JPH02141465A - Refractory material - Google Patents
Refractory materialInfo
- Publication number
- JPH02141465A JPH02141465A JP1225795A JP22579589A JPH02141465A JP H02141465 A JPH02141465 A JP H02141465A JP 1225795 A JP1225795 A JP 1225795A JP 22579589 A JP22579589 A JP 22579589A JP H02141465 A JPH02141465 A JP H02141465A
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- refractory material
- magnesia
- powder
- oxide powder
- 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
- 239000011819 refractory material Substances 0.000 title claims abstract description 49
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 74
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 59
- 239000011651 chromium Substances 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 44
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052596 spinel Inorganic materials 0.000 claims description 6
- 239000011029 spinel Substances 0.000 claims description 6
- 230000003628 erosive effect Effects 0.000 abstract description 18
- 150000002739 metals Chemical class 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000006835 compression Effects 0.000 abstract 1
- 238000007906 compression Methods 0.000 abstract 1
- 239000011449 brick Substances 0.000 description 29
- 238000010304 firing Methods 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000000280 densification Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 229910000599 Cr alloy Inorganic materials 0.000 description 6
- 239000000788 chromium alloy Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 235000013980 iron oxide Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 239000011451 fired brick Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000008223 ribosides Chemical class 0.000 description 2
- 239000011452 unfired brick Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- -1 metallic iron Chemical compound 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011823 monolithic refractory Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は溶融金属容器の内張材に使用される耐火物に用
いられる素材に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a material used for a refractory used as a lining material for a molten metal container.
［従来の技術及び発明が解決しようとするｉ！ｌＩ題コ
従来より製鐵プロセスでは転炉で製錬した後、溶鋼中の
不純物除去のために、ＤＩ、 ＲＨ設備等真空容器で脱
ガス処理している。此等の真空容器の内張材には高温真
空下で特に安定な材質が使用されている。一般にシリカ
を主成分とする耐火物は高温真空下で解離しやすく、こ
の用途には不向であるが、マグネシア、スピネル、クロ
ム質耐火物は安定であり、溶鋼流に対する耐摩耗性にす
ぐれた焼成タイプのマグネシア、マグネシア・スピネル
、マグネシア・クロム質耐火物が好適と云える。[Prior art and inventions attempt to solve i! Conventionally, in the steelmaking process, after smelting in a converter, molten steel is degassed in a vacuum vessel such as DI or RH equipment to remove impurities. The lining material of these vacuum vessels uses a material that is particularly stable under high-temperature vacuum conditions. In general, silica-based refractories tend to dissociate under high-temperature vacuum conditions, making them unsuitable for this purpose, but magnesia, spinel, and chromium refractories are stable and have excellent wear resistance against molten steel flow. Sintered type magnesia, magnesia spinel, and magnesia chromium refractories are preferred.
一般的には、この中でスラグ・溶鋼との反応による化学
的浸食、温度変化による熱衝撃に強い、すなわち耐スポ
ール性に優れたマグネシア・クロム質煉瓦が使用される
ている。Generally, magnesia-chromium bricks are used because they are resistant to chemical erosion due to reactions with slag and molten steel and thermal shock due to temperature changes, that is, they have excellent spalling resistance.
このマグネシア・クロム質煉瓦は、その原料構成からダ
イレクトボンドとりボンドの二種類に大別で幹る。ダイ
レクトボンドは、マグネシア源として高純度のマグネシ
アクリンカ−を、またクロム源としては天然クロム鉱が
使用されており、これらの配合物をプレス成形し、１７
００℃以上の高温で焼成して得られたものである。一方
すボンドはマグネシアクリンカ−と、マグネシアクリン
カ−とクロム鉱を事前に電気炉で融解・冷却後粉砕した
低不純物の電融マグクロを配合、成形し、焼成して得ら
れたものである。These magnesia chromium bricks can be broadly divided into two types, direct bond and bond, based on their raw material composition. Direct Bond uses high-purity magnesia clinker as the magnesia source and natural chromite as the chromium source.
It is obtained by firing at a high temperature of 00°C or higher. On the other hand, the bond is obtained by blending magnesia clinker and low-impurity electrofused tuna which is obtained by melting magnesia clinker and chromium ore in an electric furnace, cooling and pulverizing, molding, and firing.
ところで、耐火物の耐食性を左右する因子の一つとして
気孔率がある。By the way, porosity is one of the factors that influences the corrosion resistance of refractories.
すなわち、煉瓦組織内の気孔を介してスラグ・溶鋼等の
外来成分が煉瓦内に浸入し、さらに煉瓦成分と反応する
ことによって容易に摩耗損傷するため、この気孔率は小
さい程、この現象を抑制し、煉瓦の摩耗損傷を軽減する
ことができるので、高耐食性である。In other words, foreign components such as slag and molten steel penetrate into the brick through the pores in the brick structure, and further react with the brick components, resulting in easy wear and damage, so the smaller the porosity, the less this phenomenon can be suppressed. It also has high corrosion resistance as it can reduce abrasion damage to bricks.
