KR100508521B1 - A castable refractories composition containing carbon - Google Patents
A castable refractories composition containing carbon Download PDFInfo
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- KR100508521B1 KR100508521B1 KR10-2002-0081684A KR20020081684A KR100508521B1 KR 100508521 B1 KR100508521 B1 KR 100508521B1 KR 20020081684 A KR20020081684 A KR 20020081684A KR 100508521 B1 KR100508521 B1 KR 100508521B1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
Abstract
본 발명은 제철, 제강분야에서 사용되는 부정형 내화조성물에 관한 것이다.The present invention relates to an amorphous refractory composition used in steelmaking and steelmaking.
이 내화조성물은 중량%로, 스피넬 클링커: 20~50%, 입도가 2㎛ 이하인 초미분 알루미나: 5~10%, 입도가 0.1~3mm인 SiC분말: 2~4%, 인조흑연: 3~7%, 알루미나 시멘트: 1~2%, 입도가 0.075mm 이하인 실리카 초미분: 1~3%, 나머지 마그네시아 클링커 및 기타 불가피한 불순물로 조성되는 주원료와 상기 주원료 100중량부에 대하여 인산염: 0.05~0.15중량부, 알루미늄-피치 복합체: 1~3중량부를 포함하여 이루어진다.This refractory composition is in weight percent, spinel clinker: 20-50%, ultrafine powder alumina with a particle size of 2 μm or less: 5-10%, SiC powder with a particle size of 0.1-3mm: 2-4%, artificial graphite: 3-7 %, Alumina cement: 1 to 2%, silica fine powder with particle size of 0.075 mm or less: 1 to 3%, phosphate: 0.05 to 0.15 parts by weight based on the main raw material and 100 parts by weight of the remaining magnesia clinker and other unavoidable impurities , Aluminum-pitch composite: 1 to 3 parts by weight.
이 내화조성물은 산화방지제로 알루미늄 표면을 피치로 코팅처리한 알루미늄-피치 복합체를 사용함으로써, 카본함유 부정형 내화물의 내산화성 및 내식성을 향상시킬 수 있을 뿐만 아니라 제조비용도 저감되는 효과가 있다.By using the aluminum-pitch composite coated on the aluminum surface with pitch as an antioxidant, the refractory composition can not only improve oxidation resistance and corrosion resistance of carbon-containing amorphous refractory materials, but also reduce manufacturing costs.
Description
본 발명은 제철, 제강분야에서 사용되는 부정형 내화조성물에 관한 것으로, 보다 상세하게는 알루미늄 표면을 피치로 코팅처리한 알루미늄-피치 복합체를 산화방지제로 사용함으로써 내산화성 및 내식성을 향상시킨 카본함유 부정형 내화조성물에 관한 것이다.The present invention relates to an amorphous refractory composition used in the field of steelmaking and steelmaking, and more particularly, to an amorphous refractory containing carbon which has improved oxidation resistance and corrosion resistance by using an aluminum-pitch composite coated with aluminum on a pitch as an antioxidant. It relates to a composition.
일반적으로, 내화물에는 무기산화물과 슬라그간의 반응 억제 및 급격한 사용 온도변화로 인한 스폴링 발생을 개선하기 위하여 카본을 사용한다.Generally, carbon is used in the refractory to suppress the reaction between the inorganic oxide and the slag and to improve the spalling caused by the rapid change in the use temperature.
정형 내화물의 경우, 보통 13~20중량%의 카본을 사용하는데, 이는 카본량이 13중량% 미만이면 내스폴링성이 저하되어 박리 탈락이 증가됨으로써 내화물의 내용성이 크게 떨어지고, 20중량%를 초과하면 조직의 치밀화 및 강도저하, 카본산화 억제를 위한 산화방지제의 사용량이 증가하게 되어 저융점 생성물이 증가되고 내화물의 물성이 저하되기 때문이다.In the case of standard refractory materials, 13 to 20% by weight of carbon is usually used. If the amount of carbon is less than 13% by weight, the spalling resistance is lowered and the peeling and dropping is increased. This is because the use of antioxidants for densification and strength reduction of tissues and the inhibition of carbon oxidation is increased, thereby increasing the low melting point product and deteriorating the properties of the refractory.
