JPH092870A - High zirconia electro brick - Google Patents
High zirconia electro brickInfo
- Publication number
- JPH092870A JPH092870A JP7175616A JP17561695A JPH092870A JP H092870 A JPH092870 A JP H092870A JP 7175616 A JP7175616 A JP 7175616A JP 17561695 A JP17561695 A JP 17561695A JP H092870 A JPH092870 A JP H092870A
- Authority
- JP
- Japan
- Prior art keywords
- less
- weight
- brick
- cracks
- 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 37
- 239000011449 brick Substances 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- 229910017344 Fe2 O3 Inorganic materials 0.000 abstract 1
- 229910004742 Na2 O Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000005336 cracking Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 229910052845 zircon Inorganic materials 0.000 description 7
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 7
- 239000006060 molten glass Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005382 thermal cycling Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005187 foaming 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
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はガラス溶解炉に適した高
ジルコニア電鋳煉瓦、特に製作による割れや、熱サイク
ル試験による割れが発生しない高ジルコニア電鋳煉瓦に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high zirconia electroformed brick suitable for a glass melting furnace, and more particularly to a high zirconia electroformed brick which is free from cracks due to manufacturing or thermal cycle tests.
【０００２】[0002]
【従来の技術】ガラス溶解炉用の耐火物として、従来よ
りＺｒＯ2 を８０重量％以上含む高ジルコニア電鋳煉瓦
が使用されている。この理由は、ＺｒＯ2 が溶融ガラス
に対して特に耐食性の大きい金属酸化物だからである。
高ジルコニア電鋳煉瓦は、その大部分を占める単斜晶系
ジルコニア結晶と少量のガラス相から構成されている。
電鋳煉瓦は溶融状態の組成物を鋳型に流し込んで（つま
り鋳造して）ゆっくり室温まで冷却する方法によって作
られる。 2. Description of the Related Art As a refractory for a glass melting furnace, a high-zirconia electroformed brick containing 80% by weight or more of ZrO 2 has been used. The reason for this is that ZrO 2 is a metal oxide having particularly high corrosion resistance to molten glass.
High-zirconia electroformed bricks are composed of monoclinic zirconia crystals which occupy most of them and a small amount of glass phase.
Electrocast bricks are made by pouring (ie, casting) a molten composition into a mold and slowly cooling it to room temperature.
【０００３】一方、ジルコニア結晶は、１１５０℃付近
で急激な体積変化を伴って単斜晶系と正方晶系の可逆的
な変態を起こすことがよく知られている。On the other hand, it is well known that zirconia crystals undergo a reversible transformation between a monoclinic system and a tetragonal system with a rapid volume change near 1150 ° C.
【０００４】従って、割れのない高ジルコニア電鋳煉瓦
を得るためには、このジルコニア結晶の変態に伴う体積
変化をいかにしてガラス相に吸収させるかが大きな課題
となる。この課題を解決するために、従来いろいろとガ
ラス相の改善について提案がなされている。Therefore, in order to obtain a high-zirconia electroformed brick without cracks, how to absorb the volume change accompanying the transformation of the zirconia crystal into the glass phase becomes a major problem. In order to solve this problem, various proposals have been made in the past for improving the glass phase.
【０００５】例えば、特開昭４８−８５６１０号公報に
は、ＣｕＯとＢ2 Ｏ3 を添加してガラス相の粘性を調整
して製作による割れを防止することが提案されている。For example, Japanese Unexamined Patent Publication (Kokai) No. 48-85610 proposes that CuO and B 2 O 3 are added to adjust the viscosity of the glass phase to prevent cracking during manufacture.
【０００６】また、特開昭６２−５９５７６号公報に
は、Ｂ2 Ｏ3 とＰ2 Ｏ5 を添加してガラス相を柔らかく
して製作による割れを防止することが提案されている。Further, Japanese Patent Application Laid-Open No. 62-59576 proposes to add B 2 O 3 and P 2 O 5 to soften the glass phase to prevent cracking due to production.
