KR20040016493A - High intensity castable refractories with good adiabatic and high thermal shock resistance - Google Patents

High intensity castable refractories with good adiabatic and high thermal shock resistance Download PDF

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KR20040016493A
KR20040016493A KR1020020048690A KR20020048690A KR20040016493A KR 20040016493 A KR20040016493 A KR 20040016493A KR 1020020048690 A KR1020020048690 A KR 1020020048690A KR 20020048690 A KR20020048690 A KR 20020048690A KR 20040016493 A KR20040016493 A KR 20040016493A
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refractory
alumina
shock resistance
thermal shock
ceramic fiber
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KR100491123B1 (en
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김봉회
김효준
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주식회사 포스코
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66Monolithic refractories or refractory mortars, including those whether or not containing clay
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607Thermal properties, e.g. thermal expansion coefficient

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

PURPOSE: Provided is a high strength castable refractory excellent in insulating property and heat impact resistance, which contains ceramic fiber and increases an insulating effect between an iron ware and a refractory in a high temperature furnace facility. CONSTITUTION: The high strength castable refractory comprises 40-64wt% of fused alumina, 5-12wt% of calcined alumina, 3-6wt% of silica ultrafine powder, 20-30wt% of ceramic fiber, 3-5wt% of vinyl fiber, and 5-7wt% of alumina cement. The ceramic fiber increases a buffer action of the refractory and the insulating effect by forming fine pores.

Description

단열성 및 열충격저항성이 우수한 고강도 캐스터블 내화물{HIGH INTENSITY CASTABLE REFRACTORIES WITH GOOD ADIABATIC AND HIGH THERMAL SHOCK RESISTANCE}HIGH INTENSITY CASTABLE REFRACTORIES WITH GOOD ADIABATIC AND HIGH THERMAL SHOCK RESISTANCE}

본 발명은 일반 가열로, 혼선차 및 제강 래들 등 각종 고온로 설비에서 단열효과를 높이기 위하여 철피와 내화물 간의 틈사이에 충전되는 세라믹 화이버를 함유한 단열성 및 열충격저항성이 우수한 고강도 캐스타블 내화물에 관한 것이다.The present invention relates to a high-strength castable refractory having excellent thermal insulation and thermal shock resistance containing ceramic fibers filled between the gap between the shell and the refractory to increase the thermal insulation effect in various high temperature furnace equipment such as general heating furnaces, crosstalk cars and steelmaking ladles. will be.

일반적으로, 고온에서 사용되는 로 설비는 열손실이 많으므로 열손실을 줄이기 위하여 철피와 내장내화물 사이에 단열성이 우수한 벽돌 또는 유사재질로 충전하여 열을 차단하고 있으며 충전두께가 얇으면서 단열성이 우수한 내화물이 요구된다.In general, furnace equipment used at high temperatures has a lot of heat loss, so in order to reduce heat loss, it is blocked with heat by filling with a heat insulating brick or similar material between the shell and the interior refractories, and refractory material with a thin filling thickness and excellent heat insulation. Is required.

충전용 내화물에 관해 공개된 종래기술중의 일 예로 일본국 특허공개공보 평6-279129호 및 평9-142944호를 들 수 있다.Japanese Patent Laid-Open Nos. Hei 6-279129 and Hei 9-142944 are mentioned as examples of the prior art disclosed regarding filling refractory materials.

상기 공개공보 평6-279129호는 용융금속용기에 있어 고열팽창성 연와를 사용하여 축조하는 경우에 사용하는 몰탈로서 마그네슘, 알루미늄 등의 탄산염이나 수산화물의 1종 또는 2종이상의 분말 10중량% 이상과 내화분말로 된 내화몰탈에 관한 것이며, 평9-142944호는 공업로의 철피와 내장내화물간 또는 내화물 상호의 틈새부에 압입하는 압입보수재로서 분말골재와 방향족 탄화수소 수지액과의 혼합물로 구성되고, 200℃에서 24시간 유지후 체적감소율이 2.0% 이하이고 열경화되지 않는 것을 특징으로 하는 틈새부 압입재에 관한 것이다.Publication No. 6-279129 discloses a mortar used when a molten metal container is constructed using a high thermally expansible lead and is 10% by weight or more of powders of one or two or more kinds of carbonates and hydroxides such as magnesium and aluminum, and hydroxides. Regarding powdered refractory mortar, No. 9-142944 is a press-fitting repair material press-fitted into the gap between steel bar and internal refractories of an industrial furnace or between refractory materials, consisting of a mixture of powdered aggregate and aromatic hydrocarbon resin liquid. It relates to a crevice press-fitting material characterized in that the volume reduction rate is 2.0% or less and not thermally cured after holding at 24 ° C. for 24 hours.