부정형 내화물의 경우, 상기 정형 내화물보다 카본 사용량에 보다 큰 제약이 따르는데, 이는 카본 사용량이 많으면 소요 수분량이 증가하게 됨으로써 조직이 치밀하게 형성되지 못하여 제반 물성이 떨어지기 때문이다. 따라서, 부정형 내화물에서는 일반적으로 카본 사용량이 10중량% 이하로 제한된다. 또한, 부정형 내화물은 카본함유 정형 내화물과는 달리 수분과 혼합하여 사용되기 때문에 정형 내화물보다 조직 치밀화가 떨어지며, 그로 인하여 카본의 산화 정도가 증가하게 된다. 상기 카본의 산화를 억제하기 위하여 산화방지제를 사용하게 되며, 상기 산화방지제는 수분과의 반응 등을 고려하여 선택하여야 한다. 최근에는 산화방지제의 수화반응 문제를 해결하기 위하여 고가의 탄화물계 또는 붕소화합물계 등의 산화방지제(B4C, ZrB2, CaB6등)를 사용하고 있는 실정이다.In the case of the amorphous refractory material, there is a greater restriction on the amount of carbon used than the standard refractory material, because when the amount of carbon is used, the required amount of water is increased, so that the structure is not formed densely and the overall physical properties are inferior. Therefore, in the amorphous refractory material, the carbon usage is generally limited to 10% by weight or less. In addition, since amorphous refractory materials are used in combination with moisture unlike carbon-containing standard refractory materials, the densification of tissues is lower than that of standard refractory materials, thereby increasing the degree of oxidation of carbon. An antioxidant is used to inhibit oxidation of the carbon, and the antioxidant should be selected in consideration of reaction with moisture. Recently, in order to solve the problem of the hydration reaction of the antioxidant, an expensive antioxidant (B 4 C, ZrB 2 , CaB 6, etc.) such as carbide-based or boron compound-based has been used.
본 발명은 상기한 종래기술의 문제점을 해결하기 위한 것으로, 고가의 산화방지제를 사용하는 대신에 알루미늄 표면을 피치로 코팅처리한 알루미늄-피치 복합체를 산화방지제로 사용함으로써, 카본함유 부정형 내화물의 내산화성 및 내식성을 향상시키는데, 그 목적이 있다. The present invention is to solve the above problems of the prior art, by using an aluminum-pitch composite coated with an aluminum surface pitch as an antioxidant instead of using an expensive antioxidant, the oxidation resistance of carbon-containing amorphous refractory And to improve corrosion resistance.
상기한 목적을 달성하기 위한 본 발명은 중량%로, 스피넬 클링커: 20~50%, 입도가 2㎛ 이하인 초미분 알루미나: 5~10%, 입도가 0.1~3mm인 SiC분말: 2~4%, 인조흑연: 3~7%, 알루미나 시멘트: 1~2%, 입도가 0.075mm 이하인 실리카 초미분: 1~3%, 나머지 마그네시아 클링커 및 기타 불가피한 불순물로 조성되는 주원료와 상기 주원료 100중량부에 대하여 인산염: 0.05~0.15중량부, 알루미늄-피치 복합체: 1~3중량부를 포함하여 이루어진다.The present invention for achieving the above object by weight%, spinel clinker: 20-50%, ultrafine powder alumina having a particle size of 2㎛ or less: 5-10%, SiC powder having a particle size of 0.1-3mm: 2-4%, Artificial Graphite: 3 ~ 7%, Alumina Cement: 1 ~ 2%, Silica Ultrafine Particles with Particle Size 0.075mm or Less: 1 ~ 3%, Main Magnesium Clinker and Other Unavoidable Impurities : 0.05 to 0.15 parts by weight, aluminum-pitch composite: 1 to 3 parts by weight.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명은 카본함유 부정형 내화물의 내산화성 및 내식성을 향상시키기 위하여, 고가의 산화방지제를 사용하는 대신에 알루미늄 표면을 피치로 코팅처리한 알루미늄-피치 복합체를 산화방지제로 사용하는데 특징이 있는 것으로, 이하 본 발명의 성분한정 이유부터 살펴본다.The present invention is characterized in that, in order to improve the oxidation resistance and corrosion resistance of the carbon-containing amorphous refractory, an aluminum-pitch composite coated with an aluminum surface as a pitch instead of using an expensive antioxidant, It looks at the reason for the limitation of the present invention.