マグネシア・クロム質煉瓦の場合、ダイレクトボンド、
リボシドにかかわらず、低気孔率確保手段としては、従
来より配合原料を細密充填となる粒度に調整し、高圧プ
ルスによ）て充填成形し、これを超高温で焼成するのが
普通である。しかしこのような手段によっては気孔率は
、ダイレクトボンドの場合１４％、リボシドで１２％が
下限でありいずれも特に耐食性の点で改善の余地がある
。For magnesia/chromium bricks, direct bond,
Regardless of riboside, the conventional means of ensuring low porosity is to adjust the blended raw materials to a particle size that results in close packing, fill and mold using a high-pressure pulsing machine, and then sinter this at an ultra-high temperature. However, depending on such means, the lower limit of the porosity is 14% for direct bonding and 12% for riboside, and in both cases there is room for improvement, especially in terms of corrosion resistance.
ところで、煉瓦組織の緻密化を図る方法の一つとして、
酸化クロム粉末と金属クロム粉末の混合物を添加して焼
成する方法が公開されている（特開昭６２−２０７７５
７号）。By the way, one of the methods for densifying the brick structure is
A method of adding and firing a mixture of chromium oxide powder and metal chromium powder has been disclosed (Japanese Unexamined Patent Publication No. 62-20775).
No. 7).
この方法では、酸化クロム粉末と金属クロム粉末を混合
することで融点が低下し、焼結が促進され煉瓦の緻密化
が図れるとしているが、両者の共融点は１６６０℃と高
く煉瓦組織の緻密化という観点からは充分とは云い難く
、また、焼成むらが生じ易いことが懸念される。すなわ
ち、煉瓦の周辺部は十分に焼成され、組織が緻密化する
か、中心部では金属クロムが未焼成のまま残留し、組織
も緻密化していない。その耐食性は、焼結が進んだ煉瓦
周囲の緻密な部分と比較すると、約半分程度であり、加
えて混線時に金属クロム粉末が均一に混合しにくい。そ
のためこの金属クロムの混合効果が充分に発揮されず、
煉瓦組織全体に亘って、均一に緻密化することは難しい
。In this method, the melting point is lowered by mixing chromium oxide powder and metallic chromium powder, promoting sintering and making the brick more compact. From this point of view, it is difficult to say that it is sufficient, and there is a concern that uneven firing is likely to occur. That is, either the peripheral part of the brick is sufficiently fired and the structure is densified, or the metallic chromium remains unfired in the center part, and the structure is not densified. Its corrosion resistance is about half that of the dense area around the brick where sintering has progressed, and in addition, it is difficult for the metal chromium powder to mix uniformly during cross-contact. Therefore, the mixing effect of this metallic chromium is not fully demonstrated,
It is difficult to uniformly densify the entire brick structure.
したがって、煉瓦全体として充分な耐用性が確保できな
い。Therefore, sufficient durability cannot be ensured for the brick as a whole.
一方金属クロムは、非常に高価であり、これを添加した
耐火物はコスト面でも問題がある。On the other hand, metallic chromium is very expensive, and refractories containing it have problems in terms of cost.
本発明は、このような問題を有しないマグネシア・クロ
ム質煉瓦を得るための耐火物素材を提供するものである
。The present invention provides a refractory material for obtaining magnesia-chromium bricks that does not have such problems.
［課題を解決するための手段］
本発明の、第１の発明は、マグネシア又はマグネシアを
含有する耐火材に、金属クロムと金属鉄、金属マグネシ
ウム、金属アルミニウム、金属シリコンなどの金属との
合金又は化合物あるいは混合物粉末を１〜２０重量％混
合したことを特徴とする耐火物素材およびこの耐火物素
材に必要に応じて酸化クロム粉末、酸化アルミニウム粉
末、酸化鉄粉末を適宜添加したことを特徴とする耐火物
素材であり、又第２の発明は、金属クロムを含有させた
電融マグクロに、マグネシア又はマグネシアを含有する
スピネル、クロム鉱等を混合したことを特徴とする耐火
物素材、およびこの耐火物素材に必要に応じて酸化クロ
ム粉末、酸化アルミニウム粉末、酸化鉄粉末を添加した
ことを特徴とする耐火物素材である。[Means for Solving the Problems] A first aspect of the present invention is to add an alloy of metallic chromium and a metal such as metallic iron, metallic magnesium, metallic aluminum, metallic silicon, or the like to magnesia or a refractory material containing magnesia. A refractory material characterized by a mixture of 1 to 20% by weight of a compound or mixture powder, and a chromium oxide powder, an aluminum oxide powder, or an iron oxide powder added to this refractory material as necessary. A second invention is a refractory material, characterized in that magnesia or a spinel containing magnesia, chromite, etc. is mixed with electrofused maguro containing metallic chromium, and this refractory material. This is a refractory material characterized by adding chromium oxide powder, aluminum oxide powder, and iron oxide powder to the material as necessary.
前記のように煉瓦組織内の気孔率を低下させるためには
いくつかの方法があるが、プレス能力向上、超高温焼成
化には経済面で限界がある。As mentioned above, there are several methods for reducing the porosity within the brick structure, but there are economic limits to improving pressing ability and ultra-high temperature firing.
