WO2003027040A1 - Materiau de revetement thermo-isolant destine a un refractaire contenant du carbone - Google Patents

Materiau de revetement thermo-isolant destine a un refractaire contenant du carbone Download PDF

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Publication number
WO2003027040A1
WO2003027040A1 PCT/JP2002/009765 JP0209765W WO03027040A1 WO 2003027040 A1 WO2003027040 A1 WO 2003027040A1 JP 0209765 W JP0209765 W JP 0209765W WO 03027040 A1 WO03027040 A1 WO 03027040A1
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Prior art keywords
weight
refractory
coating material
carbon
hollow
Prior art date
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PCT/JP2002/009765
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English (en)
French (fr)
Inventor
Noboru Tsukamoto
Shuji Shike
Eishi Iida
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Shinagawa Refractories Co., Ltd.
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Application filed by Shinagawa Refractories Co., Ltd. filed Critical Shinagawa Refractories Co., Ltd.
Priority to US10/489,620 priority Critical patent/US20040241446A1/en
Priority to EP02768012A priority patent/EP1443031A1/en
Publication of WO2003027040A1 publication Critical patent/WO2003027040A1/ja

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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • the present invention relates to a heat insulating coating material which prevents surface oxidation of a carbon-containing refractory, suppresses heat dissipation from the surface as a heat insulating layer, and does not cause environmental health problems.
  • Carbon-containing refractories such as alumina-graphite and zirconia-graphite, are used as refractories for construction used in continuous production of steel.
  • the carbon-containing refractory is coated with an antioxidant mainly composed of glass powder on the surface to prevent carbon oxidation during preheating and during use.
  • heat insulating material consisting of glass fiber or ceramic fiber is usually wound around the outer surface of carbon-containing refractories. Is widely practiced.
  • heat insulation materials made of fibrous materials such as glass fibers or ceramic fibers have become an environmental health problem.
  • Japanese Patent Application Laid-Open No. 7-147174 discloses that vermiculite heat-treated at 300 to 1200 ° C. is 3 to 30% by weight, Obsidian that forms a hollow structure with heat of 800 ° C or more ⁇ Pearlite ⁇ Pinestone ⁇
  • One or more types of expansive shale are 1 to 30% by weight in an unheated state, and 400 to 150% Glass powder that softens and melts in the range of ° C, or pyroxene 'silica stone' chamotte 'mullitealumina' fused silica-zirconiamagnesia or refractory powder of at least 40 to 96% by weight
  • a heat-insulating antioxidant for graphite-containing refractories having a heat-insulating property in which a liquid binder is blended in an amount of 20 to 250% by weight with the mixture is disclosed.
  • Japanese Unexamined Patent Publication (Kokai) No. Hei 9-157,045 discloses that refractory raw materials having a particle size of 0.5 to 6.0 mm, having a hollow particle size of 15 to 70% by weight, and having a particle size of 1 mm or less. 0-3 5% by weight, d, Xy-alumina intermediate 10 to 40% by weight, microsilica 0.5 to 5.0% by weight, air entrainer 0.01 to 0.4% by weight, and thickening Disclosed is a refractory insulated castable refractory comprising 0.1 to 0.5% by weight of an agent.
  • Japanese Patent Application Laid-Open No. 11-49757 discloses that alumina hollow particles having a particle size of 0.5 to 6.0 mm are 15 to 70% by weight, and magnesia having a particle size of 1 mm or less. 2 to 30% by weight of at least one of the first fine refractory raw materials mainly containing subinel, and a main component mainly containing at least one of alumina, mullite, silica, and zirconia having a particle size of 1 mm or less. 8 to 60% by weight of the second fine refractory raw material, and 5 to 45% by weight of at least one of alumina cement having hydraulic component and alumina component of 65% by weight or more, and 5 to 45% by weight of air entraining agent. Disclosed is an amorphous refractory characterized by the fact that it comprises a mixture of 0.4% by weight and a thickener (0.1-0.5% by weight).
  • the heat-insulating antioxidant for graphite-containing refractories disclosed in Japanese Patent Application Laid-Open No. 7-24771-4 is an unheated obsidian, perlite, pinestone, expansive shale (hereinafter referred to as foaming). Content is defined as 1 to 30% by weight. However, even if 30% by weight of expandable pearlite is blended, a sufficient foamed heat insulating layer can be obtained during heating. I can't.
  • the foamable foam is foamed when heated, but when foamed, the adhesion to the graphite-containing refractory as a base material is deteriorated, and a gap is formed between the base material and the foamed layer, and the foamed layer may also come off. is there.
  • the fire-resistant heat-insulated cast refractory disclosed in Japanese Patent Application Laid-Open No. 9-157045 uses refractory hollow particles having a large particle size. When it is used for heat treatment, it becomes difficult to form a heat insulating layer. In addition, since it does not contain a glass phase forming component, there is a problem that the bonding strength of the heat insulating layer in the operating temperature range of the carbon-containing refractory is insufficient.