【０００７】前述の提案に対して、特開平３−２１８９
８０号公報においては、Ｂ2 Ｏ3 とＰ2 Ｏ5 はジルコン
結晶が析出するのを助長して、熱サイクルによる割れを
発生させるので好ましくないと記載している。In response to the above-mentioned proposal, Japanese Patent Laid-Open No. 3-2189
In Japanese Patent Laid-Open No. 80, it is described that B 2 O 3 and P 2 O 5 are not preferable because they promote the precipitation of zircon crystals and cause cracks due to thermal cycles.
【０００８】Ｂ2 Ｏ3 とＰ2 Ｏ5 は製作による割れを発
生しない煉瓦を得るために有効ではあるが、しかし、熱
サイクルによる割れを発生させる問題がある。この理由
により、Ｂ2 Ｏ3 とＰ2 Ｏ5 はいずれも好ましくない特
性を有する化学組成であると考えられてきた。B 2 O 3 and P 2 O 5 are effective for obtaining bricks which are free from cracks caused by production, but there is a problem that cracks are caused by thermal cycles. For this reason, it has been believed that both B 2 O 3 and P 2 O 5 are chemical compositions with unfavorable properties.
【０００９】ここで、熱サイクルによる割れとは、熱衝
撃によって破壊しない程度のゆっくりとした昇温及び冷
却の熱負荷を繰り返して製品にかけた際に発生する割れ
である。製品に及ぼす経時変化により内部に化学変化が
生じ、それが容積変化を伴った際に割れ発生の原因とな
る。Here, the cracking due to the heat cycle is a crack which occurs when the product is repeatedly subjected to a heat load of slowly increasing the temperature and cooling so as not to be broken by a thermal shock. Chemical changes occur inside the product due to changes over time, which causes cracking when accompanied by volume changes.
【００１０】[0010]
【発明が解決しようとする課題】Ｂ2 Ｏ3 とＰ2 Ｏ
5 は、高ジルコニア電鋳煉瓦を製作する際の原料中に、
微量ながら不可避的に混入している場合があるが、その
ように原料中に混入している場合には、従来は、原料を
精製するか、それを避けるために予め特別に純度の高い
高価な原料を使用しなければ、熱サイクルによる割れを
完全に解決することはできなかった。Problems to be Solved by the Invention B 2 O 3 and P 2 O
5 is in the raw material when manufacturing high zirconia electroformed brick,
There is a case where it is inevitably mixed in a small amount, but if it is mixed in the raw material in such a way, conventionally, it is necessary to purify the raw material or to avoid it, a special high purity and expensive Without the use of raw materials, cracking due to thermal cycling could not be completely resolved.
【００１１】本発明は、Ｂ2 Ｏ3 とＰ2 Ｏ5 を多少含有
していても、割れのない高ジルコニア電鋳煉瓦を得るこ
とを目的としている。An object of the present invention is to obtain a high zirconia electroformed brick which does not crack even if it contains a small amount of B 2 O 3 and P 2 O 5 .
【００１２】[0012]
【課題を解決するための手段】本発明の要旨は次のとお
りである。すなわち、化学組成が酸化物重量％で以下の
とおりである高ジルコニア電鋳煉瓦。The gist of the present invention is as follows. That is, a high zirconia electroformed brick whose chemical composition is as follows in terms of oxide weight%.
