JP2008081360A - Amorphous refractory molding material and Amorphous refractory molding - Google Patents
Amorphous refractory molding material and Amorphous refractory molding Download PDFInfo
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Abstract
【課題】断熱性及び機械的強度の両方に優れ、更に耐熱性や機械加工性も良好な不定形耐火物成形体、並びにその成形材料を提供する。
【解決手段】無機中空粒子を２〜２０質量％、非晶質シリカ及びワラストナイトの少なくとも一方を５０〜９３質量％及びアルミナセメントを５〜５０質量％の割合で含む不定形耐火物成形材料、並びに前記不定形耐火物成形材料に水を加えた混練物を硬化させてなり、かつ、密度が０．８〜２．０ｇ／ｃｍ３で、曲げ強度が２〜２０ＭＰａで、熱膨張係数が０．１〜７×１０−６／℃ある不定形耐火物成形体。
【選択図】なしThe present invention provides an amorphous refractory molded article excellent in both heat insulating properties and mechanical strength, and further having good heat resistance and machinability, and a molding material thereof.
An amorphous refractory molding material containing 2 to 20% by mass of inorganic hollow particles, 50 to 93% by mass of at least one of amorphous silica and wollastonite, and 5 to 50% by mass of alumina cement. In addition, a kneaded material obtained by adding water to the amorphous refractory molding material is cured, and the density is 0.8 to 2.0 g / cm 3 , the bending strength is 2 to 20 MPa, and the thermal expansion coefficient is An amorphous refractory molded body having a size of 0.1 to 7 × 10 −6 / ° C.
[Selection figure] None
Description
本発明は、耐熱性及び機械的強度の両方に優れ、更に断熱性や機械加工性も良好で、耐火材や断熱材として好適な不定形耐火物成形体を与える水硬性の成形材料に関する。また、本発明は、前記成形材料からなり、アルミニウム、亜鉛、スズ、鉛、マグネシウムあるいはこれらの合金等のように概ね融点が８００℃以下である比較的低融点の金属を鋳造する鋳造装置において、これら低融点金属の溶湯と接触する部位に使用される不定形耐火物成形体に関する。 The present invention relates to a hydraulic molding material which is excellent in both heat resistance and mechanical strength, further has good heat insulation and machinability, and gives an amorphous refractory molded article suitable as a refractory material or a heat insulation material. Further, the present invention is a casting apparatus for casting a relatively low melting point metal having a melting point of approximately 800 ° C. or lower, such as aluminum, zinc, tin, lead, magnesium, or an alloy thereof made of the molding material. The present invention relates to an indeterminate refractory molded body used in a portion that comes into contact with a molten metal of these low melting point metals.
上記に挙げた低融点金属の鋳造装置において、溶湯と接触する部材、例えば樋、溶湯保持炉、取鍋等を製造、構築もしくは補修するための内張材として、キャスタブル耐火物が広く利用されている。キャスタブル耐火物は適量の水と混練してから型枠に流し込んで硬化させ、乾燥後、焼成して、付着水および結晶水を除くことにより、使用中に水蒸気の発生が無く、耐火性も良い内張材を形成させるものである。 Casting refractories are widely used as lining materials for manufacturing, constructing or repairing members that come into contact with molten metal, such as firewood, molten metal holding furnaces, ladles, etc. Yes. Castable refractories are kneaded with an appropriate amount of water, then poured into a mold and cured, dried, baked, and free of water vapor and crystallization water so that no water vapor is generated during use, and fire resistance is good A lining material is formed.
上述のような鋳造装置の内張り用のキャスタブル耐火物として、溶湯に濡れ難く、耐食性も比較的良好なことから、アルミナセメントやワラストナイト系のものが従来使用されている（例えば、特許文献１参照）。 As a castable refractory for the lining of the casting apparatus as described above, alumina cement and wollastonite are conventionally used because they are difficult to wet with molten metal and have relatively good corrosion resistance (for example, Patent Document 1). reference).
