KR20030051107A - Porous ceramic fire-resistant materials and preparation thereof - Google Patents
Porous ceramic fire-resistant materials and preparation thereof Download PDFInfo
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Abstract
Description
본 발명은 내화재에 관한 것으로서, 보다 상세하게는 급열, 급냉에서도 손상이 없고 성형이 용이하며 단열성이 높으면서 견고하고 수축팽창률이 최소화되어 전기로용 다공질 세라믹 내화재 및 그 제조방법에 관한 것이다.The present invention relates to a refractory material, and more particularly, to a porous ceramic refractory material for an electric furnace and a method of manufacturing the same, which are free from damage even in rapid heat and quenching, are easy to mold, have high thermal insulation properties, and minimize shrinkage expansion.
일반적으로, 전기를 이용하여 금속을 용해하는 전기로는 중앙하단의 도가니받침대 위에 도가니가 놓여있고 그 외측에 중공부분을 갖도록 내화벽돌과 단열벽돌로 벽체가 형성되며 상기 벽체의 내화벽돌에는 도가니외면을 향하여 발열히터가 설치되어 있다.In general, an electric furnace for melting metal using electricity has a crucible placed on the crucible support at the bottom of the center, and a wall is formed of a refractory brick and a heat insulating brick so as to have a hollow portion on the outside thereof, and the refractory brick of the wall faces the crucible outer surface. Heating heater is installed.
상기와 같은 전기로는 발열히터에 전원이 공급되면 발열부분에서 발열되는 열과, 발열히터로부터 발열되는 열을 내화벽돌에서 흡수하였다가 발산되는 열에 의하여 도가니로 전달되므로 도가니 내부의 피용융물이 용해되게 된다.The electric furnace as described above is transferred to the crucible by the heat emitted from the heat generating portion, the heat generated from the heat generating portion and the heat generated from the refractory brick when the power is supplied to the heating heater is dissolved in the molten material inside the crucible.
이러한 전기로에서의 가장 어려운 과제는 첫째, 발열히터의 절단이 이뤄지지 않고 발열히터의 취부가 용이하며, 고온에서도 전기로의 내면인 내화벽돌부분이 손상되지 않고 에너지를 최대한 줄이는데 있다.The most difficult task in such an electric furnace is first, it is easy to attach the heating heater without cutting the heating heater, and to reduce the energy as much as possible without damaging the refractory brick part, which is the inner surface of the electric furnace, even at a high temperature.
그러나 기존의 전기로에 있어서, 단열벽돌은 알루미나와 실리카를 섬유화하고 이에 바인더를 첨가하여 압축 성형한 것으로 보온효과는 좋으나 강도가 약하여 로 내부에 직접 취부하기가 곤란하다는 문제점이 있었으며, 일반 내화벽돌은 강도는 좋고 고열에 견디나 단열효과가 떨어지므로 내화벽돌의 두께가 두꺼워져야 하고이로 인하여 전체적인 사이즈가 비대해지는 문제점이 있었다.However, in the existing electric furnace, the thermal insulation brick is formed by fiberizing alumina and silica and adding a binder to the compression molding, which has a good thermal insulation effect, but has a problem that it is difficult to install directly inside the furnace due to its weak strength. Is good and withstands high heat, but the heat insulation effect is low, so the thickness of the firebrick should be thick, which causes the overall size to be enlarged.
본 발명의 목적은 상기한 바와 같은 종래의 제반 문제점을 감안하여 급열, 급냉에서도 손상이 없고 낮은 두께에서도 높은 단열성을 나타내고, 견고하면서도 수축팽창률이 거의 없는 세라믹 내화재를 제공하는 데에 있다.An object of the present invention is to provide a ceramic refractory material that exhibits high thermal insulation even at low thickness without damage even in rapid quenching and quenching in view of the above-mentioned conventional problems.