그러나, 본 발명의 분야는 모두 장기간 사용되는 용융금속용기 및 공업로의 보수에 사용되는 내화물이기 때문에 내화벽돌에 의한 팽창을 억제하는 강도가 강해야 함에 도 불구하고 이들 공개기술들은 강도가 낮고 단열효과가 작으므로 사용에 많은 제한을 받고 있어 그 활용도가 유명무실하여 새로운 대체물의 필요성이 강하게 대두되었다.However, although all of the fields of the present invention are refractory materials used for repairing molten metal containers and industrial furnaces that are used for long periods of time, these disclosed technologies have low strength and thermal insulation effect even though the strength to suppress expansion by refractory bricks should be strong. Because of their small size, their use has been severely limited, and their use is not well known.

본 발명은 상술한 바와 같은 종래 기술이 갖는 제반 문제점들을 감안하여 이를 해결하고자 창출한 것으로, 다년간에 걸친 연구와 실험을 거듭하고 그 결과에 근거하여 세라믹 화이버와 유기 화이버를 사용하여 단열성과 열충격저항성을 높이고 고온에서의 소성강도가 큰 캐스타블 내화물을 제공함으로써 그러한 문제를 극복할 수 있도록 한 것을 그 목적으로 한다.The present invention was created in view of the above-mentioned problems of the prior art, and has been created to solve this problem, and after many years of research and experiments, based on the results, using ceramic fibers and organic fibers, It is an object of the present invention to overcome such problems by providing a castable refractory material having a high plastic strength with high plastic strength at high temperatures.

상기 목적을 달성하기 위한 본 발명은 세라믹 화이버 함유 캐스타블 내화물 내화조성물에 있어서, 중량%로 전융질 알루미나: 40-64, 하소알루미나: 5-12, 실리카 초미분: 3-6, 세라믹 화이버: 20-30, 유기 화이버: 3-5, 알루미나 시멘트: 5-7로 조성되는 것을 특징으로 하는 단열성 및 열충격저항성이 우수한 고강도 캐스터블 내화물을 제공함으로써 달성된다.In order to achieve the above object, the present invention provides a castable refractory refractory composition containing ceramic fiber, in terms of weight% of an all-hot alumina: 40-64, calcined alumina: 5-12, silica ultrafine powder: 3-6, ceramic fiber: 20-30, organic fibers: 3-5, alumina cement: 5-7 is achieved by providing a high-strength castable refractory excellent in insulation and thermal shock resistance.

이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 조성중 알루미나는 주원료로 사용되며 고온에서 사용되는 내화물의 내화도 및 내침식성을 촉진시켜 소성강도를 높이는 역할을 한다.Alumina in the composition of the present invention is used as a main raw material and serves to increase the plastic strength by promoting the fire resistance and erosion resistance of the refractory used at high temperatures.

이들 원료에는 제조방법에 따라서 소결알루미나와 전융알루미나(FUSED ALUMINA)가 있으며, 본 발명에서는 불순물이 적고 소결성이 좋은 전융알루미나를 사용하였다.These raw materials include sintered alumina and fusing alumina (FUSED ALUMINA) according to the production method. In the present invention, fused alumina having low impurities and good sinterability was used.

전융알루미나의 사용량이 40중량% 미만이 되면 내화물의 내화도가 낮아서 고온에서의 사용에 부적합하고, 사용량이 64중량% 이상에서는 지나치게 내화도가 높아져서 소결성이 충분치 못하므로 상기 전융알루미나의 첨가량은 40-64중량%가 바람직하다.When the amount of the molten alumina used is less than 40% by weight, the refractory degree of the refractory is low, which is unsuitable for use at high temperatures. When the amount of the molten alumina used is more than 64% by weight, the refractory degree is too high and the sinterability is not sufficient. % Is preferred.