  • the heat-insulating coating material for refractory containing carbon is used because refractory hollow particles having a large particle size are used. When it is used for heat treatment, it becomes difficult to form a heat insulating layer.
  • it contains hydraulic alumina and alumina cement, when it is applied as a heat-insulating coating material for refractories containing carbon, the heat-insulating layer cracks during use, and the There is a problem that it is easy to release.
  • an object of the present invention is to provide a heat-insulating coating material for carbon-containing refractories which can prevent surface oxidation of a carbon-containing refractory at the time of high-temperature heating and can form a heat-insulating layer.
  • the heat insulating coating material for a carbon-containing refractory of the present invention employs a hollow refractory powder.
  • the heat-insulating coating material for a carbon-containing refractory of the present invention contains hollow refractory particles, the content of the hollow particles is 597% by weight, the remaining part or all is clay, and A liquid binder is added to a refractory material having a clay content of 30% by weight or less, and 210.70% by weight of a liquid binder is added.
  • the heat insulating coating material for refractory containing carbon of the present invention contains hollow refractory particles, the content of the hollow particles is 509% by weight, and the content of the clay is 225% by weight. % Or the remaining part is vermiculite in which water of crystallization is dehydrated and / or glass powder that softens and melts in a temperature range of 500 1100 ° C., and / or vermiculite in which the water of crystallization is dehydrated. Liquid binder is added to the refractory material whose total amount of glass powder softening and melting in the temperature range of 500 ° C. is not more than 30% by weight, and a liquid binder is added at a rate of 201% to 0% by weight. And
  • the heat-insulating coating material for the refractory containing carbon of the present invention is one or two or more selected from fused quartz, magnesite, magnesia, zirconia, spinel, alumina, chamotte, limestone, and clay shale. It is characterized by containing at least 10% by weight of at least one compound.
  • insulation co one coating material forces one carbon-containing refractory of the present invention, the hollow refractory particles child, S i 0 2 and A 1 2 0 3 containing, the content S i 0 2: 40 to 80% by weight,
  • a 1 2 0 3 wherein the 2 0 6 0% by weight.
  • the heat-insulating coating material for refractory containing carbon according to the present invention is characterized in that the particle size range of the hollow refractory particles is in the range of 380 microns.
  • FIG. 1 is a schematic diagram of an apparatus for explaining measurement of a temperature drop in an embodiment.
  • 1 denotes a heating box
  • 2 denotes an immersion nozzle for continuous production
  • 3 denotes a coating material coating film
  • 4 denotes a gas burner
  • 5 denotes a temperature measurement position.
  • the present inventors have applied hollow refractory particles to solve the above-described problems and achieve a stable antioxidant effect and the formation of a heat insulating layer, thereby minimizing the volume change of the heat insulating layer during heating.
  • the present invention was completed by studying in detail the amount of refractory raw materials to be added to maintain the bonding of the structure of the heat insulating material and to improve the adhesion between the heat insulating layer and the refractory base material. is there. '
  • the heat-insulating coating material for refractory containing carbon according to the present invention is characterized by containing hollow refractory particles, and the content of the hollow refractory particles is 50 to 97 in the refractory material. % By weight. More preferably, it is 55 to 94% by weight.
  • the content of the hollow refractory particles is less than 50% by weight, a sufficient heat insulating effect cannot be obtained, which is not preferable.
  • the content of the hollow refractory particles exceeds 97% by weight, the structure of the heat insulating layer becomes insufficiently bonded, causing problems such as peeling and cracking, which is also unsuitable.
  • the hollow refractory particles used in the present invention represent hollow particles having a hollow center, and the thickness of the shell and the shape of the hollow particles are not particularly specified. These hollow particles include not only spherical closed hollow particles but also hollow particles partially having a hole. Generally, those having an open area of 1 to 4 or less on the particle surface can be used as the hollow particles of the present invention.
  • the hollow volume of these hollow particles is usually 50 to 90%, preferably 60 to 80%.
  • These hollow particles are obtained by crushing, sintering, flotation, drying, and classification of mineral raw materials mainly composed of silica and alumina, and are commercially available under trade names such as ES pheres. be able to.
  • S i 0 2 content of the hollow refractory particles child is less than 4 0% by weight
  • a 1 2 0 3 content exceeds 6 0 wt% If, sinterability of the hollow refractory particles And the bonding of the structure of the heat insulating layer at the time of heating at a high temperature becomes insufficient, and the coating material is easily peeled off from the base material, which is not preferable.
  • S i 0 2 content of the hollow refractory particles is more than 8 0% by weight
  • the content of A 1 2 0 3 is less than 2 0% by weight
  • the use of carbon-containing refractories causes problems such as increased erosion of the thermal insulation coating.
  • the content of S i 0 2 and A 1 2 0 3 is more preferably S i 0 2 5 0-7 0 wt%, A 1 2 0 3 is 3 0-5 0% by weight.
