-04-22 JP JP11476599A patent/JP4979047B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01100068A (en) * | 1987-10-13 | 1989-04-18 | Asahi Glass Co Ltd | Hot melt refractory having high zirconia content |
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