스피넬 클링커: 20~50중량%Spinel Clinker: 20-50% by weight
상기 스피넬 클링커는 마그네시아계 부정형 내화물의 내스폴링성을 증진하기 위하여 첨가되는 성분으로, 20중량% 미만 첨가되면 상기 내스폴링성 증진 효과가 적으며, 50중량%를 초과하여 첨가되면 내스폴링성의 증진 효과보다는 내침식성이 크게 저하되는 단점이 있으므로, 그 함량을 20~50중량%로 제한하는 것이 바람직하다.The spinel clinker is a component added to enhance the spalling resistance of the magnesia-based amorphous refractory, and when added in an amount less than 20% by weight, the spalling resistance is less enhanced, and when added in excess of 50% by weight, the spalling resistance is enhanced. Rather than having a disadvantage in that the corrosion resistance is greatly reduced, it is preferable to limit the content to 20 to 50% by weight.
또한, 상기 스피넬 클링커는 25~35중량%의 MgO와 64~74중량%의 Al2O3, 나머지 CaO 및 기타 불가피한 불순물로 이루어지는 것을 사용하면 상기 내스폴링성 증진에 보다 효과적이다.In addition, the spinel clinker is more effective in improving the spalling resistance by using 25 to 35% by weight of MgO and 64 to 74% by weight of Al 2 O 3 , the remaining CaO and other unavoidable impurities.
입도가 2㎛ 이하인 초미분 알루미나: 5~10중량%Ultrafine powdered alumina with a particle size of 2 μm or less: 5 to 10 wt%
상기 초미분 알루미나는 마그네시아와 반응하여 스피넬을 형성함으로써 슬라그 침투를 억제하고 강도 및 내스폴링성을 증진시킬 뿐만 아니라 혼련물의 유동성을 증가시키는 역할도 한다. 상기 초미분 알루미나의 입도가 2㎛를 초과하면 유동성 증가 효과가 적으므로, 그 입도를 2㎛ 이하로 제한하는 것이 바람직하다. 또한, 상기 초미분 알루미나의 함량이 5중량% 미만이면 시공 가능한 유동성을 얻을 수 없으며, 10중량%를 초과하면 내침식성이 저하되므로, 그 함량을 5~10중량%로 제한하는 것이 바람직하다.The ultra fine alumina reacts with magnesia to form spinel, thereby inhibiting slag penetration and enhancing strength and spalling resistance as well as increasing flowability of the kneaded material. When the particle size of the ultra fine alumina exceeds 2 μm, the effect of increasing fluidity is small, and therefore, the particle size is preferably limited to 2 μm or less. In addition, if the content of the ultra-fine alumina is less than 5% by weight can not be obtained fluidity, construction exceeds 10% by weight, so erosion resistance is lowered, it is preferable to limit the content to 5 to 10% by weight.