よって本発明においては、マグネシア又はマグネシアを
含有する耐火材に、金属クロムと金属鉄、金属アルミニ
ウム、金属マグネラム、金属シリコン等の金属との合金
、化合物、混合物あるいは金属クロム、更には必要に応
じて酸化クロム粉末、酸化アルミニウム粉末、酸化鉄等
の低融化物を添加した耐火物素材を用いるものであり、
これを酸化雰囲気下で焼成することによりあるいは不焼
成で施工・使用することにより、金属を酸化させ、さら
にマグネシアと反応させることにより、その際の体積膨
張により、気孔を充填し、低気孔率化を図る。Therefore, in the present invention, magnesia or a refractory material containing magnesia is combined with alloys, compounds, or mixtures of metallic chromium and metals such as metallic iron, metallic aluminum, metallic magnesium, metallic silicon, or metallic chromium, and further, as necessary. It uses refractory materials to which low-melting substances such as chromium oxide powder, aluminum oxide powder, and iron oxide are added.
By firing this in an oxidizing atmosphere or by applying and using it without firing, the metal is oxidized and further reacted with magnesia, and the volume expansion at that time fills the pores and lowers the porosity. We aim to
又、同時に金属酸化物によって低融化して、焼結反応を
煉瓦中心部まで促進させることによって、煉瓦組織を均
一化し、特にその耐食性強度を安定的に強化するもので
ある。At the same time, the metal oxide lowers the melting point and promotes the sintering reaction to the center of the brick, thereby making the brick structure uniform and, in particular, stably strengthening its corrosion-resistant strength.
金属クロムの添加方法としては適当な粒度の金属クロム
あるいはクロム合金又はクロム化合物、混合物粉末を耐
火物原料粉末に添加、混練する方法、電融マグクロを製
造する際に、融解用の炭素電極を利用してクロム鉱を還
元し、金属クロムを電融マグクロ中に生成せさる方法で
ある。前者の方法を適用したのが請求項１の耐火物素材
、後者を適用したのが請求項２の耐火物素材である。Methods for adding metallic chromium include adding and kneading metallic chromium, chromium alloy, chromium compound, or mixture powder of appropriate particle size to refractory raw material powder, and using a carbon electrode for melting when producing electrofused maguro. This is a method in which chromium ore is reduced and metallic chromium is produced in fused maguro. The refractory material according to claim 1 is obtained by applying the former method, and the refractory material according to claim 2 is obtained by applying the latter method.
先ず、金属クロム添加マグネシア・クロム貿ダイレクト
ボンド煉瓦の気孔率低減について第１図に従って説明す
る。第１図は本発明の耐火物素材を従来レベルでプレス
成形した後の充填状況である。マグネシア粒１とクロム
鉱粒２の間には微細粒の金属クロム粉末３が均一に分散
されている。これを大気雰囲気下で焼成することにより
金属クロム粉末は酸化し、新たに微細のクロム鉱４が生
成する。この際、１．８倍の体積膨張を伴うため、気孔
は充填される。また気孔が充填されるため、全体の強度
も向上する。First, the reduction in porosity of a magnesia/chromium trade direct bond brick containing metallic chromium will be explained with reference to FIG. FIG. 1 shows the filling state after the refractory material of the present invention was press-molded at a conventional level. Fine metallic chromium powder 3 is uniformly dispersed between magnesia grains 1 and chromium ore grains 2. By firing this in an air atmosphere, the metal chromium powder is oxidized, and fine chromium ore 4 is newly generated. At this time, the pores are filled because the volume is expanded by 1.8 times. Furthermore, since the pores are filled, the overall strength is also improved.
金属クロム粉末の添加量は、２０％を越えた場合、焼成
中あるいは使用中に体積膨張に起因する割れが生じする
。また添加量１％未満の場合、金属クロム粉末を均一に
分散させることは困難であり、又、金属クロム添加効果
がない。If the amount of metal chromium powder added exceeds 20%, cracks will occur due to volume expansion during firing or use. Further, if the amount added is less than 1%, it is difficult to uniformly disperse the metallic chromium powder, and there is no effect of adding metallic chromium.
ゆえに適正添加量は１〜２０％である。また、金属クロ
ム粉末の粒度は、反応性を低下させない５００μｍ以下
が望ましい。Therefore, the appropriate amount to add is 1 to 20%. Further, the particle size of the metallic chromium powder is preferably 500 μm or less so as not to reduce the reactivity.
表１は、マグネシア、クロム鉱を主成分とし、金属クロ
ムを１．０〜３０％配合し、成形、焼成したマグクロダ
イレクトボンド煉瓦の品質例を示す。Table 1 shows an example of the quality of a magcro direct bond brick that is made of magnesia and chromite as main components, mixed with 1.0 to 30% of metallic chromium, molded and fired.
表 １
表
１ （続き）
試作条件
試料の大ぎさ ７５ Ｘ１１４ Ｘ２３０ｍｍ焼成温度
１８００℃
１未焼成部最大長は１１４ｘ２３０ｍｍの面に平行に三
等分した断面で観察した。Table 1 Table 1 (Continued) Prototype conditions Sample size 75 x 114 x 230 mm Firing temperature 1800°C 1 The maximum length of the unfired part was observed on a cross section divided into three equal parts parallel to a 114 x 230 mm surface.