  • the content in this case S i 0 2, A 1 2 0 3 other components is preferably 1 0% by weight or less. If the total of these components exceeds 10% by weight, the heat resistance of the hollow refractory particles decreases, and the coating material softens and melts when used at a high temperature.
  • the particle size range of the hollow refractory particles of the present invention is in the range of 30 to 800 microns. If it is less than 30 microns, the kneadability with the liquid binder will be poor, and the workability on refractory containing carbon fiber will be poor, which is inappropriate. Further, when the hollow refractory particles are smaller than 30 microns, there is a problem that the heat insulating property is deteriorated. On the other hand, if the particle size of the hollow refractory particles exceeds 800 ⁇ m, the heat insulating layer is not suitable because the tissue bonding force of the heat insulating layer at the time of heating is reduced, causing cracks and easy detachment from the base material. .
  • the size range of the hollow refractory particles is more preferably between 50 and 700 microns.
  • the particle size referred to here indicates the average particle size of the hollow refractory particles.
  • the compounding amount of the clay in the heat insulating coating material of the carbon-containing refractory of the present invention is not more than 30% by weight, and preferably in the range of 3 to 20% by weight. If the amount of the clay exceeds 30% by weight, the sintering shrinkage of the heat insulating layer due to the clay component increases during preheating and use, and cracks tend to occur in the heat insulating coating layer. Appropriate.
  • the heat-insulating coating material for a carbon-containing refractory of the present invention comprises As components other than the fire particles and clay, vermiculite dehydrated from water of crystallization and / or glass powder that softens and melts in a temperature range of 500 to 110 ° C. can be used in combination. By using the vermiculite together, the heat insulating effect can be exhibited from a lower temperature range. Also, by using a glass powder that softens and melts in a temperature range of 500 to 110 ° C., the structure of the heat insulating layer can be bonded from a lower temperature.
  • the mixing ratio of vermiculite is desirably 20% by weight or less.
  • the amount of glass powder added is preferably 10% by weight or less. This is because if it exceeds 10% by weight, the melting of the glass at a high temperature becomes excessive, and it becomes difficult to hold the coating layer. Further, it is desirable that the total added amount of vermiculite and glass powder is 30% by weight or less.
  • the softening temperature of the glass powder is optimally within the range of 500 to 110 ° C considering the general preheating conditions and the temperature conditions during use of the carbon-containing refractory. .
  • the heat-insulating coating material for carbon-containing refractories of the present invention comprises, as components other than the hollow refractory particles, clay, vermiculite, and glass powder, fused quartz, mullite, magnesium, zirconia, spinel, alumina, It is also possible to use one or two or more selected from the group of the compounds of chamotte, pyroxene, and clay shale. These compounds are used to adjust the heat resistance of the heat-insulating coating layer at high temperatures and to control cracking and peeling of the heat-insulating coating material during use, depending on the heating and use conditions of the refractory containing carbon. Is to be blended.
  • the addition amount of these compounds is desirably 10% by weight or less. If the content exceeds 10% by weight, sintering shrinkage due to these components will increase during heating and during use, causing cracks in the heat insulating layer and problems such as easy separation of the base material and the heat insulating layer. It is inappropriate.
  • the above-mentioned hollow heat-resistant particles and refractory raw materials such as clay, vermiculite and glass powder are mixed using a liquid binder.
  • a liquid binder it is preferable to apply a coating material to the surface of the carbon-containing refractory and then dry it at a temperature of 300 ° C. or less to form a coating film.
  • a coating material for example, potassium silicate, aluminum phosphate, colloidal Silica or the like can be used. It is also possible to use several kinds of liquid binders together
  • the amount of liquid binder to be added is 20 to 170 weight per unit of refractory material. %, Preferably 30 to 150% by weight. If the added amount of the liquid binder is less than 20% by weight, the effect of the addition is not exhibited, and it is difficult to apply the liquid binder to the surface of the refractory containing carbon. On the other hand, if the amount is more than 170% by weight, it is not preferable because the coating property on the carbon-containing refractory decreases due to the decrease in viscosity.
  • the method of applying to the surface of the refractory containing carbon is not limited, and the method may be selected according to the shape and size of the refractory containing carbon to be applied, the construction environment, and the like. it can.
  • the coating material of the carbon-containing refractory of the present invention will be further described with reference to examples.
  • the present invention is not limited by the examples.
  • the coating materials of the present invention and comparative products were obtained at the mixing ratios shown in Table 1 below.