입도가 0.1~3mm인 SiC분말: 2~4중량%SiC powder with a particle size of 0.1 to 3 mm: 2 to 4 wt%
상기 SiC분말은 카본의 산화를 억제시켜 내화물의 내침식성을 증진시키는데 유효한 성분으로, 그 입도가 0.1mm 미만이면 마그네시아 및 다른 산화물과의 반응성이 증대되어 저융점 복합산화물의 생성속도가 빨라져 내침식성이 저하되고, 3mm를 초과하면 SiC의 산화속도 및 저융점 복합산화물의 생성속도가 늦어져 카본 산화억제 효과가 떨어지므로, 상기 SiC분말의 입도는 0.1~3mm로 제한하는 것이 바람직하다. 또한, 상기 SiC분말의 함량이 2중량% 미만이면 카본산화 억제효과가 적어 내침식성이 열화되고, 4중량%를 초과하면 SiC 산화에 의하여 생성된 산화물에 기인한 저융점 복합산화물의 생성량이 증가하여 내침식성이 오히려 저하되므로, 그 함량을 2~4중량%로 제한하는 것이 바람직하다.The SiC powder is an effective ingredient for inhibiting the oxidation of carbon to enhance the corrosion resistance of the refractory. If the particle size is less than 0.1 mm, the reactivity with magnesia and other oxides is increased, and thus the formation rate of the low melting point composite oxide is increased, and the corrosion resistance is increased. When it is lowered and exceeds 3 mm, the oxidation rate of SiC and the production rate of the low melting point composite oxide are slowed, and the carbon oxidation inhibitory effect is lowered. Therefore, the particle size of the SiC powder is preferably limited to 0.1 to 3 mm. In addition, when the content of the SiC powder is less than 2% by weight, the effect of inhibiting carbon oxidation is small, and corrosion resistance is deteriorated. When the content of the SiC powder is more than 4% by weight, the amount of low melting point composite oxide due to the oxide produced by the oxidation of SiC increases. Since erosion resistance is rather reduced, it is preferable to limit the content to 2 to 4% by weight.
인조흑연: 3~7중량%Artificial Graphite: 3 ~ 7 wt%
상기 인조흑연은 내화원료인 산화물과 슬라그간의 반응을 억제하고 내스폴링성을 증진시키는데 유효한 성분으로, 3중량% 미만 첨가되면 슬라그 침투에 의한 무기산화물의 침식을 억제하는 효과가 떨어지고, 7중량%를 초과하여 첨가되면 시공시 소요되는 수분량이 증가하여 조직이 치밀하게 형성되지 못하므로, 그 함량을 3~7중량%로 제한하는 것이 바람직하다.The artificial graphite is an effective ingredient for suppressing the reaction between the oxide and slag of refractory raw materials and enhancing the spalling resistance, and when less than 3 wt% is added, the effect of inhibiting the erosion of the inorganic oxide due to slag penetration is reduced, and the weight is 7 wt. If it is added in excess of%, the amount of moisture required during construction is increased, so that the tissue is not formed precisely, it is preferable to limit the content to 3 to 7% by weight.
또한, 본 발명에서 소요 수분량을 감소시켜 조직을 보다 치밀하게 하기 위해서는 부피비중이 1.5~1.8g/cm3이고 기공율이 18~26%인 고밀도, 저기공율의 박판상이 아닌 인조흑연을 사용하는 것이 보다 바람직하다. 또한, 상기 인조흑연의 입도가 0.025mm 미만이면 혼련시 수분의 사용량이 증가될 뿐만 아니라 산화속도가 빨라져 내화물의 물성을 저하시키고, 0.5mm를 초과하면 고온에서 산화로 인하여 내화물 조직내에 큰 기공이 형성되어 내화물의 내식성을 저하시키므로, 상기 입도는 0.025~0.5mm로 제한하는 것이 바람직하다.In addition, in order to reduce the amount of moisture required in the present invention to make the tissue more dense, it is more preferable to use a high-density, low-porosity artificial graphite, which has a volume specific gravity of 1.5 to 1.8 g / cm 3 and a porosity of 18 to 26%. desirable. In addition, if the particle size of the artificial graphite is less than 0.025mm, not only the amount of water used during kneading is increased, but also the oxidation rate is increased, thereby reducing the physical properties of the refractory material. Since the corrosion resistance of a refractory material is reduced, it is preferable to limit the said particle size to 0.025-0.5 mm.