하소알루미나는 초미분원료로서 활성이 있으므로 내화물의 소결성을 좋게 하여 고온강도를 높이는 역할을 한다.Since calcined alumina is active as an ultra fine powder, it acts to improve the sinterability of the refractory and to increase the high temperature strength.

이러한 하소알루미나의 사용량이 5중량% 이하에서는 사용량이 부족하여 소결성이 저하되고, 사용량이 12중량% 이상에서는 과소결로 인하여 수축이 심하므로 상기 하소알루미나의 적당한 사용량은 5-12중량%가 바람직하다.When the amount of the calcined alumina is 5 wt% or less, the amount of the calcined alumina is insufficient, and the sinterability is lowered. When the amount of the calcined alumina is 12 wt% or more, the shrinkage is severe due to oversintering, so the suitable amount of the calcined alumina is preferably 5-12 wt%.

실리카 초미분은 내화물의 분산성을 높이고 중간온도, 즉 1000℃정도에서 소결촉진효과가 있어 중간온도에서의 소성강도를 높이는 역할을 한다.The ultrafine silica powder increases the dispersibility of the refractory and has a sintering promoting effect at an intermediate temperature, that is, about 1000 ° C., thereby increasing the plastic strength at an intermediate temperature.

이러한 실리카 초미분의 사용량이 3중량% 미만에서는 사용량이 부족하여 내화물의 분산효과가 적을 뿐 만 아니라 소결성이 부족하여 소성강도 증진효과가 적고, 사용량이 6중량% 이상에서는 실리카 초미분의 체적이 크므로 사용량이 과다하여 혼련성이 저하되고 지나치게 소결촉진효과가 크므로 가축성을 저하시킨다.When the amount of the ultrafine silica is less than 3% by weight, the amount of the ultrafine powder is not only insufficient, so the dispersing effect of the refractory is not only small, but the sinterability is insufficient, so that the effect of enhancing the plastic strength is small. Due to excessive use of the furnace, the kneading property is lowered and the sintering promoting effect is too large, thus reducing the livestock property.

따라서, 상기 실리카 초미분은 3-6중량% 범위에서 첨가됨이 바람직하다.Therefore, the ultrafine silica powder is preferably added in the range of 3-6% by weight.

세라믹 화이버는 내화물의 완충작용을 높이고 미세기공을 형성하여 단열효과를 높이는 역할을 한다.Ceramic fiber increases the buffering effect of the refractory and forms a micro-pores to increase the thermal insulation effect.

이러한 세라믹 화이버에는 성분에 따라서 여러가지 종류가 있으나 본 발명에서는 알루미나 함량이 30-60중량%의 범위에 있고 섬유길이가 1-5mm의 것을 사용한다.There are various kinds of ceramic fibers according to the components, but in the present invention, the alumina content is in the range of 30-60 wt% and the fiber length is 1-5 mm.

이는, 섬유길이가 1mm 이하에서는 너무 미세하여 인성증진에 효과적이지 못하고, 5mm 이상에서는 섬유끼리 얽혀서 잘 풀어지지않아 혼련이 잘 되지 않기 때문이며, 또한 화이버의 알루미나 함량이 30중량% 미만에서는 화이버의 내열온도가 낮아서 고온에서 사용하기에 부적합하고, 60중량% 이상에서는 알루미나 함량이 과다하여 화이버를 감싸고있는 주원료인 알루미나와 접착성이 좋지 않기 때문이다.This is because the fiber length is too fine at 1 mm or less, which is not effective for increasing toughness, and when the fiber length is 5 mm or more, the fibers are entangled and do not loosen well, and kneading is difficult. It is because it is not suitable for use at high temperatures because it is low, and at 60% by weight or more, the alumina content is excessive, and the adhesion between the main material and the alumina surrounding the fiber is poor.