  • the hollow refractory particles used here had the following appearance: white, bulk specific gravity: 0.25-0.42 g / cm 3 , and the composition and particle size were as follows:
  • the obtained coating material A 1 2 0 3 5 0 wt%, S i 0 2 2 5 wt%, the immersion nozzle for continuous ⁇ made of carbon-containing refractory having a composition of carbon 2 5 wt% After spray coating the outer surface to a thickness of about 3 mm and drying at 130 ° C for 4 hours, set the continuous production immersion nozzle (2) in the heating box (1) shown in Fig. 1 Heat to 125 ° C with a submerged (4), hold at that temperature for 6 hours, Remove from the box (1), leave the continuous production immersion nozzle (2) in the air, and check the temperature drop (after 10 minutes) at the temperature measurement position (5) under the coating material coating (3). It was measured. After cooling, the state of the coating film of the coating material was visually observed.
  • the glass powder used in the product 1 of the present invention had a melting softening temperature of 1000 ° C.
  • Comparative product 1 was a blank that was not sprayed with a coating material.
  • Comparative product 2 was a 3 mm-thick ceramic paper stuck to a continuous production immersion nozzle of the same material as above. Things.
  • Example 3 Compounds of the present invention and comparative products were obtained at the compounding ratios shown in Table 3 below.
  • the hollow refractory particles D of Example 1 were used as the hollow refractory particles used in Example 2.
  • the same raw materials as those used in Example 1 were used for glass powder, clay and vermiculite.
  • Fused quartz, mullite, magnesia, zirconia, spinel, alumina, chamotte, pyroxene, and sand shale were all made from raw materials of 0.3 mm or less.
  • the resulting coating material A 1 2 0 3 60 wt%, Si0 2 10 wt%, the continuous ⁇ kiln immersion nozzle outer surface of Le composed of carbon-containing refractory having a composition of forces one carbon 30 wt% to about
  • a heating test and evaluation were performed in the same manner as in Example 1. Table 3 shows the obtained results.
  • the heat insulation layer which consists of a coating material coating film can be formed, and it has the effect that the continuous Useful as thermal insulation coating material in construction 0