浸食試験条件
方法 誘導炉による内張浸食試験
温度 １６５０℃
時間 ４時間
雰囲気 真空
スラグ Ｃ／Ｓ−３ＣａＦ２＝２０％添加４００ｇ
Ｘ ２回鋼 ５ＩＪＳ３０４１０ｋｇ
′”浸食試験後、各試料の最大溶損部の減寸量を測定し
、符号１の試料の減寸量を１００として基準化し、溶損
指数とした。溶損指数が小さいほど高耐食性である。Erosion test conditions and methods Lining erosion test using induction furnace Temperature: 1650°C Time: 4 hours Atmosphere: Vacuum slag C/S-3CaF2 = 20% addition 400g
X 2 times Steel 5IJS30410kg'' After the erosion test, the amount of reduction in the maximum erosion part of each sample was measured, and the amount of reduction in size of the sample with code 1 was set as 100, and this was taken as the erosion index.The erosion index was The smaller the value, the higher the corrosion resistance.
尚、試験片は完全に焼成された部分から作成した。Note that the test piece was created from a completely fired part.
金属クロム粉末の配合効果は１．０％以上特に４〜１０
％の範囲が顕著であり、２０％を越えると焼成中に亀裂
が発生し緻密性、強度低下が大きくなり、耐用性が低下
する傾向を示す。The mixing effect of metallic chromium powder is 1.0% or more, especially 4 to 10%.
% range is significant, and if it exceeds 20%, cracks will occur during firing, resulting in a large decrease in compactness and strength, and a tendency for durability to decrease.
金属クロムとして、例えば金属クロムと金属鉄、金属ア
ルミニウム、金属マグネシウム、金属シリコン等との合
金を用いた場合には、金属クロム又は酸化クロムあるい
は金属クロムと酸化クロムを用いた場合に比し金属クロ
ムの分散性が良好でありかつ、融点２００℃程度下げる
ことができ、煉瓦の中心部まで酸化反応と焼結反応を促
進させることができるので焼成ムラもなく煉瓦組織全体
の緻密化を一層促進させ耐食性と共に煉瓦強度を大巾に
向上で籾る。For example, when an alloy of metallic chromium and metallic iron, metallic aluminum, metallic magnesium, metallic silicon, etc. is used as metallic chromium, the amount of metallic chromium is lower than when metallic chromium or chromium oxide or metallic chromium and chromium oxide is used. It has good dispersibility and can lower the melting point by about 200℃, promoting the oxidation reaction and sintering reaction to the center of the brick, thereby eliminating uneven firing and further promoting the densification of the entire brick structure. Significantly improves brick strength as well as corrosion resistance.
第３図に１例として金属クロム合金粉末中の金属鉄、金
属アルミニウム、金属マグネシウム、金属シリコンの含
有量と、焼成煉瓦中の未焼成部分の最大長との関係を示
す。ここで用いられた試料は原料組成比がマグネシア７
ｏニクロム鉱３０のマグクロダイレクトボンド煉瓦で、
金属クロムと他の金属との混合物を４％添加して混練し
、７５ ｘ １１４ Ｘ ２３０ｍｍの大きさにプレス
成形し、 １８００℃で焼成したものであり、冷却後に
１１４ Ｘ ２３０ｍｍの面に平行に三等分し、中心部
の未焼成部分の最大長を測定した。未焼成部分の大きさ
は金属クロム合金粉末中の金属クロム以外の金属の配合
量の増加と共に減少しており、いずれの金属の場合も１
０〜１５％配合することにより金属クロム以外の金属無
配合の場合に比し、煉瓦組織内の未焼成部分の最大長は
格段に小さくなり、未焼成部分も大巾に減少している。FIG. 3 shows, as an example, the relationship between the content of metal iron, metal aluminum, metal magnesium, and metal silicon in the metal chromium alloy powder and the maximum length of the unfired portion in the fired brick. The sample used here had a raw material composition ratio of magnesia of 7.
o Nichrome ore 30 magkuro direct bond brick,
It is made by adding 4% of a mixture of metallic chromium and other metals, kneading it, press-forming it into a size of 75 x 114 x 230 mm, firing it at 1800°C, and after cooling it in parallel to a 114 x 230 mm surface. It was divided into three equal parts, and the maximum length of the unfired part at the center was measured. The size of the unfired part decreases with the increase in the amount of metals other than metal chromium in the metal chromium alloy powder.
By blending 0 to 15%, the maximum length of the unfired portion in the brick structure becomes much smaller than when no metal other than metallic chromium is mixed, and the unfired portion also decreases significantly.
金属粉末中の金属クロム成分の濃度は、希釈効果や融点
を低下させる意味で、９０％以下であることが望ましく
、耐火物の耐食性、特に高塩基度スラグに対する耐食性
を低下させないためには５０％以上であることが望まし
い。各金属粉末の粒度は、反応性を低下させない５００
μｍ程度以下が望ましい。The concentration of the metallic chromium component in the metal powder is preferably 90% or less in order to reduce the dilution effect and melting point, and is preferably 50% or less in order not to reduce the corrosion resistance of refractories, especially against high basicity slag. The above is desirable. The particle size of each metal powder is 500, which does not reduce the reactivity.
It is desirable that the thickness be about μm or less.
金属クロムは非常に高価であるが、クロムと鉄あるいは
シリコンなどの合金、化合物あるいは混合物は安価に入
手可能で、価格は金属クロム数分の１から１０分の１程
度以下である。このため経済的問題も解決される。Metallic chromium is very expensive, but alloys, compounds, or mixtures of chromium and iron or silicon are available at low cost, and the price is about one-tenth to one-tenth that of metal chromium. This also solves the economic problem.