그리고, 본 발명에서는 상기 인조흑연으로 제강분야에서 전기로를 이용하여 용강을 제조할 때 발생되는 폐전극봉을 분쇄하여 얻을 수 있는 구형 또는 구형에 가까운 분말을 사용하는 것이 가능하다.In the present invention, it is possible to use spherical or near spherical powder that can be obtained by pulverizing the waste electrode generated when manufacturing molten steel using an electric furnace in the steelmaking field with the artificial graphite.
알루미나 시멘트: 1~2중량%Alumina Cement: 1-2 wt%
상기 알루미나 시멘트는 결합제로서, 1중량% 미만 첨가되면 결합 효과를 얻을 수 없고, 2중량%를 초과하여 첨가되면 저융점 복합산화물의 생성이 증가하여 내식성이 저하되므로, 그 함량을 1~2중량%로 제한하는 것이 바람직하다.The alumina cement is a binder, when less than 1% by weight can not be obtained when the binding effect, when added in excess of 2% by weight of the low melting point composite oxide to increase the corrosion resistance is lowered, the content is 1 to 2% by weight It is preferable to limit to.
입도가 0.075mm 이하인 실리카 초미분: 1~3중량%Ultrafine silica powder with a particle size of 0.075 mm or less: 1-3 wt%
상기 실리카 초미분은 알루미나 시멘트와 같이 결합제로 첨가되며, 1중량% 미만 첨가되면 결합 효과를 얻을 수 없고, 3중량%를 초과하여 첨가되면 저융점 복합산화물의 생성이 증가하여 내식성이 저하되므로, 그 함량을 1~3중량%로 제한하는 것이 바람직하다. 또한, 상기 실리카 초미분의 입도가 0.075mm를 초과하면 유동성이 저하되므로, 상기 입도는 0.075mm 이하로 제한하는 것이 바람직하다.The ultrafine silica powder is added as a binder, such as alumina cement, and when added in an amount less than 1% by weight, no binding effect is obtained. It is preferable to limit the content to 1 to 3% by weight. In addition, since the fluidity decreases when the particle size of the ultrafine silica powder exceeds 0.075 mm, the particle size is preferably limited to 0.075 mm or less.
상기한 조성 이외에 나머지는 마그네시아 클링커 및 기타 불가피한 불순물로 조성된다.In addition to the above compositions, the remainder is composed of magnesia clinker and other unavoidable impurities.
상기와 같이 조성되는 주원료 100중량부에 대하여 인산염 및 알루미늄-피치 복합체가 외삽으로 첨가된다.The phosphate and aluminum-pitch composites are extrapolated based on 100 parts by weight of the main raw material prepared as described above.
인산염: 0.05~0.15중량부Phosphate: 0.05 ~ 0.15 parts by weight
상기 인산염은 분산제로서, 0.05중량부 미만 첨가되면 원료의 분산효과가 떨어져 유동성이 저하되며, 0.15중량부를 초과하여 첨가되면 혼련물의 점도가 증가하여 유동성이 저하되므로, 그 첨가량은 주원료 100중량부에 대하여 0.05~0.15중량부로 제한하는 것이 바람직하다.As the phosphate is a dispersant, when the content is less than 0.05 parts by weight, the dispersing effect of the raw material is lowered, and the fluidity is lowered. It is preferable to limit it to 0.05-0.15 weight part.