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Description

明 細 書 カーボン含有耐火物の断熱コ一ティング材
技術分野
本発明は、 カーボン含有耐火物の表面酸化を防止し、 断熱層として表面からの 熱放散を抑制すると共に環境衛生上の問題を生じない、 断熱コ一ティング材に関 するものである。
背景技術
鋼の連続鎵造に使用される鎵造用耐火物には、 例えばアルミナ—黒鉛質、 ジル コニァ一黒鉛質などのカーボン含有耐火物が使用されている。 カーボン含有耐火 物は、 予熱中及び使用中のカーボン酸化を防止するために表面に主としてガラス 粉末よりなる酸化防止剤が塗布されている。 また、 カーボン含有耐火物は、 通常 予熱終了後及び使用中に表面からの熱放散による温度降下を防止するために、 ガ ラスフアイバーあるいはセラミックファイバ一よりなる断熱保温材を外表面に卷 き付けることが広く行われている。 しかしながら、 近年、 ガラスフアイパーある いはセラミックフアイバーなどの繊維状物質からなる保温断熱材が環境衛生上の 問題となっている。
この問題を解決するために、 例えば特開平 7— 1 4 7 1 7 4号公報には、 3 0 0〜1 2 0 0 °Cで加熱処理された蛭石を 3〜3 0重量％と、 8 0 0 °C以上の熱で 中空組織化する黒曜石 ·真珠岩 ·松脂岩 ·膨張頁岩の一種もしくは二種以上を未 加熱状態で 1〜3 0重量％と、 4 0 0〜1 5 0 0 °Cの範囲で軟化溶融するガラス 粉末、 または、 ろう石 'けい石 'シャモット 'ムライト ·アルミナ '溶融シリカ -ジルコニァ ·マグネシアの一種もしくは二種以上の耐火粉末を 4 0〜9 6重量 %とからなる混合物に液体バインダーを外掛けで 2 0〜2 5 0重量％配合した断 熱性を有する黒鉛含有耐火物の断熱性酸化防止剤が開示されている。
また、 特開平 9一 1 5 7 0 4 5号公報には、 粒度 0 . 5〜6 . 0 mmの高耐火 性セラミヅクスの中空粒 1 5〜7 0重量％、 粒度 1 mm以下の耐火原料 1 0〜3 5重量％、 、 d、 X y—アルミナ中間体 1 0〜4 0重量％、 マイクロシリカ 0 . 5〜5 . 0重量％、 空気連行剤 0 . 0 1〜0 . 4重量％、 及び増粘剤 0 . 0 1〜0 . 5重量％からなることを特徴とする耐火断熱キャス夕ブル耐火物が開示 されている。
更に、 特開平 1 1—4 9 5 7 7号公報には、 粒径が 0 . 5〜6 . O mmのアル ミナ中空粒 1 5〜7 0重量％と、 粒径が 1 mm以下のマグネシア、 スビネルを主 成分とする少なくともいずれか一種の第一の微粒の耐火原料の 2〜3 0重量％、 粒径が l mm以下のアルミナ、 ムライト、 シリカ、 ジルコニァの少なくとも一種 を主成分とする第二の微粒の耐火原料 8〜 6 0重量％と、 水硬性アルミナ、 アル ミナ成分 6 5重量％以上のアルミナセメントの少なくともいずれか一種 5〜 4 5 重量％と、 空気連行剤 0 . 0 1〜0 . 4重量％と、 増粘剤ひ. ' 0 1〜0 . 5重量 %との混合物から成ることを特徴とする不定形耐火物が開示されている。
しかしながら、 特開平 7— 2 4 7 1 7 4号公報に開示されている黒鉛含有耐火 物の断熱性酸化防止剤は、 未加熱状態の黒曜石 ·真珠岩 ·松脂岩■膨張頁岩 （以 下、 発泡性パ一ライトと称す） の含有量が 1〜3 0重量％と規定されているが、 発泡性パーライトを 3 0重量％配合しても、 実質的には加熱時に充分な発泡断熱 層は得られない。 また、 発泡性パ一ライ トは加熱時に発泡するが、 発泡すると母 材である黒鉛含有耐火物との密着性が悪くなり、 母材と発泡層の間に隙間を生じ 、 剥落に至ることもある。
また、 特開平 9— 1 5 7 0 4 5号公報に開示されている耐火断熱キャス夕プル 耐火物は、 粒度の大きい耐火性中空粒を使用しているため、 カーボン含有耐火物 用断熱コーティング材用として使用した場合、 断熱層の形成が困難となる。 また 、 ガラス相形成成分を含まないため、 カーボン含有耐火物の使用温度域での断熱 層の結合力が不充分という問題がある。
更に、 特開平 1 1— 4 9 5 7 7号公報に開示されている不定形耐火物において も、 粒度の大きい耐火性中空粒を使用しているため、 力一ボン含有耐火物用断熱 コーティング材用として使用した場合、 断熱層の形成が困難となる。 また、 水硬 性アルミナやアルミナセメントを含有しているため、 力一ボン含有耐火物の断熱 コーティング材として適用した場合、 使用時に断熱層に亀裂が生じ、 母材から剝 離し易くなるという問題がある。
発明の開示
従って、 本発明の目的は、 高温加熱時に力一ボン含有耐火物の表面酸化を防止 すると共に断熱層を形成することができるカーボン含有耐火物用断熱コ一ティン グ材を提供することにある。
上記課題を解決し、 安定した酸化防止効果と断熱層の形成を実現するため、 本 発明のカーボン含有耐火物の断熱コ一ティング材では、 中空の耐火性粉末を適用 するものである。