【００１３】 ＺｒＯ2 ８９〜９６ ＳｉＯ2 ２．５〜８．５ Ａｌ2 Ｏ3 ０．２〜１．５ Ｐ2 Ｏ5 ０．５未満 Ｂ2 Ｏ3 １．２未満 ＣｕＯ ０．３未満 Ｐ2 Ｏ5 ＋Ｂ2 Ｏ3 ０．０１を超え、かつ１．７未満 Ｎａ2 Ｏ＋Ｋ2 Ｏ ０．０５〜１．０ ＢａＯ ０．０１〜０．５ ＳｎＯ2 ０．５未満 Ｆｅ2 Ｏ3 ＋ＴｉＯ2 ０．３以下ZrO 2 89-96 SiO 2 2.5-8.5 Al 2 O 3 0.2-1.5 P 2 O 5 less than 0.5 B 2 O 3 less than 1.2 CuO less than 0.3 P 2 O 5 + B 2 O 3 More than 0.01 and less than 1.7 Na 2 O + K 2 O 0.05 to 1.0 BaO 0.01 to 0.5 SnO 2 less than 0.5 Fe 2 O 3 + TiO 2 0.3 or less
【００１４】[0014]
【作用】本発明では、Ｎａ2 Ｏ＋Ｋ2 ＯとＢａＯを所定
量添加することによって、Ｐ2Ｏ5 とＢ2 Ｏ3 を多少含
有していても、割れのないように改良した。In the present invention, by adding a predetermined amount of Na 2 O + K 2 O and BaO, even if a small amount of P 2 O 5 and B 2 O 3 is contained, it is improved so as not to crack.
【００１５】各成分の役割について説明する。The role of each component will be described.
【００１６】ＺｒＯ2 の含有量は、８９〜９６重量％で
ある。ＺｒＯ2 が９６重量％より多い場合は、製作の際
に割れのない耐火物が得られず、８９重量％より少ない
場合は、使用の際に溶融ガラスに対する耐食性が劣る。The ZrO 2 content is 89 to 96% by weight. If ZrO 2 is more than 96% by weight, a crack-free refractory cannot be obtained at the time of production, and if less than 89% by weight, the corrosion resistance to molten glass is poor at the time of use.
【００１７】ＳｉＯ2 の含有量は、２．５〜８．５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。下限値より少ない場合は、ガラス相を形成す
ることができない。上限値より多い場合は、溶融ガラス
に対する耐食性が劣る。The content of SiO 2 is 2.5 to 8.5% by weight. SiO 2 is an essential component for forming a glass phase. When the amount is less than the lower limit value, the glass phase cannot be formed. If it is more than the upper limit, the corrosion resistance to molten glass is poor.
【００１８】Ａｌ2 Ｏ3 の含有量は、０．２〜１．５重
量％である。Ａｌ2 Ｏ3 はガラス相を形成するための重
要な成分である。ガラス相の中へジルコニアが溶解する
のを抑えて、ジルコンの生成を防止して、熱サイクルに
よる割れを抑える働きがある。また、ガラス相の耐食性
を高める作用もある。０．２重量％の下限値より少ない
場合は、ジルコンの生成を防止できない。１．５重量％
の上限値より多い場合は、ガラス相の中のＳｉＯ2 と反
応してムライトを生成する。極端にＡｌ2 Ｏ3が多い場
合は、コランダムを生成して、割れのない製品が得られ
ない。The content of Al 2 O 3 is 0.2 to 1.5% by weight. Al 2 O 3 is an important component for forming a glass phase. It suppresses the dissolution of zirconia into the glass phase, prevents the formation of zircon, and suppresses cracking due to thermal cycling. It also has the effect of increasing the corrosion resistance of the glass phase. If it is less than the lower limit of 0.2% by weight, the formation of zircon cannot be prevented. 1.5% by weight
When it is more than the upper limit value of, mullite is generated by reacting with SiO 2 in the glass phase. When the amount of Al 2 O 3 is extremely large, corundum is generated and a product without cracks cannot be obtained.