しかしながら従来のアルミナセメントやワラストナイト系キャスタブルは、耐食性は優れているものの、溶湯の保温性を重視し断熱性に優れた製品にする場合は、密度を低くする必要があるため、曲げ強度等の機械的強度が不足して、施工時や、溶湯が激しく接触し大きな応力が発生するような使用箇所では、亀裂や割れが発生しやすいという問題があった。一方で、密度を高めて機械的強度を増すと、断熱性能が低下するようになる。このように、従来のキャスタブル耐火物は、断熱性と機械的強度がトレードオフの関係にあり、両立することは困難であった。 However, conventional alumina cements and wollastonite castables are excellent in corrosion resistance, but when making products with excellent heat insulation with an emphasis on heat insulation, it is necessary to lower the density, so bending strength, etc. There is a problem in that cracks and cracks are likely to occur at the time of construction or in places where the molten metal comes into intense contact and generates large stress. On the other hand, when the density is increased and the mechanical strength is increased, the heat insulation performance is lowered. Thus, conventional castable refractories have a trade-off relationship between heat insulation and mechanical strength, and it has been difficult to achieve both.
本発明の目的は、断熱性及び機械的強度の両方に優れ、更に耐熱性や機械加工性も良好な不定形耐火物成形体、並びにその成形材料を提供することにある。 An object of the present invention is to provide an amorphous refractory molded article that is excellent in both heat insulation and mechanical strength, and also has good heat resistance and machinability, and a molding material thereof.
上記目的を達成するために、本発明は以下の不定形耐火物成形材料及び不定形耐火物成形体を提供する。
（１）無機中空粒子を２〜２０質量％、非晶質シリカ及びワラストナイトの少なくとも一方を５０〜９３質量％及びアルミナセメントを５〜５０質量％の割合で含むことを特徴とする不定形耐火物成形材料。
（２）無機中空粒子が、粒径１ｍｍ以下で、ＳｉＯ２及びＡｌ２Ｏ３の少なくとも一方を７０質量％以上の割合で含むことを特徴とする上記（１）記載の不定形耐火物成形材料。
（３）無機中空粒子が、フライアッシュバルーンまたはシラスバルーンであることを特徴とする上記（２）記載の不定形耐火物用成形材料。
（４）上記（１）〜（３）の何れか１項に記載の不定形耐火物成形材料に水を加えた混練物の成形体を硬化させてなり、かつ、密度が０．８〜２．０ｇ／ｃｍ３で、曲げ強度が２〜２０ＭＰａで、熱膨張係数が０．１〜７×１０−６／℃あることを特徴とする不定形耐火物成形体。
（５）融点が８００℃以下の低融点金属の溶湯と接触する部位に使用されることを特徴とする上記（４）記載の不定形耐火物成形体。
In order to achieve the above object, the present invention provides the following amorphous refractory molding material and amorphous refractory molded article.
(1) An amorphous form containing 2 to 20% by mass of inorganic hollow particles, 50 to 93% by mass of at least one of amorphous silica and wollastonite, and 5 to 50% by mass of alumina cement. Refractory molding material.
(2) The amorphous refractory molding material as described in (1) above, wherein the inorganic hollow particles have a particle size of 1 mm or less and contain at least one of SiO 2 and Al 2 O 3 in a proportion of 70% by mass or more. .
(3) The inorganic refractory molding material as described in (2) above, wherein the inorganic hollow particles are fly ash balloons or shirasu balloons.
(4) A molded product of a kneaded product obtained by adding water to the amorphous refractory molding material described in any one of (1) to (3) above, and having a density of 0.8 to 2 An amorphous refractory molded body having a bending strength of 2 to 20 MPa and a thermal expansion coefficient of 0.1 to 7 × 10 −6 / ° C. at 0.0 g / cm 3 .
(5) The amorphous refractory molded article according to the above (4), wherein the molded article is used for a portion that comes into contact with a melt of a low melting point metal having a melting point of 800 ° C. or lower.