即ち、 本発明のカーボン含有耐火物の断熱コーティング材は、 中空の耐火性粒 子を含有し、 該中空粒子の含有量が 5 0 9 7重量％、 残部の 部または全てが 粘土であり、 且つ粘土の含有量が 3 0重量％以下である耐火材料に、 液状バイン ダ一を外掛で 2 0 1 7 0重量％添加したことを特徴とする。
また、 本発明の力一ボン含有耐火物の断熱コーティング材は、 中空の耐火性粒 子を含有し、 該中空粒子の含有量が 5 0 9 4重量％、 粘土の含有量が 2 2 5 重量％、 残部の一部または全てが、 結晶水を脱水した蛭石及びまたは 5 0 0 1 1 0 0 °Cの温度範囲で軟化溶融するガラス粉末であり、 該結晶水を脱水した蛭石 及びまたは 5 0 0 1 1 0 0 °Cの温度範囲で軟化溶融するガラス粉末の合計量が 3 0重量％以下である耐火材料に、 液状バインダーを外掛で 2 0 1 Ί 0重量％ 添加したことを特徴とする。
更に、 本発明の力一ボン含有耐火物の断熱コ一ティング材は、 溶融石英、 ムラ ィ ト、 マグネシア、 ジルコニァ、 スピネル、 アルミナ、 シャモヅト、 ろう石、 ば ん土頁岩から選ばれた一種または二種以上の化合物を 1 0重量％以下含有するこ とを特徴とする。
また、 本発明の力一ボン含有耐火物の断熱コ一ティング材は、 中空の耐火性粒 子が、 S i 02及び A 1203を含有し、 その含有量が S i 02 : 4 0 ~ 8 0重量％、
A 1203： 2 0 6 0重量％であることを特徴とする。
更に、 本発明の力一ボン含有耐火物の断熱コーティング材は、 中空の耐火性粒 子の粒度範囲が、 3 0 8 0 0ミクロンの範囲内にあることを特徴とする。 図面の簡単な説明 '
図 1は、 実施例における温度降下の測定を説明する装置の概略図である。 図 1において、 1は加熱ボックス、 2は連続鎵造用浸漬ノズル、 3はコ一ティ ング材塗膜、 4はガスバーナー、 5は温度測定位置、 をそれぞれ示す。
発明を実施するための最良の形態
本発明者らは、 前述した問題を解決し、 安定した酸化防止効果と断熱層の形成 を実現するため、 中空の耐火性粒子を適用することで、 加熱時の断熱層の体積変 化を極力抑え、 断熱材の組織の結合を保つとともに、 断熱層と耐火物母材間の密 着性を高める為の適量の耐火性原料の添加量などを詳細に検討し、 本発明を完成 したものである。 '
本発明の力一ボン含有耐火物の断熱コーティング材は、 中空の耐火性粒子を含 有することを特徴とするものであり、 該中空の耐火性粒子の含有量は耐火材料中 5 0〜9 7重量％の範囲内である。 更に好適には、 5 5 ~ 9 4重量％である。 こ こで、 中空の耐火性粒子の含有量が 5 0重量％未満では充分な断熱効果が得られ ず好ましくない。 また、 中空の耐火性粒子の含有量が 9 7重量％をこえると、 断 熱層の組織の結合が不充分となり、 剥離や亀裂の問題を生じ、 やはり不適当であ る。
なお、 本発明で使用する中空の耐火性粒子は、 中央部が空洞になっている中空 粒を示すものであり、 殻部の厚さや中空粒の形状については特に規定するもので はない。 これらの中空粒子には、 球状の閉鎖中空粒子は勿論、 一部に閧孔を有す る中空粒子も含まれる。 一般的には、 開孔部分の面積が粒子表面の 1ノ4以下の ものは、 本発明の中空粒子として使用し得るものである。 また、 これら中空粒子 の空洞容積は、 通常 5 0〜9 0 %、 好ましくは 6 0〜8 0 %である。 これらの中 空粒子は、 シリカ、 アルミナを主成分とする鉱物原料を粉砕、 焼成、 浮遊選鉱、 乾燥、分級等して得られるもので、商業的には E S p h e r e s等の商品名で入 手することができる。
また、 本発明のカーボン含有耐火物の断熱コーティング材において、 中空の耐 火性粒子は S i 02及び A 1203を含有し、 その含有量は S i 02が 4 0〜8 0重量 %の範囲、 A 1203が 2 0〜6 0重量％の範囲である。 ここで、 中空の耐火性粒 子の S i 02含有量が 4 0重量％未満、 A 1203の含有量が 6 0重量％を超える場 合、 中空の耐火性粒子の焼結性が低下し、 高温加熱時における断熱層の組織の結 合が不充分となり、 コーティング材が母材から剥がれ易くなるために好ましくな い。 また、 中空の耐火性粒子の S i 02含有量が 8 0重量％を超えると、 A 1203 の含有量が 2 0重量％未満の場合、 中空の耐火性粒子の耐熱性が低下し、 カーボ ン含有耐火物の使用時に断熱コ一ティング部の溶損が大きくなるなどの問題が生 じる。 S i 02及び A 1203の含有量は、 より好適には S i 02が 5 0〜7 0重量％ 、 A 1203が 3 0〜5 0重量％である。更に、 上記 S i〇2、 A 1203の含有率の範 囲で、 中空の耐火性粒子中には、 S i 02、 A 1203以外の成分を含有することも 可能である。 その場合 S i 02、 A 1203以外の成分の含有量は 1 0重量％以下が 好ましい。 これらの成分の合計が 1 0重量％を超えると中空の耐火性粒子の耐熱 性が低下し、 高温での使用時にコーティング材が軟化溶融する問題を生じる。 S i 02、 A 1203以外の成分としては、 例えば T i 02、 F e 203、 N a20、 K20、 C a O、 M g O、 L i 20などが挙げられる。