그런데, 본 발명에서 사용되는 상기 30-60중량%의 범위에 있고 섬유길이가 1-5mm의 범위에 있는 세라믹 화이버를 20-30중량%로 한정하여 첨가하여야 하는데 이는 세라믹 화이버가 20중량% 미만에서는 화이버량이 적어서 가축성이 작고 인성증진효과가 작으므로 부적합하고, 사용량이 30중량% 이상에서는 가축성은 좋으나 화이버량이 많아서 화이버끼리 서로 얽혀서 잘 풀어지지 않아 미세기공 형성에는 부적합하기 때문이다.By the way, the ceramic fiber in the range of 30-60% by weight used in the present invention and the fiber length in the range of 1-5mm should be limited to 20-30% by weight, which is less than 20% by weight of the ceramic fiber This is because the amount of fibers is small and the animal properties are small and the toughness-promoting effect is inadequate, and when the amount of use is more than 30% by weight, the animal properties are good, but the amount of fibers is large, and the fibers are not entangled with each other and are not suitable for forming micropores.

따라서, 본 발명에서 첨가되는 세라믹 화이버는 20-30중량% 정도가 가장 바람직하다.Therefore, the ceramic fiber added in the present invention is most preferably about 20-30% by weight.

유기 화이버(vinyl fiber)는 내화물에서 첨가되어 500℃이상의 온도에서 소실되어 미세기공을 형성하여 단열성을 높이는 역할을 한다.Organic fibers (vinyl fiber) is added in the refractory is lost at a temperature above 500 ℃ to form a micro-pores to play a role to increase the thermal insulation.

이러한 유기 화이버의 길이는 1-3mm의 것을 사용함이 바람직한 바, 이는 유기 화이버의 길이가 1mm 미만에서는 너무 미세하여 미세기공 형성에 효과가 적고, 화이버의 길이가 3mm 이상에서는 화이버의 길이가 길어서 소실된 후에 생성된 기공경이 커서 균일한 내화물조직을 얻을 수가 없어 부적합하기 때문이다.It is preferable that the length of the organic fiber is 1-3mm, which is too fine when the length of the organic fiber is less than 1mm, so that it is less effective in forming micropores. This is because the pore diameter generated later is not suitable to obtain a uniform refractory structure.

또한, 유기 화이버의 첨가량이 3중량% 미만에서는 사용량이 부족하여 기공형성 효과가 적고, 5중량% 이상에서는 형성된 기공면적이 과다하여 강도를 저하시키므로 3-5중량% 정도 첨가됨이 바람직하다.In addition, when the amount of the organic fibers added is less than 3% by weight, the amount of use thereof is insufficient, so that the pore-forming effect is small, and in the case of 5% by weight or more, it is preferable to add about 3-5% by weight because the formed pore area is excessive and the strength is lowered.

알루미나 시멘트는 내화물의 상온강도와 1200℃ 이상에서 소성강도를 높이는 역할을 한다.Alumina cement plays a role of increasing the plastic strength at room temperature strength and 1200 ℃ or more of the refractory.

이러한 알루미나 시멘트의 사용량이 5중량% 미만에서는 사용량이 부족하여 강도 증진효과가 작고, 사용량이 7중량% 이상에서는 사용량이 과다하여 경화속도가 빠르고 강도가 지나치게 크므로 사용에 부적합하다.When the amount of the alumina cement is less than 5% by weight, the amount is insufficient to enhance the strength, and when the amount is more than 7% by weight, the amount is excessive, the curing speed is too high and the strength is not suitable for use.

따라서, 알루미나 시멘트의 적당한 사용량은 5-7중량%이다.Therefore, a suitable amount of alumina cement is 5-7% by weight.

이하, 본 발명을 실시예를 통하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

[실시예]EXAMPLE

하기 표 1과 같은 조성비를 가진 캐스타블 내화물을 제조하기 위해서는 캐스타블 내화물 혼련용 만능혼련기에서 분말 원료를 물과 함께 먼저 투입하여 미리 혼련한 후에 세라믹 화이버와 유기 화이버를 조금씩 첨가하여 균일하게 혼련이 되도록 하였다.In order to manufacture a castable refractory having a composition ratio as shown in Table 1 below, the powder raw material is first mixed with water in a universal mixer for castable refractory kneading, and then kneaded in advance to uniformly add ceramic fibers and organic fibers little by little. It was kneaded.

이와같이 하여 제조된 시료를 40 ×40 ×160mm의 크기로 성형한 후 이 시편을 1200℃에서 3시간 소성후 선변화율, 곡강도, 비중, 기공율을 측정하고 그 결과를 나타내었다.The sample prepared in this way was molded into a size of 40 × 40 × 160 mm, and then the specimen was calcined at 1200 ° C. for 3 hours, and then the linear change rate, bending strength, specific gravity, and porosity were measured, and the results were shown.