以上、金属クロム成分を合金化合物と云った形で直接加
える方法について述べたが、金属クロム成分の添加の方
法としてもう一つ考えられる。それは電融マグクロを製
造する際に、融解用の炭素電極を利用してクロム鉱を還
元し、金属クロムを電融マグクロ中に生成させ、これを
そのまま使用する方法である。この方法によれば、耐火
物原料中に均一に金属が分散しているので、混練が容易
でかつ安価に金属クロム成分を添加することができる。The method of directly adding the metallic chromium component in the form of an alloy compound has been described above, but there is another method of adding the metallic chromium component. This is a method in which chromium ore is reduced using a carbon electrode for melting when producing electrofused maguro, producing metallic chromium in electrofused maguro, and this is used as is. According to this method, since the metal is uniformly dispersed in the refractory raw material, kneading is easy and the metallic chromium component can be added at low cost.
主成分となるマグネシア、スピネル、クロム鉱あるいは
金属クロム含有の電融マグクロは、通常使用される範囲
の品質のものでさしつかえない。すなわちマグネシアの
場合ＭｇＯ＞９０％、スピネルの場合ＭｇＯ−Ａｌ２Ｏ
５＞ ９０％、クロム鉱の場合ＭｇＯ・Ｃｒ２Ｏ３〉５
０％、電融マグクロの場合ＭｇＯ１Ｃｒ２０３、以外の
成分３０％以下のものが好ましい。金属クロムを生成さ
せた電融マグクロの場合、金属クロムの生成量は３〜７
％位が好適であり、その他の成分については３０％以下
のものが好ましい。The main components, magnesia, spinel, chromite, or electrofused maguro containing metallic chromium, may be of a quality within the range normally used. That is, in the case of magnesia, MgO>90%, in the case of spinel, MgO-Al2O
5>90%, MgO・Cr2O3>5 for chromite
0%, and in the case of electrofused maguro, it is preferable that components other than MgO1Cr203 are 30% or less. In the case of electrofused maguro that has produced metallic chromium, the amount of metallic chromium produced is 3 to 7.
%, and other components preferably 30% or less.
酸化クロム粉末、酸化アルミニウム粉末又はこれらの混
合物は、耐火物の焼結助剤として通常配合されている程
度配合する。特開昭６２２０７７５７号によれば金属ク
ロムと酸化クロムは必須成分となっているが、金属クロ
ム合金、化合物、混合物に金属クロム以外の金属粉末の
添加で緻密化の効果は得られ、これに必要に応じて酸化
クロム粉末、酸化アルミニウム又はこれらの混合粉末を
添加した場合には、その効果か層明確になる。Chromium oxide powder, aluminum oxide powder, or a mixture thereof is blended to the extent that it is normally blended as a sintering aid for refractories. According to JP-A-62207757, metallic chromium and chromium oxide are essential components, but the densification effect can be obtained by adding metal powders other than metallic chromium to metallic chromium alloys, compounds, and mixtures. When chromium oxide powder, aluminum oxide, or a mixed powder of these is added depending on the situation, the effect becomes clearer.
ところで、未酸化・未焼成部分をなくすためには、酸化
剤を添加することが有効である。この酸化剤としては、
焼成段階までは安定で焼成時には金属を酸化させ、かつ
耐火物の耐食性に大きな悪影響を与えず、また焼成炉に
害を及ぼさないものである必要がある。これらの点に適
合するのがＦｅ２Ｏ３と Ｆｅ３Ｏ４である。これらは
焼成時に他の金属を酸化させ、また自身はＦｅ０Ｏ形と
なりマグネシアやクロム鉱中に拡散し、添加量の制御を
うまく行えば耐火物の耐食性に大きな悪影響を及ぼすこ
とは少ない。また、焼成炉に悪影響を及ぼすこともない
。By the way, in order to eliminate unoxidized and unfired parts, it is effective to add an oxidizing agent. This oxidizing agent is
It needs to be stable up to the firing stage, not oxidize the metal during firing, and not have a major negative effect on the corrosion resistance of the refractory, nor cause any harm to the firing furnace. Fe2O3 and Fe3O4 meet these requirements. These oxidize other metals during firing, and themselves become Fe0O and diffuse into magnesia and chromite, so if the amount added is well controlled, it is unlikely to have a major adverse effect on the corrosion resistance of refractories. Moreover, it does not have any adverse effect on the firing furnace.
表２はマグネシア、クロム鉱を主成分とし、金属クロム
４％、ｐｅ２０．を０．５〜５％配合し、成形・焼成し
たマグクロダイレクトボンド煉瓦の品質例を示す。Table 2 shows that the main components are magnesia and chromite, 4% metallic chromium, and PE20. An example of the quality of magcro direct bonded bricks formed and fired with 0.5 to 5% blended is shown below.
表 ２
試作条件
試料の大ぎさ ７５ ｘｌ１４ ｘ２３０ｍｍ焼成温度
１８００℃
°未焼成部最大長は１１４ｘ２３０ｍｍの面に平行に三
等分した断面で観察した。Table 2 Prototype conditions Sample size 75 x 14 x 230 mm Firing temperature 1800°C ° The maximum length of the unfired part was observed on a cross section parallel to the 114 x 230 mm plane divided into three equal parts.