また、 本発明の中空の耐火性粒子の粒度範囲は、 3 0〜 8 0 0ミクロンの範囲 内である。 3 0ミクロン未満の場合、 液状バインダ一との混練性が不良となるた め力一ボン含有耐火物への施工性が不良となり不適当である。 さらに中空の耐火 性粒子が 3 0ミクロン未満の場合断熱特性が低下する問題も生じる。 また、 中空 の耐火性粒子の粒度が 8 0 0ミクロンを超えると、 加熱時の断熱層の組織結合力 が低下し、 亀裂が生じたり、 母材と剥がれやすくなる問題が生じるため不適当で ある。 中空の耐火性粒子の粒度範囲はより好適には、 5 0〜7 0 0ミクロンであ る。 なお、 ここで言う粒度は、 中空の耐火性粒子の平均粒径を示すものである。 本発明のカーボン含有耐火物の断熱コーティング材中における粘土の配合量は 、 3 0重量％以下でぁり、 好ましくは 3 ~ 2 0重量％の範囲である。 ここで、 粘 土の配合量が 3 0重量％を超えると、 予熱時及び使用時に粘土成分に起因する断 熱層の焼結収縮が大きくなり、 断熱コ一ティング層に亀裂が生じ易くなり不適当 である。
更に、 本発明のカーボン含有耐火物の断熱コーティング材は、 上記の中空の耐 火性粒子や粘土以外の成分として、 結晶水を脱水した蛭石及びまたは 5 0 0〜1 1 0 0 °Cの温度範囲で軟化溶融するガラス粉末を併用することも可能である。 蛭 石を併用することで、 より低い温度域から断熱効果を発揮させることができる。 また、 5 0 0〜 1 1 0 0 °Cの温度範囲で軟化溶融するガラス粉末を併用すること により、 断熱層の組織をより低温から結合させることが可能となる。 ここで、 蛭 石の配合割合は、 2 0重量％以下とすることが望ましい。 これは、 熱処理を施し 、 結晶水を脱水した蛭石は多孔質でかつ密度が小さいことから、 コーティング材 として使用した場合に体積が嵩張るためである。 一方、 ガラス粉末の添加量は 1 0重量％以下が好ましい。 これは、 1 0重量％を超えると、 高温でのガラスの溶 融が過大となり、 コ一ティング層の保持が困難となるためである。 また、 蛭石と ガラス粉末の合計の添加量は 3 0重量％以下とすることが望ましい。 なお、 ガラ ス粉末の軟化温度は、 カーボン含有耐火物の一般的な予熱条件及び使用中の温度 条件を考慮して 5 0 0〜1 1 0 0 °Cの範囲内とすることが最適である。
更に、 本発明のカーボン含有耐火物の断熱コーティング材は、 上記の中空の耐 火性粒子や粘土、 蛭石、 ガラス粉末以外の成分として、 溶融石英、 ムライト、 マ グネシァ、 ジルコニァ、 スピネル、 アルミナ、 シャモヅト、 ろう石、 ばん土頁岩 の各化合物の群から選択された 1種または 2種以上を併用することも可能である 。 これらの化合物は、 力一ボン含有耐火物の加熱条件や使用条件に応じて、 高温 での断熱コ一ティング層の耐熱性の調整、 使用時の断熱コーティング材の亀裂や 剥離抑制の調整のために配合されるものである。 ここで、 これらの化合物の添加 量は 1 0重量％以下とすることが望ましい。 1 0重量％を超える場合は、 加熱時 及び使用時にこれらの成分に起因する焼結収縮が大きくなり、 断熱層に亀裂が生 じたり、 母材と断熱層が剥離し易くなるなどの問題が生じ不適当である。
上記の中空の耐熱性粒子や粘土、 蛭石、 ガラス粉末等の耐火'性原料は液状バイ ンダーを用いて混合する。 液状バインダーとしては、 コ一ティング材をカーボン 含有耐火物表面へ施工後、 3 0 0 °C以下の温度で乾燥して塗膜を形成するものが 好ましく、 例えば、 珪酸カリウム、 リン酸アルミニウム、 コロイダルシリカ等を 用いることができる。 また、 数種の液状バインダーを併用することも可能である
。 なお、 液状バインダーの添加量は、 耐火材料に対して外掛で 2 0〜1 7 0重量 %の範囲であり、 好適には 3 0〜 1 5 0重量％である。 ここで液状バインダーの 添加量が外掛で 2 0重量％未満であるとその添加効果が発現せず、 カーボン含有 耐火物表面への施工が困難となり好ましくない。 また、 該配合量が外掛で 1 7 0 重量％を超えると、 粘性低下による力一ボン含有耐火物への塗布性が低下するた めに好ましくない。
カーボン含有耐火物表面への施工については、 刷毛塗り、 吹付け、 デイツピン グ等を適用できるが、 各々の施工方法において、 液状バインダーの添加量を 2 0 〜 1 7 0重量％の範囲で調整する。 なお、 本発明では、 カーボン含有耐火物表面 への施工方法は限定されるものではなく、 施工する力一ボン含有耐火物の形状や 大きさ、 施工環境等に応じてその方法を選択することができる。
実施例
以下に、 実施例を挙げて本発明のカーボン含有耐火物のコ一ティング材をさら に説明する。 なお、 本発明は実施例によって限定されるものではない。
(実施例 1 )
以下の表 1に記載する配合割合にて、 本発明品及び比較品のコ一ティング材を 得た。 なお、 ここで使用した中空の耐火性粒子は、 外観： 白色、 かさ比重： 0 . 2 5 - 0 . 4 2 g/ c m3であり、 その組成及び粒度は、 次の通りであった：
Figure imgf000009_0001