상기한 목적을 달성하기 위한 연구에서 본 발명자는 산화알루미늄(Al2O3)에 선택적으로 산화지르코늄(ZrO2)을 함유하는 분말상 세라믹 성분과, 산화알루미늄과 이산화규소(SiO2)를 함유하는 섬유상 세라믹 성분 및 바인더를 배합하여 상기 목적에 부합하는 다공질 세라믹 내화재를 얻을 수 있게 되었다.In the research for achieving the above object, the present inventors have a powdery ceramic component selectively containing zirconium oxide (ZrO 2 ) in aluminum oxide (Al 2 O 3 ), and a fibrous form containing aluminum oxide and silicon dioxide (SiO 2 ). By blending the ceramic component and the binder, it is possible to obtain a porous ceramic refractory material meeting the above objectives.
그러므로 본 발명에 의하면, (a) 산화알루미늄의 분말상 세라믹 성분 40∼50 중량부와, (b) 산화알루미늄 40∼50중량%와 이산화규소 50∼60중량%를 함유하는 섬유상 세라믹 성분 50∼60중량부, 및 (c) 바인더 3∼10중량부를 함유하는 것을 특징으로 하는 다공질 세라믹 내화재가 제공된다.Therefore, according to the present invention, (a) 40 to 50 parts by weight of powdered ceramic component of aluminum oxide, (b) 50 to 60 weight of fibrous ceramic component containing 40 to 50% by weight of aluminum oxide and 50 to 60% by weight of silicon dioxide And, (c) 3 to 10 parts by weight of the binder, a porous ceramic fireproof material is provided.
상기 분말상 세라믹 성분은 산화알루미늄에 대하여 산화지르코늄 1∼10중량%를 함유시킬 수 있다.The powdery ceramic component may contain 1 to 10% by weight of zirconium oxide based on aluminum oxide.
또한 본 발명에 의하면 상기한 다공질 새라믹 내화재를 제조하기 위한 바람직한 방법의 하나로서, 산화알루미늄에 대하여 선택적으로 산화지르코늄 0∼10중량%를 함유하는 분말상 세라믹 성분 40∼50중량부와, 산화알루미늄 40∼50중량%와 이산화규소 50∼60중량%를 함유하는 섬유상 세라믹 성분 50∼60중량부 및 바인더 3∼10중량부로 되는 조성물을 물과 혼합하고 반죽하여 몰탈을 제조하고, 얻어진 몰탈을 소망하는 형태로 성형하고, 건조한 후 소성하는 것을 특징으로 하는 다공질 세라믹 내화재의 제조방법이 제공된다.In addition, according to the present invention, as one of the preferred methods for producing the above-mentioned porous ceramic refractory material, 40 to 50 parts by weight of a powdered ceramic component containing 0 to 10% by weight of zirconium oxide, and aluminum oxide 40 50 to 60 parts by weight of a fibrous ceramic component containing 50 to 60% by weight and 50 to 60% by weight of silicon dioxide and 3 to 10 parts by weight of a binder are mixed with water and kneaded to prepare mortar to obtain a mortar obtained. There is provided a method for producing a porous ceramic refractory material, characterized in that the forming, drying and firing.
이하, 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명에서 다공질 세라믹 내화재는 보드형태, 벌크형태 또는 이들을 성형하기 위한 몰탈 형태의 내화재를 모두 포함하는 의미로 사용된다.In the present invention, the porous ceramic refractory material is used in the sense of including a refractory material in the form of a board, bulk or mortar for molding them.
본 발명의 다공질 세라믹 내화재는 분말상 세라믹 성분, 섬유상 세라믹 성분 및 바인더를 주재로 하며, 이들의 배합비는 분말상 세라믹 성분 40∼50중량부, 섬유상 세라믹 성분 50∼60중량부 및 바인더 3∼12중량부로 하는 것이 바람직하다.The porous ceramic refractory material of the present invention is mainly composed of a powdered ceramic component, a fibrous ceramic component and a binder, and the blending ratio thereof is 40 to 50 parts by weight of the powdered ceramic component, 50 to 60 parts by weight of the fibrous ceramic component and 3 to 12 parts by weight of the binder. It is preferable.