本発明による不定形耐火物成形体は、優れた断熱性と機械的強度とを兼ね備え、更に耐熱性や機械加工性も良好であり、従来品と比較して溶湯が激しく接触し大きな応力が発生する箇所に使用した場合でも、亀裂や割れの発生が少なくなり、材料の交換、補修をする頻度は従来と比較して大幅に少なくて済む。また、材料自体のコストも従来品と比較してほぼ同等である。そのため、交換や補修の所要時間と成形体購入コストで、従来と比較してトータル的に非常に安価で低融点金属の鋳造が可能になる。 The irregular-shaped refractory molded body according to the present invention has excellent heat insulation and mechanical strength, and also has good heat resistance and machinability, and the molten metal comes in contact with the violently compared with the conventional product and generates large stress. Even when it is used in a location where the material is used, cracks and cracks are less likely to occur, and the frequency of material replacement and repair is significantly lower than in the past. In addition, the cost of the material itself is almost the same as that of the conventional product. Therefore, in terms of the time required for replacement and repair and the cost of purchasing the compact, it is possible to cast a low-melting-point metal at a very low total cost compared to the conventional case.
以下、本発明に関して詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の不定形耐火物成形材料は、無機中空粒子と、非晶質シリカ及びワラストナイトの少なくとも一方と、アルミナセメントとを含む粉状混合物である。 The amorphous refractory molding material of the present invention is a powder mixture containing inorganic hollow particles, at least one of amorphous silica and wollastonite, and alumina cement.
無機中空粒子は、熱伝導率が低いことから断熱性能の向上に寄与する。また、後述するように、不定形耐火物成形材料に水を加えた混練物を成形することで本発明の不定形耐火物成形体が得られるが、無機中空粒子は、混練物の流動性を高める作用もあり、加工性の向上にも寄与する。更に、無機中空粒子は、不定形耐火物成形体において非晶質シリカやワラストナイト、アルミナセメントの隙間に入り込み、高充填化により機械的強度を増す効果もある。更には、不定形耐火物成形体の軽量化を図ることもできる。 Inorganic hollow particles contribute to improvement of heat insulation performance because of their low thermal conductivity. In addition, as described later, the amorphous refractory molded article of the present invention can be obtained by molding a kneaded product obtained by adding water to an amorphous refractory molding material. There is also an action to increase, contributing to improvement of workability. Further, the inorganic hollow particles enter the gaps between amorphous silica, wollastonite, and alumina cement in the amorphous refractory molded body, and have the effect of increasing the mechanical strength by increasing the filling. Furthermore, it is possible to reduce the weight of the amorphous refractory molded body.
また、無機中空粒子は、同一含有量で比較すると、より小径である方がより多数となり、上記の効果がより高まる。本発明では、粒径が１ｍｍ以下の無機中空粒子を用いることが好ましく、粒径３００μｍ以下の無機中空粒子がより好ましい。 Moreover, when compared with the same content, the inorganic hollow particles have a smaller number of smaller diameters, and the above effect is further enhanced. In the present invention, inorganic hollow particles having a particle size of 1 mm or less are preferably used, and inorganic hollow particles having a particle size of 300 μm or less are more preferable.
更に、無機中空粒子は、化学的な劣化成分であるアルカリ分が少ないことが好ましく、また耐熱性も有することからＳｉＯ２及びＡｌ２Ｏ３の少なくとも一方を７０質量％以上の割合で含むことがより好ましい。 Furthermore, it is preferable that the inorganic hollow particles have a low alkali content as a chemically deteriorated component and also have heat resistance, so that at least one of SiO 2 and Al 2 O 3 is contained in a proportion of 70% by mass or more. More preferred.
これらを考慮すると、無機中空粒子として、フライアッシュバルーン及びシラスバルーンが好ましい。フライアッシュバルーンやシラスバルーンは、安価であるという利点もある。また、その粒径は、平均粒径で１０〜３００μｍであることが好ましく、５０〜１５０μｍであることがより好ましい。 Considering these, fly ash balloons and shirasu balloons are preferable as the inorganic hollow particles. Fly ash balloons and shirasu balloons also have the advantage of being inexpensive. The average particle size is preferably 10 to 300 μm, and more preferably 50 to 150 μm.