浸食試験条件
方法 誂導炉による内張浸食試験
温度 １６５０℃
時間 ４時間
雰囲気 真空
スラグ ｃ７’５−３ＣａＦ２＝２０％添加４００ｇ
ｘ ２回鋼 ５ｔｌＳ３０４１０ｋｇ
Ｆｅ２０．、、Ｆｅ３Ｏ４粒の添加量は、１％未満では
効果はなく、また、５０％を越えて添加すると耐火物の
耐食性に悪影響を与える。このため適正添加量は１〜５
０％、より好ましくは１〜５％である。またその粒度は
、金属と効率よく反応する必要性があるので、 ５００
μｍ以下が望ましい。純度に関しては、不要な低融点物
質生成防止の観点から、鉄酸化物以外の不純物が２０％
以下程度であることが望ましい。Erosion test conditions and methods: Lining erosion test using a convection furnace Temperature: 1650°C Time: 4 hours Atmosphere: Vacuum slag c7'5-3CaF2 = 20% addition 400g
x 2 times steel 5tlS30410kg Fe20. If the amount of Fe3O4 grains added is less than 1%, there will be no effect, and if it is added in excess of 50%, it will adversely affect the corrosion resistance of the refractory. Therefore, the appropriate amount to add is 1 to 5
0%, more preferably 1-5%. In addition, the particle size is 500 because it is necessary to react efficiently with the metal.
It is desirable that the thickness be less than μm. Regarding purity, from the perspective of preventing the formation of unnecessary low melting point substances, impurities other than iron oxides are 20%.
It is desirable that it be about the following.
以上、主にマグネシア・クロム質焼成煉瓦の場合を説明
したが、焼成煉瓦の場合は、焼成段階および使用中にお
いて又不焼成煉瓦の場合は使用中に金属クロムの酸化、
さらにマグネシアとの反応に伴う体積膨張により気孔率
の低減を図ることは、請求項２〜８の発明とも同様であ
る。すなわち本発明の耐火物素材はプレス成形後焼成す
れば焼成煉瓦として使用でき、プレス成形のみならば不
焼成煉瓦、そのまま、あるいは適当なバインダーを加え
れば不定形耐火物として使用できる。Above, we have mainly explained the case of magnesia-chromium fired bricks, but in the case of fired bricks, oxidation of metallic chromium occurs during the firing stage and during use, and in the case of unfired bricks, during use.
Furthermore, it is the same as the invention of claims 2 to 8 that the porosity is reduced by the volume expansion accompanying the reaction with magnesia. That is, the refractory material of the present invention can be used as a fired brick if it is press-formed and fired, or can be used as an unfired brick if only press-formed, or as a monolithic refractory as it is, or by adding a suitable binder.
［実 施 例］
金属クロム合金あるいは混合物の粉末を各種耐火物に添
加したものを試作し、さらに酸化クロム粉末、酸化アル
ミニウム粉末、Ｆｅ２Ｏ３粉末などを添加し、その効果
を調査した。その結果を表３に示す。[Example] Prototypes of various refractories were made by adding powder of a metal chromium alloy or a mixture thereof, and further, chromium oxide powder, aluminum oxide powder, Fe2O3 powder, etc. were added, and the effects thereof were investigated. The results are shown in Table 3.
試作条件
試料の大きさ ７５ ｘ １１４ ｘ ２３０ｍｍ焼
成温度 １８５０℃
６焼成むらは１１４ｘ ２３０ｍｍの面に平行に三等分
した断面で観察した。Prototype conditions Sample size: 75 x 114 x 230 mm Firing temperature: 1850°C 6. Firing unevenness was observed on a cross section that was divided into three equal parts parallel to a 114 x 230 mm surface.
浸食試験条件
方法 誘導炉による内張浸食試験
温度 １６５０℃
時間 ２時間
雰囲気 真空
スラグ ｃ／５−３ＣａＦ２＝ ２０％添加４００ｇ
ｘ ２回
ｔＩ４ＳＵＳ３０４１０ｋｇ
”″浸食試験後、各試料の最大溶損部の減寸量を測定し
、符号１の試料の減寸量を１００として基準化し、溶損
指数とした。溶損指数が小さいほど高耐食性である。Erosion test conditions and methods Lining erosion test using induction furnace Temperature: 1650°C Time: 2 hours Atmosphere: Vacuum slag c/5-3CaF2 = 20% addition 400g
x 2 times tI4SUS30410kg ``'' After the erosion test, the amount of reduction in size of the maximum erosion part of each sample was measured, and the amount of reduction in size of the sample with code 1 was standardized as 100, and this was used as the erosion index. The smaller the erosion index, the higher the corrosion resistance.
表３に示すように本発明によるクロム−鉄合金粉末を添
加した素材を使用したダイレクトボンド煉瓦である１は
、従来技術を用いて試作した１２よりも低気孔率であり
、緻密化がより進んていることがわかり、酸化クロムを
添加せずども緻密化することがわかる。酸化クロムを添
加した２では、更に緻密化が進んでいる。クロム−アル
ミニウム合金粉末を使用した３やあるいは４の場合も、
緻密化の効果が確認できた。As shown in Table 3, direct bond brick 1, which uses the material added with chromium-iron alloy powder according to the present invention, has a lower porosity than 12, which was prototyped using the conventional technology, and is more densified. It can be seen that densification can be achieved even without adding chromium oxide. In No. 2 to which chromium oxide was added, densification is further advanced. In the case of 3 or 4 using chromium-aluminum alloy powder,
The effect of densification was confirmed.