【００１９】Ｐ2 Ｏ5 の含有量は０．５重量％未満であ
る。Ｂ2 Ｏ3 の含有量は１．２重量％未満である。そし
てＰ2 Ｏ5 とＢ2 Ｏ3 を合わせた含有量は、０．０１重
量％を越え、かつ１．７重量％未満である。Ｐ2 Ｏ5 お
よびＢ2 Ｏ3 はガラス相の所定の温度での粘性及び熱膨
張率を最適にする上で非常に都合がよく、本発明におい
ては、とくに製作による割れを抑制するのに重要な役割
を果たしている。さらに、Ｐ2 Ｏ5 は製品を製作する際
に、溶融に必要な電力量を低減させる作用がある。Ｐ2
Ｏ5 およびＢ2 Ｏ3 が極端に少ない場合は、このような
役割を果たせない。Ｐ2 Ｏ5 が０．５重量％以上である
場合およびＢ2 Ｏ3 が１．２重量％以上である場合は、
ジルコンを生成させる好ましくない作用が顕著になる。The content of P 2 O 5 is less than 0.5% by weight. The content of B 2 O 3 is less than 1.2% by weight. The combined content of P 2 O 5 and B 2 O 3 is more than 0.01% by weight and less than 1.7% by weight. P 2 O 5 and B 2 O 3 are very convenient for optimizing the viscosity and the coefficient of thermal expansion of the glass phase at a given temperature, and are important in the present invention especially for suppressing cracks caused by fabrication. Plays a role. Further, P 2 O 5 has an effect of reducing the amount of electric power required for melting when manufacturing a product. P 2
If O 5 and B 2 O 3 are extremely small, such a role cannot be fulfilled. When P 2 O 5 is 0.5 wt% or more and B 2 O 3 is 1.2 wt% or more,
The undesirable effect of producing zircon becomes significant.
【００２０】ＣｕＯの含有量は０．３重量％未満であ
る。ＣｕＯはガラス相の所定の温度での粘性及び熱膨張
率を最適にするのに都合がよい。また、高ジルコニア電
鋳煉瓦を製作する際に、溶融に必要な電力量を低減させ
る作用がある。しかし、ＣｕＯが０．３重量％以上であ
ると、溶融ガラスを着色したり、溶融ガラスに泡を生成
させる発泡の原因になる。The CuO content is less than 0.3% by weight. CuO is convenient for optimizing the viscosity and coefficient of thermal expansion of the glass phase at a given temperature. In addition, when producing a high-zirconia electroformed brick, it has an effect of reducing the amount of electric power required for melting. However, if the content of CuO is 0.3% by weight or more, it may cause coloring of the molten glass or foaming of the molten glass.
【００２１】Ｎａ2 ＯとＫ2 Ｏの合わせた含有量は０．
０５〜１．０重量％である。ＢａＯの含有量は０．０１
〜０．５重量％である。これらを添加することによっ
て、Ｐ2 Ｏ5 やＢ2 Ｏ3 が持っているジルコンを生成す
るという不都合な特性を消失させ、ガラス相を形成する
成分としての有益な特性のみを取り出すことができる。
これは本発明の特徴の一つである。The combined content of Na 2 O and K 2 O is 0.
05 to 1.0% by weight. BaO content is 0.01
~ 0.5% by weight. By adding these, it is possible to eliminate the inconvenient characteristics of P 2 O 5 and B 2 O 3 that form zircon, and to take out only the beneficial characteristics as a component forming a glass phase.
This is one of the features of the present invention.
【００２２】ＳｎＯ2 の含有量は０．５重量％未満であ
る。ＳｎＯ2 はガラス相の粘性を下げ、耐食性のあるガ
ラス相を形成するのに有効である。ＳｎＯ2 が０．５重
量％以上であると、ガラス溶融炉に使用された場合、溶
融ガラスを発泡させることがある。The SnO 2 content is less than 0.5% by weight. SnO 2 is effective in lowering the viscosity of the glass phase and forming a glass phase having corrosion resistance. When SnO 2 is 0.5% by weight or more, the molten glass may be foamed when used in a glass melting furnace.
【００２３】[0023]
【実施例】本発明の好適な実施例による高ジルコニア電
鋳煉瓦について説明する。EXAMPLE A high zirconia electroformed brick according to a preferred embodiment of the present invention will be described.