非晶質シリカ及びワラストナイトは、共に耐熱性を付与する成分である。非晶質シリカとしては、各種溶融シリカを好適に使用できる。非晶質シリカの粒径は、０．５〜５００μｍであることが好ましく、１〜５００μｍであることがより好ましい。また、平均粒径１００〜５００μｍの粗粒と、平均粒径１〜５０μｍの微粒とを組み合わせることが好ましい。一方、ワラストナイトは針状結晶鉱物であり、鉱物ワラストナイト及び合成ワラストナイトがあるが、鉱物ワラストナイトの方が細長い針状であることから機械的強度の点で好ましく、更に軽量化や熱伝導率の低下を図ることもできる。そのため、ワラストナイトは、その平均繊維長で３５μｍ以上のものが好ましく、６０〜１００μｍのものがより好ましい。 Both amorphous silica and wollastonite are components that impart heat resistance. As the amorphous silica, various fused silicas can be suitably used. The particle size of the amorphous silica is preferably 0.5 to 500 μm, and more preferably 1 to 500 μm. Further, it is preferable to combine coarse particles having an average particle size of 100 to 500 μm and fine particles having an average particle size of 1 to 50 μm. On the other hand, wollastonite is a needle-like crystal mineral, and there are mineral wollastonite and synthetic wollastonite. Mineral wollastonite is more preferable in terms of mechanical strength because it is in the form of elongated needles, and it is lighter in weight. It is also possible to reduce the thermal conductivity. Therefore, wollastonite having an average fiber length of 35 μm or more is preferable, and 60 to 100 μm is more preferable.
アルミナセメントは、耐熱性の結合材として寄与する。アルミナセメントの種類には制限が無く、従来から耐火物等に使用されているものを使用することができる。中でも、得られる不定形耐火物成形体の外観に優れることから、Ａｌ2Ｏ3成分が５５質量％以上を占めるハイアルミナセメントが好ましい。 Alumina cement contributes as a heat-resistant binder. There is no restriction | limiting in the kind of alumina cement, The thing conventionally used for a refractory etc. can be used. Among them, a high alumina cement in which the Al 2 O 3 component accounts for 55% by mass or more is preferable because the appearance of the obtained amorphous refractory molded article is excellent.
不定形耐火物成形材料の組成は、断熱性と機械的強度とを両立するために、何れも成形材料全量に対し、無機中空粒子を２〜２０質量％、好ましくは４〜１２質量％、更に好ましくは６〜１０質量％とし、非晶質シリカ及びワラストナイトの少なくとも一方を５０〜９３質量％、好ましくは６０〜８０質量％とし、アルミナセメントを５〜５０質量％、好ましくは１０〜３０質量％とする。 The composition of the amorphous refractory molding material is 2 to 20% by mass, preferably 4 to 12% by mass, and preferably 4 to 12% by mass, based on the total amount of the molding material in order to achieve both heat insulation and mechanical strength. Preferably, the content is 6 to 10% by mass, at least one of amorphous silica and wollastonite is 50 to 93% by mass, preferably 60 to 80% by mass, and the alumina cement is 5 to 50% by mass, preferably 10 to 30%. Mass%.
尚、耐熱衝撃性を重視する場合は、熱衝撃性に優れた低熱膨張率の非晶質シリカと、バインダーであるアルミナセメントとからなる配合が望ましく、低熱伝導率性を重視する場合は、低密度化に効果が大きいワラストナイトとバインダーであるアルミナセメントとからなる配合が望ましい。また、その中間的な性能を重視する場合は非晶質シリカ、ワラストナイト、アルミナセメントからなる配合が望ましい。 In addition, when placing importance on thermal shock resistance, a combination of low thermal expansion amorphous silica with excellent thermal shock resistance and alumina cement as a binder is desirable, and when placing importance on low thermal conductivity, low A blend composed of wollastonite, which is highly effective in densification, and alumina cement as a binder is desirable. Further, when importance is placed on the intermediate performance, a blend of amorphous silica, wollastonite, and alumina cement is desirable.