본 발명의 내화재에 있어서, 분말상 세라믹 성분이 상기한 범위보다 적게 함유되면 과도한 다공성으로 인해 너무 소프트하여 강도가 약한 문제점이 있고, 상기 범위보다 많이 함유되면 다공도가 줄어들어 조밀하여 취성이 발생되기 쉽다는 문제점이 있으며,In the refractory material of the present invention, when the powdery ceramic component is contained in less than the above range, too soft due to excessive porosity, the strength is weak, and if more than the above range, the porosity is reduced, dense, brittleness is likely to occur There are,
섬유상 세라믹 성분이 상기한 범위보다 적게 함유되면 분말상 세라믹 성분이 상기한 범위보다 적게 함유되었을 때와 마찬가지로 다공도가 줄어들어 조밀하여 취성이 발생되기 쉽다는 문제점이 있고, 상기 범위보다 많이 함유되면 분말상 세라믹 성분이 상기한 범위보다 많이 함유되었을 때와 마찬가지로 과도한 다공성으로 인해 너무 소프트하여 강도가 약한 문제점이 있으며,When the fibrous ceramic component is contained in less than the above-mentioned range, the porosity decreases and the brittleness tends to occur as in the case where the powdery ceramic component is contained below the above-mentioned range. As when contained in more than the above range there is a problem of weak strength due to excessive porosity, weak strength,
바인더가 상기한 범위보다 적게 함유되면 세라믹의 결합력이 다소 미흡하게 되어 내화재의 물성이 취약하게 되고, 상기 범위보다 많이 함유되면 결합력의 증가로 강도가 증가되면서 취성이 발생되게 된다.If the binder is contained in less than the above range, the bonding strength of the ceramic is somewhat insufficient, so that the physical properties of the refractory material become weak. If the binder is contained in the above range, the brittleness occurs as the strength increases due to the increase in the bonding force.
상기한 분말상 세라믹 성분은 전량의 산화알루미늄이다. 이 산화알루미늄에 선택적으로 산화지르코늄 1∼10중량%를 함유시킬 수 있다. 이때, 산화지르코늄을 함유시키는 이유는 내화재의 고온성을 향상시키기 위해서이다. 분말상 세라믹 성분의 구성원료중 산화알루미늄이 상기한 범위보다 적게 함유되면 강도가 크게되어 급가열 또는 급냉시 균열이 발생되기 쉽고, 상기 범위보다 많이 함유되면 내화재의 융점이 낮아진다는 문제점이 있으며, 산화지르코늄이 상기한 범위보다 적게 함유되면 내열온도가 산화알루미늄의 용융점과 거의 동일하게 되어 바람직하지 못하고 많이 함유될수록 내식성이 증가되고 저열팽창률이 향상되나 그 함량이 너무 많게 되면 산화지르코늄 자체의 강도가 커서 급열, 급냉시 균열이 발생되기 쉽다는 문제점이 있다.The powdery ceramic component described above is the entire amount of aluminum oxide. The aluminum oxide may be optionally contained 1 to 10% by weight of zirconium oxide. At this time, the reason for containing zirconium oxide is to improve the high temperature property of a fireproof material. If the aluminum oxide is contained in the powder of the ceramic component less than the above-mentioned range, the strength is increased, so that cracking occurs easily during rapid heating or quenching, and if it is more than the above-mentioned range, the melting point of the refractory material is lowered. If the content is less than the above-mentioned range, the heat resistance temperature becomes almost the same as the melting point of aluminum oxide, which is undesirable. The higher the content, the higher the corrosion resistance and the lower the coefficient of thermal expansion. There is a problem that cracks are likely to occur during quenching.
상기한 섬유상 세라믹 성분은 산화알루미늄 40∼50중량%와 이산화규소 50∼60중량%를 함유한다. 이러한 세라믹 성분의 섬유화는 공지되어 있는 방법으로 제조가능하며, 바람직한 섬유상 세라믹 성분의 입자크기는 300nm 이하이다.The fibrous ceramic component contains 40 to 50% by weight of aluminum oxide and 50 to 60% by weight of silicon dioxide. Fibrosis of such ceramic components can be made by known methods, and the particle size of the preferred fibrous ceramic component is 300 nm or less.