【００２４】出発原料としてジルコンを脱珪して得られ
た人工ジルコニアを用意し、この人工ジルコニアに、Ａ
ｌ2 Ｏ3 、ＳｉＯ2 、Ｐ2 Ｏ5 、Ｂ2 Ｏ3 、ＣｕＯ、Ｎ
ａ2Ｏ、Ｋ2 Ｏ、ＢａＯ、ＳｎＯ2 等を粉末原料として
各実施例の所定の割合で加え、これらを混合した後、ア
ーク電気炉内で溶融し、用意した鋳型に鋳造し、バイヤ
ーアルミナの粉末中に埋没して室温近くになるまで徐冷
した。As a starting material, an artificial zirconia obtained by desiliconizing zircon was prepared.
l 2 O 3 , SiO 2 , P 2 O 5 , B 2 O 3 , CuO, N
a 2 O, K 2 O, BaO, SnO 2 and the like were added as powder raw materials at a predetermined ratio of each example, and after mixing them, they were melted in an arc electric furnace and cast in a prepared mold to prepare a Bayer alumina. It was embedded in the powder of 1. and slowly cooled to near room temperature.
【００２５】この時使用した鋳型は黒鉛製で製品部分の
内部寸法が１００ｍｍ×１５０ｍｍ×３５０ｍｍで、そ
の上に内部寸法が１４０ｍｍ×２３５ｍｍ×２００ｍｍ
の押し湯部分を一体に接続したものである。徐冷後、製
品部分を押し湯部分から切り離して試験に供した。The mold used at this time was made of graphite, and the internal dimensions of the product part were 100 mm × 150 mm × 350 mm, and the internal dimensions were 140 mm × 235 mm × 200 mm.
The riser part of is connected together. After the slow cooling, the product part was separated from the riser part and used for the test.
【００２６】[0026]
【表１】 このようにして製作した製品の化学組成の割合及び割れ
の特性を表１に示す。[Table 1] Table 1 shows the chemical composition ratios and crack characteristics of the products thus manufactured.
【００２７】[0027]
【表２】 本発明の範囲外である比較例を同様に表２に示す。[Table 2] Comparative examples that are outside the scope of the present invention are also shown in Table 2.
【００２８】表１〜２中の含有量の欄に記載の記号
「−」は、０．０１重量％未満の含有量を示し、実質的
に含まないことを意味する。The symbol "-" described in the content column in Tables 1 and 2 means that the content is less than 0.01% by weight, and that it is substantially free.
【００２９】製品の割れの特性として製作による割れと
熱サイクルによる割れを調べた。ただし、割れの有無を
判断するとき、煉瓦を肉眼で観察した際に長さ５ｃｍ以
下の割れのものは割れ無と認定した。As the characteristics of product cracking, cracks due to fabrication and cracks due to thermal cycles were examined. However, when judging the presence or absence of cracks, when the bricks were observed with the naked eye, cracks with a length of 5 cm or less were judged to be uncracked.
【００３０】製作による割れは、製品を製作した際、冷
却中に発生する割れである。冷却後、ほぼ２等分に切断
して切断面を含み外観の観察によって割れの有無を調べ
た。The cracks due to manufacturing are cracks that occur during cooling when a product is manufactured. After cooling, the material was cut into approximately two equal parts, and the presence of cracks was examined by observing the appearance including the cut surface.
【００３１】熱サイクルによる割れは次の方法で試験を
行った後、外観の観察によって割れの有無を調べた。The cracks due to the heat cycle were tested by the following method, and then the presence or absence of cracks was examined by observing the appearance.
【００３２】試験方法を述べると、まず大きさ３０ｍｍ
×４０ｍｍ×４０ｍｍの試料を各実施例および比較例の
製品から切り出した。次に、各試料を電気炉に入れて、
室温から８００℃に昇温し、８００℃で１時間保持した
後、８００℃から１２５０℃に昇温し、１２５０℃で１
時間保持した。その後、１２５０℃から８００℃に降温
した。この８００℃で１時間保持してから、８００℃に
降温するまでの諸工程を１回のサイクルとして２０回繰
り返した。その後、室温まで冷却した。昇温および降温
は全て４００℃／Hrで行った。The test method is as follows. First, the size is 30 mm.