また、不定形耐火物成形材料には、必要に応じて、従来からキャスタブル材料に使用されている耐火材料を適量配合することもできる。但し、本発明ではアルミニウム、亜鉛、スズ、鉛、マグネシウムあるいはこれらの合金等のように概ね融点が８００℃以下の低融点金属の溶湯と接触する部材を対象としていることから、融点が８００℃以上のものを使用する。具体的には、ムライト、ジルコニア、マグネシア、ジルコン等の酸化物系耐火物、窒化ホウ素や窒化珪素、窒化アルミニウム、サイアロン等の窒化物系耐火物、炭化珪素等の炭化物系耐火物、グラファイトや黒鉛等のカーボン系耐火物が挙げられる。これらの添加量は、全体の０．１〜１０質量％が好ましい。 In addition, an appropriate amount of a refractory material that has been conventionally used for castable materials can be blended into the amorphous refractory molding material, if necessary. However, since the present invention is intended for members that are in contact with a molten metal of a low melting point metal having a melting point of 800 ° C. or lower, such as aluminum, zinc, tin, lead, magnesium, or alloys thereof, the melting point is 800 ° C. or higher. Use one. Specifically, oxide refractories such as mullite, zirconia, magnesia and zircon, nitride refractories such as boron nitride, silicon nitride, aluminum nitride and sialon, carbide refractories such as silicon carbide, graphite and graphite And carbon-based refractories such as These addition amounts are preferably 0.1 to 10% by mass of the whole.
不定形耐火物成形材料は、水と混合され、得られた混練物を所定形状に成形し、硬化させることにより不定形耐火物成形体となる。 The amorphous refractory molding material is mixed with water, and the resulting kneaded product is molded into a predetermined shape and cured to form an irregular refractory molded body.
また、水には、ヘキサメタ燐酸ナトリウムやトリポリ燐酸ナトリウム、ウルトラポリ燐酸ナトリウム等の分散剤、炭酸リチウムや水酸化カルシウム等の硬化促進剤、ホウ酸やけいフッ化ナトリウム等の硬化遅延剤、あるいは爆裂防止目的でポリプロピレン繊維等の有機繊維を適量配合してもよい。これらの添加量は、全体の０．０５〜０．５質量％が好ましい。 For water, use a dispersant such as sodium hexametaphosphate, sodium tripolyphosphate or sodium ultrapolyphosphate, a curing accelerator such as lithium carbonate or calcium hydroxide, a curing retarder such as boric acid or sodium fluorofluoride, or an explosion. An appropriate amount of organic fiber such as polypropylene fiber may be blended for the purpose of prevention. These addition amounts are preferably 0.05 to 0.5 mass% of the whole.
不定形耐火物成形材料と水との混合比率は、混練物を成形したときに形状を保持できればよく、制限はないが、不定形耐火物成形材料１００質量部に対し、水を１０〜６０質量部とすることが好ましい。尚、成形方法は、型枠への流し込みが簡便であり、型枠内で養生、硬化させればよい。養生条件は、特に制限はないが、例えば１５〜２５℃、湿度５０〜９５ＲＨで２４時間以上行う。 The mixing ratio of the amorphous refractory molding material and water is not limited as long as the shape can be maintained when the kneaded product is molded, but water is 10 to 60 masses per 100 parts by mass of the irregular refractory molding material. Part. The molding method is easy to pour into the mold and may be cured and cured in the mold. The curing conditions are not particularly limited, but for example, the curing is performed at 15 to 25 ° C. and a humidity of 50 to 95 RH for 24 hours or more.