섬유상 세라믹 성분의 구성원료중 산화알루미늄이 상기한 범위보다 적게 함유되면 융점이 낮은 이산화규소의 비율이 낮아져 분말상 혼합물의 융점이 낮아지므로 섬유상으로의 제조는 용이하나 내화재의 융점 또한 낮아지는 문제점이 있고, 상기 범위보다 많이 함유되면 분말상 혼합물의 융점이 높아져 섬유상으로의 제조가 어렵다는 문제점이 있으며,If the aluminum oxide contained in the component of the fibrous ceramic component is less than the above-mentioned range, the ratio of silicon dioxide having a low melting point is lowered and the melting point of the powder mixture is lowered, thus making it easy to manufacture into a fibrous form but also lowering the melting point of the refractory material. If it contains more than the above range there is a problem that the melting point of the powder mixture is difficult to manufacture into a fibrous form,
이산화규소가 상기한 범위보다 적게 함유되면 융점이 높은 산화알루미늄의 혼합비율이 증대되어 분말상 혼합물의 융점이 높아지므로 섬유상으로의 제조가 어렵다는 문제점이 있고, 상기 범위보다 많이 함유되면 융점이 높은 산화알루미늄의 혼합비율이 낮아져 분말상 혼합물의 융점이 낮아지므로 섬유상으로의 제조는 용이하나 내화재의 융점 또한 낮아지는 문제점이 있다.If silicon dioxide is contained less than the above range, the mixing ratio of aluminum oxide having a high melting point is increased, so that the melting point of the powdery mixture is high, so that it is difficult to manufacture into a fibrous form. Since the mixing ratio is lowered and the melting point of the powdery mixture is lowered, it is easy to manufacture into a fibrous form, but the melting point of the refractory material is also lowered.
바인더는 통상의 세라믹계 내화재나 단열재의 제조에 사용되는 것으로서, 고온에서도 결합력이 유지되는 것이면 어떠한 것이라도 무방하다. 그 대표적인 예로는 바인더 시멘트를 들 수 있다. 이러한 바인더 시멘트 중에서도 구하기 쉽고 값이 싼 알루미나계 시멘트가 경제적인 측면에서 유리하다.A binder is used for manufacture of a normal ceramic refractory material or a heat insulating material, and it may be any thing as long as a bonding force is maintained even at high temperature. Representative examples thereof include binder cement. Among these binder cements, alumina-based cement, which is easy to obtain and inexpensive, is advantageous in terms of economy.
본 발명의 내화재에는 상기한 필수 성분이외에도 세라믹계 내화재나 단열재의 제조에 통상적으로 배합되는 기타 통상의 성분들을 적정량 함유시킬 수도 있는 것이다.In addition to the above-mentioned essential components, the refractory material of the present invention may contain an appropriate amount of other conventional components conventionally formulated in the manufacture of ceramic-based refractory materials and heat insulating materials.
바람직하게 본 발명의 다공질 세라믹 내화재는 다음과 같은 방법으로 제조할 수 있다.Preferably, the porous ceramic refractory material of the present invention can be produced by the following method.
우선 분말상 세라믹 성분, 섬유상 세라믹 성분 및 바인더를 물과 혼합하고 반죽하여 몰탈을 제조한 다음, 얻어진 몰탈을 보드나 벌크 등의 소망하는 형태의성형틀에 넣어 성형하고, 건조한 후 고온에서 소성하여 원하는 다공질 세라믹 내화재를 제조할 수 있다. 이때 건조는 180∼240℃의 온도에서 수행하는 것이 바람직하고, 1200∼1600℃의 온도에서 수행하는 것이 바람직하다.First, a powdered ceramic component, a fibrous ceramic component, and a binder are mixed with water and kneaded to prepare mortar, and then the obtained mortar is molded into a mold of a desired shape such as a board or a bulk, and then dried and fired at a high temperature to obtain a desired porous material. Ceramic refractory materials can be produced. At this time, the drying is preferably carried out at a temperature of 180 ~ 240 ℃, preferably at a temperature of 1200 ~ 1600 ℃.