Samples of x40 mm x 40 mm were cut out from the products of Examples and Comparative Examples. Next, put each sample in an electric furnace,
After raising the temperature from room temperature to 800 ° C and holding it at 800 ° C for 1 hour, the temperature is raised from 800 ° C to 1250 ° C and 1250 ° C for 1 hour.
Hold for hours. Then, the temperature was lowered from 1250 ° C to 800 ° C. The steps from holding at 800 ° C. for 1 hour to lowering the temperature to 800 ° C. were repeated 20 times as one cycle. Then, it cooled to room temperature. All the temperature rising and temperature lowering were performed at 400 ° C./Hr.
【００３３】[0033]
【発明の効果】本発明によれば、製作による亀裂の発生
や、熱サイクルによる破損または亀裂の発生を防止する
ことができる。すなわち、Ｎａ2 Ｏ、Ｋ2 ＯおよびＢａ
Ｏなどを含有させることにより、Ｂ2 Ｏ3 とＰ2 Ｏ5 の
不都合な作用である熱サイクルによる破損または割れの
原因となるジルコンの形成を抑制することができた。こ
のため、Ｂ2 Ｏ3 とＰ2 Ｏ5 の好都合な作用、すなわち
ガラス相の粘性および膨脹係数の最適にする作用を有効
に利用できる。さらに、高ジルコニア電鋳煉瓦の原料と
して、不純物にＰ2 Ｏ5 とＢ2 Ｏ3 を含有する原料でも
精製することなく使用できる。According to the present invention, it is possible to prevent the generation of cracks due to manufacturing, and the damage or cracks due to thermal cycling. That is, Na 2 O, K 2 O and Ba
By including O or the like, it was possible to suppress the formation of zircon, which is a disadvantageous effect of B 2 O 3 and P 2 O 5 and causes damage or cracking due to thermal cycling. Therefore, the advantageous action of B 2 O 3 and P 2 O 5 , that is, the action of optimizing the viscosity and expansion coefficient of the glass phase can be effectively utilized. Further, as a raw material for a high-zirconia electroformed brick, a raw material containing P 2 O 5 and B 2 O 3 as impurities can be used without purification.
Claims (1)
である高ジルコニア電鋳煉瓦。 ＺｒＯ2 ８９〜９６ ＳｉＯ2 ２．５〜８．５ Ａｌ2 Ｏ3 ０．２〜１．５ Ｐ2 Ｏ5 ０．５未満 Ｂ2 Ｏ3 １．２未満 ＣｕＯ ０．３未満 Ｐ2 Ｏ5 ＋Ｂ2 Ｏ3 ０．０１を超え、かつ１．７未満 Ｎａ2 Ｏ＋Ｋ2 Ｏ ０．０５〜１．０ ＢａＯ ０．０１〜０．５ ＳｎＯ2 ０．５未満 Ｆｅ2 Ｏ3 ＋ＴｉＯ2 ０．３以下1. A high zirconia electroformed brick having a chemical composition as follows, in wt% oxide. ZrO 2 89~96 SiO 2 2.5~8.5 Al 2 O 3 0.2~1.5 P 2 O 5 0.5 less than B 2 O 3 less than 1.2 CuO 0.3 P 2 O 5 + B 2 O 3 0.01 and less than 1.7 Na 2 O + K 2 O 0.05 to 1.0 BaO 0.01 to 0.5 SnO 2 less than 0.5 Fe 2 O 3 + TiO 2 0.3 Less than
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17561695A JP3682888B2 (en) | 1995-06-20 | 1995-06-20 | High zirconia electroformed brick |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17561695A JP3682888B2 (en) | 1995-06-20 | 1995-06-20 | High zirconia electroformed brick |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH092870A true JPH092870A (en) | 1997-01-07 |
| JP3682888B2 JP3682888B2 (en) | 2005-08-17 |
Family
ID=15999206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17561695A Expired - Lifetime JP3682888B2 (en) | 1995-06-20 | 1995-06-20 | High zirconia electroformed brick |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3682888B2 (en) |
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