次に、 得られたコーティング材を A 1203 5 0重量％、 S i 02 2 5重量％、 カーボン 2 5重量％の組成を有するカーボン含有耐火物からなる連続鎢造用浸漬 ノズルの外表面に約 3 mmの厚みに吹付け塗布し、 1 3 0 °Cで 4時間乾燥した後 、 図 1に示す加熱ボックス （ 1 ) に連続錶造用浸漬ノズル （2 ) をセットし、 ガ スバ一ナ一 （4 ) で 1 2 5 0 °Cまで加熱し、 該温度に 6時間保持した後、 加熱ボ ックス （1) から取り出し、 連続鐯造用浸漬ノズル （2) を大気中に放置し、 コ 一ティング材塗膜 （3) 下の温度測定位置 （5) での温度降下 （10分後） を測 定した。 また、 冷却後、 コ一ティング材塗膜の状態を目視により観察した。 なお 、 本発明品 1で使用したガラス粉末の溶融軟化温度は 1000°Cであり、 蛭石は
500°Cで加熱処理を行って結晶水を脱水したものである。 また、 蛭石の粒度は lmm以下のものであり、 ガラス粉末の粒度は 0. 3 mm以下のものである。 得られた結果を表 2に併記する。 なお、 比較品 1は、 コーティング材を吹付け 施工しないブランクであり、 比較品 2は、 厚さ 3 mmのセラミックべ一パ一を上 記と同材質の連続錶造用浸漬ノズルへ貼り付けたものである。
Figure imgf000010_0001
Figure imgf000011_0001
(実施例 2 )
以下の表 3に示す配合割合にて本発明品及び比較品の配合を得た。 なお、 実施 例 2で使用した中空の耐火性粒子は実施例 1の中空の耐火性粒子 Dを使用した。 また、 ガラス粉末、 粘土、 蛭石についても実施例 1で使用したものと同一の原料 を使用した。 溶融石英、 ムライ ト、 マグネシア、 ジルコニァ、 スピネル、 アルミ ナ、 シャモット、 ろう石、 ばん土頁岩はいずれも 0 . 3 mm以下の原料を使用し た。 得られたコーティング材は、 A 1203 60重量％、 Si02 10重量％、 力一 ボン 30重量％の組成を有するカーボン含有耐火物からなる連続鎵造窯浸漬ノズ ルの外表面に約 0. 3 mmの厚さで吹付け塗布し、 150°Cで 5時間乾燥した後 、 実施例 1と同様な方法で加熱試験及び評価を行った。 得られた結果を表 3に併 §3する。
Figure imgf000012_0001
Figure imgf000013_0001
産業上の利用可能性
本発明のコーティング材によれば、 高温加熱時にカーボン含有耐火物の表面酸 化を防止すると共に、 コ一ティング材塗膜よりなる断熱層を形成することができ るという効果を奏し、 鋼の連続鎵造における断熱コーティング材として有用であ る 0

Claims

請求 の 範 囲
1 . 中空の耐火性粒子を含有し、 該中空粒子の含有量が 5 0〜9 7重量％、 残部の一部または全てが粘土であり、 且つ粘土の含有量が 3 0重量％以下である 耐火材料に、 液状バインダーを外掛で 2 0〜 1 7 0重量％添加したことを特徴と し、 高温加熱時にカーボン含有耐火物の表面酸化を防止するとともに、 断熱層を 形成する力一ボン含有耐火物の断熱コーティング材。
2 . 中空の耐火性粒子を含有し、 該中空粒子の含有量が 5 0 ~ 9 4重量％、 粘土の含有量が 2 ~ 2 5重量％、 残部の一部または全てが、 結晶水を脱水した蛭 石及びまたは 5 0 0 - 1 1 0 0 °Cの温度範囲で軟化溶融するガラス粉末であり、 該結晶水を脱水した蛭石及びまたは 5 0 0〜 1 1 0 0 °Cの温度範囲で軟化溶融す るガラス粉末の合計量が 3 0重量％以下である耐火材料に、 液状バインダーを外 掛で 2 0 ~ 1 7 0重量％添加したことを特徴とし、 高温加熱時に力一ボン含有耐 火物の表面酸化を防止するとともに、 断熱層を形成する力一ボン含有耐火物のコ —ティング材。
3 . 溶融石英、 ムライト、 マグネシア、 ジルコニァ、 スビネル、 アルミナ、 シャモヅト、 ろう石、 ばん土頁岩から選ばれた一種または二種以上の化合物を 1 0重量％以下含有することを特徴とする、 請求項 1または 2記載のカーボン含有 耐火物のコ一ティング材。
4 . 中空の耐火性粒子が、 S i 02及び A 1203を含有し、 その含有量が S i 02： 4 0〜8 0重量％、 A 1203： 2 0〜6 0重量％であることを特徴とする、 請求項 1ないし 3のいずれか 1項記載のカーボン含有耐火物のコ一ティング材。
5 . 中空の耐火性粒子の粒度範囲が、 3 0〜8 0 0ミクロンの範囲内にある ことを特徴とする、 請求項 1ないし 4のいずれか 1項記載のカーボン含有耐火物 のコ一ティング材。
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JP2001335375A (ja) * 2000-05-23 2001-12-04 Shinagawa Refract Co Ltd カーボン含有耐火物用断熱コーティング材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107840671A (zh) * 2017-11-08 2018-03-27 武汉钢铁有限公司 一种焦炉用轻质保温涂层及其施工工艺

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