이와 같이 제조되는 내화재의 다공성은 배합되는 섬유상 세라믹 성분에 의해 부여되고, 분말상 세라믹 성분과 섬유상 세라믹 성분의 조합으로 급열, 급냉에서도 손상이 없고 낮은 두께에서도 높은 단열성을 나타내고, 견고하면서도 수축팽창률이 거의 없는 내화재의 특성을 얻을 수 있게 된다.The porosity of the refractory material thus produced is imparted by the fibrous ceramic component to be blended, and the combination of the powdery ceramic component and the fibrous ceramic component shows no damage even in rapid quenching and quenching, high insulation even at low thickness, and solid and almost no shrinkage expansion coefficient. The characteristics of the fireproof material can be obtained.
본 발명의 다공질 세라믹 내화재는 예를 들어 SIC히타를 사용하는 동용해 및 동합금용해용의 전기로, 메탈을 사용한 전기로, 미플식 전기로 등의 내부에 사용되는 내화재로서 이용될 수 있다.The porous ceramic refractory material of the present invention can be used, for example, as a refractory material used in copper melting furnaces and copper alloy melting furnaces using SIC heaters, electric furnaces using metals, muffle furnaces and the like.
이하, 본 발명을 실시예의 방법으로 설명하기로 한다. 단, 본 발명은 하기 실시 예로 제한되는 것은 아니다.Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to the following examples.
[실시예 1]Example 1
1. 섬유상 세라믹 성분 제조 :1.Manufacture of fibrous ceramic components:
산화알루미늄 47중량%와 이산화규소 53중량%를 골고루 혼합한 다음 이를 용해시키고 섬유화하여 300 mm이하의 입자크기를 갖는 섬유상 세라믹 성분을 제조하였다.47% by weight of aluminum oxide and 53% by weight of silicon dioxide were evenly mixed, dissolved and fibrous to prepare a fibrous ceramic component having a particle size of 300 mm or less.
2. 몰탈의 제조 :2. Preparation of mortar:
준비된 섬유상세라믹 성분 50중량부, 분말상 세라믹 성분 50중량부 및 알루미나계 시멘트 7중량부를 혼합하고 여기에 물을 부어 너무 묽지 않은 반죽상태의몰탈을 제조하였다.50 parts by weight of the prepared fibrous ceramic component, 50 parts by weight of the powdered ceramic component and 7 parts by weight of alumina cement were mixed and water was poured therein to prepare a mortar having a too thin dough.
3. 성형, 건조 및 소성3. Forming, drying and firing
얻어진 몰탈을 보드 제조용 성형틀에 채워 넣어 성형한 후 성형틀에서 분리하고, 분리된 성형물을 180∼240℃의 온도에서 24시간동안 건조시킨 다음 1200∼1600℃의 고온에서 6시간이상 소성하여, 미세 다공질의 내화 세라믹 보드를 제조하였다.The obtained mortar is filled into a mold for manufacturing a board and molded, and then separated from the mold, and the separated molding is dried at a temperature of 180 to 240 ° C. for 24 hours, and then calcined at a high temperature of 1200 to 1600 ° C. for at least 6 hours. Porous refractory ceramic boards were prepared.
이렇게 제조된 내화 세라믹보드는 기존의 내화벽돌에 비하여 강도는 떨어지나 수축팽창률이 거의 없어 급열, 급냉에서도 손상이 없고 단열성이 향상되어 낮은 두께로의 제작이 가능하였다.The refractory ceramic boards manufactured as described above have lower strengths than conventional refractory bricks, but have almost no shrinkage and expansion coefficient, and thus have no damage even in rapid heat and quenching.
[실시예 2]Example 2
1. 섬유상 세라믹 성분 제조 :1.Manufacture of fibrous ceramic components:
산화알루미늄 47중량%와 이산화규소 53중량%를 골고루 혼합한 다음 이를 용해시키고 섬유화하여 300 mm이하의 입자크기를 갖는 섬유상 세라믹 성분을 제조하였다.47% by weight of aluminum oxide and 53% by weight of silicon dioxide were evenly mixed, dissolved and fibrous to prepare a fibrous ceramic component having a particle size of 300 mm or less.