작업성의 평가는 유동성시험기(flow meter)를 이용하여 혼련된 시편에 15회 타격을 가한후 원료의 퍼짐상태에 의하여 판단하였다.Evaluation of workability was determined by spreading the raw material after 15 blows to the kneaded specimen using a flow meter (flow meter).

열충격저항성은 1300℃로 가열된 전기로에 준비된 50 ×50mm의 시편을 투입하여 30분이 경과한 후에 다시 꺼내어 공기중에서 냉각한 다음 재차 가열, 냉각하는 과정을 20회 반복할 동안의 시편에 발생하는 균열, 모서리탈락 등 외관상태를 관찰하였다.The thermal shock resistance is applied to a 50 × 50mm specimen prepared in an electric furnace heated to 1300 ℃, taken out again after 30 minutes, cooled in air, and then again cracked in the specimen during 20 times of heating and cooling. The appearance state such as edge dropping was observed.

상기 표 1에 나타난 바와 같이, 본 발명의 범위를 만족하는 발명예(1-5)는 비교예(1-4) 및 종래재와 비교하여 선변화율이 비교적 적고, 소성강도가 크며 비중이 작아 단열성이 우수함을 확인할 수 있었다.As shown in Table 1, Inventive Example (1-5), which satisfies the scope of the present invention, has a relatively small line change rate, a large plastic strength, and a specific gravity, which is relatively low as compared with Comparative Examples (1-4) and conventional materials. This excellence could be confirmed.

이상에서 상세히 설명한 바와 같이, 본 발명에 따른 세라믹 화이버 함유 캐스타블 내화물은 단열성과 열충격저항성이 좋고 고온강도가 크므로 고온로설비에서 철피와 내화물간의 단열효과를 높여 열손실 저감에 유용한 효과가 있다.As described in detail above, the ceramic fiber-containing castable refractory according to the present invention has excellent thermal insulation resistance and thermal shock resistance and has high temperature strength, thereby increasing thermal insulation effect between the shell and the refractory in a high-temperature furnace, thereby reducing heat loss. .

Claims (1)

중량%로,In weight percent, 전융질 알루미나: 40-64,Electrolytic alumina: 40-64, 하소알루미나: 5-12,Calcined alumina: 5-12, 실리카 초미분: 3-6,Ultrafine silica: 3-6, 세라믹 화이버: 20-30,Ceramic fiber: 20-30, 유기 화이버: 3-5,Organic fiber: 3-5, 알루미나 시멘트: 5-7Alumina Cement: 5-7 로 조성되는 단열성 및 열충격저항성이 우수한 고강도 캐스터블 내화물.High strength castable refractory with excellent thermal insulation and thermal shock resistance.
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KR100896648B1 (en) * 2007-10-24 2009-05-08 주식회사 포스코 Refractory composition having excellent adiabatic for spray and spraying construction method using the same
CN101152744B (en) * 2006-09-30 2010-11-10 宜兴市中宇窑炉工程材料有限公司 Fibre pouring material for glory hole inner lining and manufacturing method of the same
CN104671809A (en) * 2015-02-02 2015-06-03 中科华核电技术研究院有限公司 Processes for building and drying melting furnace for plasma heat treatment system
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JPH09249461A (en) * 1996-03-12 1997-09-22 Yotai Refractories Co Ltd Refractory heat-insulating castable
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JP2000026169A (en) * 1998-07-08 2000-01-25 Toshiba Ceramics Co Ltd Apparatus and method for executing castable refractory
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CN101152744B (en) * 2006-09-30 2010-11-10 宜兴市中宇窑炉工程材料有限公司 Fibre pouring material for glory hole inner lining and manufacturing method of the same
KR100896648B1 (en) * 2007-10-24 2009-05-08 주식회사 포스코 Refractory composition having excellent adiabatic for spray and spraying construction method using the same
CN104671809A (en) * 2015-02-02 2015-06-03 中科华核电技术研究院有限公司 Processes for building and drying melting furnace for plasma heat treatment system
KR102453669B1 (en) 2022-03-23 2022-10-12 주식회사 하이원 Water-soluble organic-inorganic binder composition and its construction method

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