所定形状に成形した後は、乾燥することが好ましく、特に制限はないが、例えば１００〜１２０℃で２４時間以上行う。また、不定形耐火物成形体は、乾燥後の成形体中のアルミナセメントの水和物を脱水するために焼成してもよく、特に制限はないが、例えば６００〜８００℃で１〜５時間行う。尚、焼成は必ずしも必要はなく、使用する際に加えられる加熱により焼成してもよい。 After forming into a predetermined shape, it is preferable to dry, and there is no particular limitation, but for example, it is performed at 100 to 120 ° C. for 24 hours or more. Further, the amorphous refractory molded body may be fired to dehydrate the alumina cement hydrate in the molded body after drying, and there is no particular limitation, but for example, at 600 to 800 ° C. for 1 to 5 hours. Do. Note that firing is not always necessary, and firing may be performed by heating applied during use.
このようにして得られる本発明の不定形耐火物成形体は、密度が０．８〜２．０ｇ／ｃｍ３で、曲げ強度が２〜２０ＭＰａで、熱膨張係数が０．１〜７×１０−６／℃あり、断熱性と機械的強度の両方に優れ、その他、耐熱性や機械加工性も良好である。そのため、アルミニウム等の低融点金属を鋳造する鋳造装置の注湯ボックスや樋、保持炉等の内張り材として好適である。 The amorphous refractory molded article of the present invention thus obtained has a density of 0.8 to 2.0 g / cm 3 , a bending strength of 2 to 20 MPa, and a thermal expansion coefficient of 0.1 to 7 × 10. -6 / ° C, excellent in both heat insulation and mechanical strength, and in addition, heat resistance and machinability are also good. Therefore, it is suitable as a lining material for a pouring box, a jar, a holding furnace or the like of a casting apparatus for casting a low melting point metal such as aluminum.
以下に実施例及び比較例を挙げて本発明について更に説明するが、本発明はこれにより制限されるものではない。 EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereby.
（実施例１〜９、比較例１〜３）
表１に示した配合の成形材料と、水とをプラネタリーミキサーにて充分に混練した混練物を、平板用型枠に流し込んで２０℃、８０％ＲＨ、２４時間の条件で養生し、脱型後１０５℃で２４時間乾燥し、更に２００℃／時間の昇温速度で７００℃まで昇温し、この温度に３時間保って焼成することにより、アルミナセメントの水和物の脱水を行い、１６０×４０×４０ｍｍサイズの試験体を作製した。尚、使用材料の詳細は以下の通りである。そして、各試験体について下記の物性評価を行った。結果を表１に示す。
(Examples 1-9, Comparative Examples 1-3)
A kneaded material obtained by sufficiently kneading the molding material shown in Table 1 and water with a planetary mixer is poured into a plate mold, cured under conditions of 20 ° C., 80% RH, 24 hours, and removed. The mold is dried at 105 ° C. for 24 hours, further heated to 700 ° C. at a heating rate of 200 ° C./hour, and kept at this temperature for 3 hours to perform dehydration of the alumina cement hydrate, A test body having a size of 160 × 40 × 40 mm was produced. The details of the materials used are as follows. And the following physical-property evaluation was performed about each test body. The results are shown in Table 1.
（１）線変化率の測定
ＪＩＳ Ｒ２５５４に準拠し、１０５℃または７００℃における線変化率を測定した。
（２）密度の測定
ＪＩＳ Ｒ２６５５に準拠して測定した。
（３）曲げ強度及び圧縮強度の測定
試験体の曲げ強度及び圧縮強度をＪＩＳ Ｒ２５５３に準拠して測定した。
（４）熱膨張係数の測定
試験体から切り出した長さ２０ｍｍ、幅５ｍｍ、厚さ５ｍｍの試験片を、理学電機工業株式会社製熱機械分析装置「ＴＭＡ８３１０」を用いて、空気中で５℃／ｍｉｎの速度で室温から８００℃まで昇温し熱膨張係数を測定した。
（５）熱伝導率の測定
周期加熱法にて測定した。
(1) Measurement of linear change rate Based on JIS R2554, the linear change rate in 105 degreeC or 700 degreeC was measured.