2. 분말상 세라믹 성분 제조 :2. Preparation of powdery ceramic components:
분말상의 산화알루미늄 95중량%와 산화지르코늄 5중량%의 비율로 골고루 혼합하여 제조하였다.It was prepared by mixing evenly in the ratio of 95% by weight of powdered aluminum oxide and 5% by weight of zirconium oxide.
3. 몰탈의 제조 :3. Preparation of mortar:
준비된 섬유상세라믹 성분 50중량부, 분말상 세라믹 성분 50중량부 및 알루미나계 시멘트 7중량부를 혼합하고 여기에 물을 부어 너무 묽지 않은 반죽상태의몰탈을 제조하였다.50 parts by weight of the prepared fibrous ceramic component, 50 parts by weight of the powdered ceramic component and 7 parts by weight of alumina cement were mixed and water was poured therein to prepare a mortar having a too thin dough.
4. 성형, 건조 및 소성4. Forming, drying and firing
얻어진 몰탈을 보드 제조용 성형틀에 채워 넣어 성형한 후 성형틀에서 분리하고, 분리된 성형물을 180∼240℃의 온도에서 24시간동안 건조시킨 다음 1200∼1600℃의 고온에서 6시간이상 소성하여, 미세 다공질의 내화 세라믹 보드를 제조하였다.The obtained mortar is filled into a mold for manufacturing a board and molded, and then separated from the mold, and the separated molding is dried at a temperature of 180 to 240 ° C. for 24 hours, and then calcined at a high temperature of 1200 to 1600 ° C. for at least 6 hours. Porous refractory ceramic boards were prepared.
이렇게 제조된 내화 세라믹보드는 기존의 내화벽돌에 비하여 강도는 떨어지나 수축팽창률이 거의 없어 급열, 급냉에서도 손상이 없고 단열성이 향상되어 낮은 두께로의 제작이 가능하였다.The refractory ceramic boards manufactured as described above have lower strengths than conventional refractory bricks, but have almost no shrinkage and expansion coefficient, and thus have no damage even in rapid heat and quenching.
이상에서 상세하게 설명한 바와 같은 본 발명에 따르는 내화재는 급열, 급냉에서도 손상이 없고 낮은 두께에서도 높은 단열성을 나타내고, 견고하면서도 수축팽창률이 거의 없어 이를 충전한 전기로의 부피를 줄일 수 있고 전기로의 성능을 향상시킬 수 있게 된다.Refractory material according to the present invention as described in detail above shows no damage even in rapid quenching and quenching, exhibits high thermal insulation even at low thickness, and is hard and shrinkage rate is small, it can reduce the volume of the electric furnace filled therein and improve the performance of the electric furnace You can do it.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605594A (en) * | 1984-08-08 | 1986-08-12 | Minnesota Mining And Manufacturing Company | Ceramic articles having a nonporous core and porous outer layer |
| JPH05310481A (en) * | 1992-05-12 | 1993-11-22 | Mitsui Mining & Smelting Co Ltd | Porous sheetlike refractory and its production |
| JP2001220260A (en) * | 2000-02-07 | 2001-08-14 | Mitsui Mining & Smelting Co Ltd | Alumina-based porous refractory sheet and method for producing the same |
| JP2001220259A (en) * | 2000-02-07 | 2001-08-14 | Mitsui Mining & Smelting Co Ltd | Alumina-mullite porous refractory sheet and method for producing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605594A (en) * | 1984-08-08 | 1986-08-12 | Minnesota Mining And Manufacturing Company | Ceramic articles having a nonporous core and porous outer layer |
| JPH05310481A (en) * | 1992-05-12 | 1993-11-22 | Mitsui Mining & Smelting Co Ltd | Porous sheetlike refractory and its production |
| JP2001220260A (en) * | 2000-02-07 | 2001-08-14 | Mitsui Mining & Smelting Co Ltd | Alumina-based porous refractory sheet and method for producing the same |
| JP2001220259A (en) * | 2000-02-07 | 2001-08-14 | Mitsui Mining & Smelting Co Ltd | Alumina-mullite porous refractory sheet and method for producing the same |
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