この緻密化が耐食性向上に貢献し、１〜４の耐食性は１
２のそれを平均で２０％以上上回っている。また、１で
は焼成むらが若干観察されたのに対して、本発明によっ
たものでは認められなかった。This densification contributes to improving corrosion resistance, and the corrosion resistance of 1 to 4 is 1
It exceeds that of 2 by more than 20% on average. Furthermore, while some unevenness in firing was observed in Sample No. 1, no unevenness was observed in the sample according to the present invention.
本発明による素材を使用したセミリボンド煉瓦である５
〜７でも、従来技術による１３と比較した場合、ダイレ
クトボンド煉瓦の場合と同様に緻密化が進行し、耐食性
が平均で１０％以上改善されている。また、焼成むらに
関しても、従来技術によるものでは認められたのに対し
て、本発明によるものでは観察されなかった。Semi-ribonded brick using the material according to the present invention 5
When compared with No. 13 made by the prior art, densification progresses in No. 7 to No. 7 as well as in the case of direct bonded bricks, and the corrosion resistance is improved by 10% or more on average. Also, regarding firing unevenness, while it was observed in the conventional technique, it was not observed in the present invention.
本発明による素材を使用したマグネシア煉瓦である１１
でも、従来技術による１４よりも緻密化が進行し、耐食
性は１６％改善された。また、１４では焼成むらがある
のに対して、１１では認められなかった。11 which is a magnesia brick using the material according to the present invention
However, the densification progressed more than that of the prior art No. 14, and the corrosion resistance was improved by 16%. In addition, in No. 14, there was uneven firing, whereas in No. 11, no unevenness was observed.
以上のように、本発明による耐火物素材を使用すること
で、従来技術によって得られる耐火物を凌ぐものが安定
して、しかも安価に製造できる。このため、本発明によ
り鉄鋼窯炉用耐火物の寿命は延長され、多大な効果がも
たらされる。ゆえに、本発明は非常に有益である。As described above, by using the refractory material according to the present invention, it is possible to stably and inexpensively produce a refractory that surpasses the refractories obtained by conventional techniques. Therefore, according to the present invention, the life of the refractory for steel kilns is extended, and a great effect is brought about. Therefore, the present invention is highly beneficial.
［発明の効果コ
本発明の耐火物素材は金属クロムを適量含有させたマグ
ネシア系のものであり、この金属クロムが耐火物製造時
酸化して酸化クロム化する際の体積膨張を利用して他の
耐火物特性を劣化させることなく耐火物組織を緻密化す
ることがで籾、特に圧縮強度、耐溶損性にすぐれた耐火
物を得ることができる。また必要に応じて、金属クロム
以外の金属、酸化アルミニウム、酸化鉄等焼結助剤を配
合することによって焼結を均一に促進し、耐火物組織の
緻密化を一層促進し耐溶損性、強度をより一層向上させ
ることができる。[Effects of the Invention] The refractory material of the present invention is a magnesia-based material containing an appropriate amount of metallic chromium, and the volumetric expansion when this metallic chromium oxidizes to chromium oxide during refractory production is utilized to produce other materials. By densifying the refractory structure without deteriorating the refractory properties of rice grains, it is possible to obtain refractories with excellent compressive strength and erosion resistance. In addition, if necessary, sintering aids such as metals other than metallic chromium, aluminum oxide, and iron oxide may be added to promote uniform sintering and further promote the densification of the refractory structure, improving corrosion resistance and strength. can be further improved.
第１図は本発明の金属クロムを含有する耐火物素材をプ
レス成形した場合の金属クロムの分散状況説明図、第２
図は第１図の耐火物素材を焼成した場合の組織説明図、
第３図はクロム合金、化合物、混合物中の金属鉄、金属
アルミニウム、金属マグネシウム、金属シリコン成分と
未焼成部分の最大長との関係を示す図である。
１ ・・・ＭｇＯ
２・・・クロム鉱
３・・・クロム粉末 ４・・・クロム鉱他４名Figure 1 is an explanatory diagram of the dispersion state of metallic chromium when the refractory material containing metallic chromium of the present invention is press-molded, and Figure 2
The figure is an explanatory diagram of the structure when the refractory material shown in Figure 1 is fired.