(2) Measurement of density It measured based on JIS R2655.
(3) Measurement of bending strength and compressive strength The bending strength and compressive strength of the specimen were measured according to JIS R2553.
(4) Measurement of thermal expansion coefficient A test piece having a length of 20 mm, a width of 5 mm, and a thickness of 5 mm cut out from a specimen was measured at 5 ° C. in the air using a thermomechanical analyzer “TMA8310” manufactured by Rigaku Corporation. The thermal expansion coefficient was measured by raising the temperature from room temperature to 800 ° C. at a rate of / min.
(5) Measurement of thermal conductivity It was measured by a periodic heating method.
表１から、本発明に従う実施例の試験体は、低密度であり、熱伝導率が小さく、機械的強度も総じて高いことがわかる。実施例の試験体と比較例の試験体とは、無機中空粒子（フライアッシュバルーン）の有無で異なっており、無機中空粒子を配合することの有意性が確認された。特に、熱膨張係数が小さく、機械的強度も高い実施例１〜３の試験体が好ましい。また、実施例７〜９の試験体は、熱伝導率が小さく、断熱性を重視する用途に特に適している。 From Table 1, it can be seen that the test specimens of the examples according to the present invention have a low density, a low thermal conductivity, and a high mechanical strength as a whole. The test body of an Example and the test body of a comparative example differed by the presence or absence of an inorganic hollow particle (fly ash balloon), and the significance of mix | blending an inorganic hollow particle was confirmed. In particular, the specimens of Examples 1 to 3 having a small coefficient of thermal expansion and high mechanical strength are preferable. Moreover, the test bodies of Examples 7 to 9 have a low thermal conductivity and are particularly suitable for applications in which heat insulation is important.
Claims (5)
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| JP2009263145A (en) * | 2008-04-22 | 2009-11-12 | Agc Ceramics Co Ltd | Powder composition for insulating castable having low thermal conductivity |
| JP2010185290A (en) * | 2009-02-10 | 2010-08-26 | Toyota Central R&D Labs Inc | Heat insulating film and method of forming the same |
| JP2010185291A (en) * | 2009-02-10 | 2010-08-26 | Toyota Central R&D Labs Inc | Heat insulating film and method of forming the same |
| JP2011068505A (en) * | 2009-09-24 | 2011-04-07 | Nichias Corp | Method for manufacturing refractory molding for metal casting and method for manufacturing refractory sintered compact for metal casting |
| CN102161212A (en) * | 2011-01-18 | 2011-08-24 | 北京利尔高温材料股份有限公司 | Method for manufacturing low-cost slag blocking dam |
| JP2017104903A (en) * | 2015-12-08 | 2017-06-15 | ドングク リフラクトリーズ アンド スティール カンパニー リミテッドＤｏｎｇｋｕｋ Ｒｅｆｒａｃｔｏｒｉｅｓ ＆ Ｓｔｅｅｌ Ｃｏ．， Ｌｔｄ． | Method for manufacturing molten metal transferring ladle |
| JP2018062438A (en) * | 2016-10-12 | 2018-04-19 | 品川リフラクトリーズ株式会社 | Thermal insulation coating material for continuous casting nozzle |
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| JP2009263145A (en) * | 2008-04-22 | 2009-11-12 | Agc Ceramics Co Ltd | Powder composition for insulating castable having low thermal conductivity |
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| JP2018062438A (en) * | 2016-10-12 | 2018-04-19 | 品川リフラクトリーズ株式会社 | Thermal insulation coating material for continuous casting nozzle |
| WO2020213629A1 (en) * | 2019-04-17 | 2020-10-22 | 黒崎播磨株式会社 | Precast block for coke oven and coke oven using same |
| JPWO2020213629A1 (en) * | 2019-04-17 | 2021-04-30 | 黒崎播磨株式会社 | Precast block for coke oven and coke oven using it |
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