FIG. 3 is a diagram showing the relationship between the components of metallic iron, metallic aluminum, metallic magnesium, and metallic silicon in chromium alloys, compounds, and mixtures and the maximum length of the unfired portion. 1...MgO 2...Chromite 3...Chromium powder 4...Chromite and 4 others
Claims (1)
属クロムと金属鉄、金属マグネシウム、金属アルミニウ
ム、金属シリコンなどの金属との合金、又は化合物ある
いは混合物粉末を１〜２０重量％混合したことを特徴と
する耐火物素材。 ２ 金属クロムを含有する電融マグクロにマグネシア、
スピネル、クロム鉱のうち１種以上を混合したことを特
徴とする耐火物素材。 ３ 請求項１の耐火物素材に、焼結助剤として酸化クロ
ム粉末又は酸化アルミニウム粉末あるいはこれらの混合
物粉末１〜２０重量％を添加したことを特徴とする耐火
物素材。 ４ 請求項１の耐火物素材に、酸化鉄粉末を１〜５０重
量％添加したことを特徴とする耐火物素材。 ５ 請求項１の耐火物素材に、酸化クロム粉末又は酸化
アルミニウムあるいはこれらの混合物を１〜２０重量％
混合し、さらに酸化鉄を１〜５０重量％混合したことを
特徴とする耐火物素材。 ６ 請求項２の耐火物素材に、酸化クロム粉末又は酸化
アルミニウム粉末あるいはこれらの混合物を１〜２０重
量％を添加したことを特徴とする耐火物素材。 ７ 請求項２の耐火物素材に、酸化鉄粉末を１〜５０重
量％混合したことを特徴とする耐火物素材。 ８ 請求項２の耐火物素材に、酸化クロム粉末又は酸化
アルミニウム粉末あるいはこれらの混合物を１〜２０重
量％添加し、さらに酸化鉄粉末を１〜５０重量％を添加
したことを特徴とする耐火物素材。[Claims] 1. 1 to 20% by weight of an alloy, compound, or mixture powder of metal chromium and metal such as metal iron, metal magnesium, metal aluminum, metal silicon, etc. is mixed into magnesia or a refractory material containing magnesia. A refractory material characterized by: 2 Magnesia is added to electrofused maguro containing metallic chromium.
A refractory material characterized by a mixture of one or more of spinel and chromite. 3. A refractory material characterized in that 1 to 20% by weight of chromium oxide powder, aluminum oxide powder, or a mixture powder thereof is added as a sintering aid to the refractory material according to claim 1. 4. A refractory material characterized in that 1 to 50% by weight of iron oxide powder is added to the refractory material according to claim 1. 5 1 to 20% by weight of chromium oxide powder, aluminum oxide, or a mixture thereof to the refractory material of claim 1.
A refractory material characterized by being mixed with 1 to 50% by weight of iron oxide. 6. A refractory material characterized in that 1 to 20% by weight of chromium oxide powder, aluminum oxide powder, or a mixture thereof is added to the refractory material according to claim 2. 7. A refractory material comprising the refractory material of claim 2 mixed with 1 to 50% by weight of iron oxide powder. 8. A refractory characterized by adding 1 to 20% by weight of chromium oxide powder, aluminum oxide powder, or a mixture thereof to the refractory material of claim 2, and further adding 1 to 50% by weight of iron oxide powder. material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1225795A JP2540214B2 (en) | 1988-08-31 | 1989-08-31 | Refractory material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-216666 | 1988-08-31 | ||
| JP21666688 | 1988-08-31 | ||
| JP1225795A JP2540214B2 (en) | 1988-08-31 | 1989-08-31 | Refractory material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02141465A true JPH02141465A (en) | 1990-05-30 |
| JP2540214B2 JP2540214B2 (en) | 1996-10-02 |
Family
ID=26521562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1225795A Expired - Fee Related JP2540214B2 (en) | 1988-08-31 | 1989-08-31 | Refractory material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2540214B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006128556A2 (en) * | 2005-05-30 | 2006-12-07 | Refractory Intellectual Property Gmbh & Co. Kg | Refractory ceramic product |
| JP2011201728A (en) * | 2010-03-25 | 2011-10-13 | Kurosaki Harima Corp | Magnesia-chromium based brick |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5632368A (en) * | 1979-08-10 | 1981-04-01 | Veitscher Magnesitwerke Ag | Nonburnt ore material containing refractory carbon whose main component is sintered magnesia |
| JPS56109867A (en) * | 1980-12-08 | 1981-08-31 | Toshiba Ceramics Co | Dipping nozzle composition for casting |
| JPS5964569A (en) * | 1982-09-29 | 1984-04-12 | 黒崎窯業株式会社 | High strength high corrosion resistance continuous casting refractories |
| JPS61205660A (en) * | 1985-03-11 | 1986-09-11 | ハリマセラミック株式会社 | Manufacture of chromium-containing magnesia refractory brick |
-
1989
- 1989-08-31 JP JP1225795A patent/JP2540214B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5632368A (en) * | 1979-08-10 | 1981-04-01 | Veitscher Magnesitwerke Ag | Nonburnt ore material containing refractory carbon whose main component is sintered magnesia |
| JPS56109867A (en) * | 1980-12-08 | 1981-08-31 | Toshiba Ceramics Co | Dipping nozzle composition for casting |
| JPS5964569A (en) * | 1982-09-29 | 1984-04-12 | 黒崎窯業株式会社 | High strength high corrosion resistance continuous casting refractories |
| JPS61205660A (en) * | 1985-03-11 | 1986-09-11 | ハリマセラミック株式会社 | Manufacture of chromium-containing magnesia refractory brick |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006128556A2 (en) * | 2005-05-30 | 2006-12-07 | Refractory Intellectual Property Gmbh & Co. Kg | Refractory ceramic product |
| WO2006128556A3 (en) * | 2005-05-30 | 2007-07-19 | Refractory Intellectual Prop | Refractory ceramic product |
| EA011907B1 (en) * | 2005-05-30 | 2009-06-30 | Рифректори Интеллектуал Проперти Гмбх & Ко.Кг | Refractory ceramic product |
| JP2011201728A (en) * | 2010-03-25 | 2011-10-13 | Kurosaki Harima Corp | Magnesia-chromium based brick |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2540214B2 (en) | 1996-10-02 |
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