알루미늄-피치 복합체: 1~3중량부Aluminum-Pitch Composite: 1-3 parts by weight
상기 알루미늄-피치 복합체는 SiC와 더불어 카본의 산화를 억제하기 위하여 첨가되는 산화방지제이다. Al은 염기성 카본함유 내화벽돌에 주로 사용되는 금속 산화방지제인데, 비교적 저온에서 용융하여 카본과 1차 반응하고, 2차로 스피넬을 생성함으로써 카본 산화억제 및 내식성 증가에 효과가 크며, 가격이 비교적 저가인 장점이 있다. 그러나, 상기 Al은 본 발명과 같이 물을 첨가하여 사용하는 부정형 내화물에 사용될 경우, 급격한 수화반응이 발생하고, Al의 첨가량이 증가되어 수화반응 정도가 심해지면 폭발의 위험성까지 있는 문제점이 있다. 따라서, 본 발명에서는 상기 수화반응을 억제하기 위하여 알루미늄 표면을 피치로 코팅(coating)처리한 알루미늄-피치 복합체를 사용한다. 상기 알루미늄-피치 복합체의 첨가량이 1중량부 미만이면 산화방지효과가 미미하고, 3중량부를 초과하면 소요 수분량이 증가하여 카본 산화억제 효과보다 조직치밀화가 떨어지므로, 그 첨가량은 주원료 100중량부에 대하여 1~3중량부로 제한하는 것이 바람직하다.The aluminum-pitch composite is an antioxidant added together with SiC to inhibit oxidation of carbon. Al is a metal antioxidant mainly used for basic carbon-containing refractory bricks. It melts at a relatively low temperature and reacts first with carbon. Secondly, it forms spinel. It is effective in increasing carbon oxidation and corrosion resistance and is relatively inexpensive. There is an advantage. However, when Al is used in an amorphous refractory to which water is added as in the present invention, a rapid hydration reaction occurs, and when the amount of Al is increased to increase the degree of hydration reaction, there is a problem of explosion. Therefore, in the present invention, to suppress the hydration reaction, an aluminum-pitch composite coated with an aluminum surface with a pitch is used. When the addition amount of the aluminum-pitch composite is less than 1 part by weight, the antioxidant effect is insignificant, and when the amount is more than 3 parts by weight, the required moisture content is increased and the tissue densification is lower than the carbon oxidation inhibitory effect. It is preferable to limit to 1-3 parts by weight.
상기 알루미늄-피치 복합체의 입도가 0.15mm를 초과하면 조직내의 균일한 분포 효과가 떨어져 내산화성 증진 효과가 저하되므로, 그 입도는 0.15mm 이하로 제한하는 것이 바람직하다. 또한, 상기 알루미늄-피치 복합체의 알루미늄과 피치의 중량비가 4:6~6:4인 것을 사용하면 내산화성 증진에 보다 바람직한데, 상기 중량비가 4:6 미만에서는 금속 Al 함량이 상대적으로 적어 내산화성 증진효과가 적으며, 6:4 에서는 피치 함량이 적어 금속 Al의 코팅 효과가 떨어지게 된다.When the particle size of the aluminum-pitch composite exceeds 0.15 mm, a uniform distribution effect in the tissue is lowered, and the oxidation resistance enhancing effect is lowered. Therefore, the particle size is preferably limited to 0.15 mm or less. In addition, when the weight ratio of aluminum and pitch of the aluminum-pitch composite is 4: 6 to 6: 4, it is more preferable to enhance oxidation resistance. When the weight ratio is less than 4: 6, the metal Al content is relatively small and thus oxidation resistance is achieved. The enhancement effect is small, and the pitch content is small at 6: 4, thereby decreasing the coating effect of the metal Al.
이하, 실시예를 통하여 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예]EXAMPLE
28중량%의 MgO와 71중량%의 Al2O3를 함유하는 스피넬 클링커, 2㎛ 이하의 초미분 알루미나, 입도가 0.1~3mm인 SiC분말을 준비하였다. 또한, 제강분야에서 전기로를 이용하여 용강을 제조할 때 발생되는 폐전극봉을 분쇄하여 인조흑연을 준비하였으며, 그 특성은 하기 표 1과 같다.Spinel clinker containing 28 wt% MgO and 71 wt% Al 2 O 3 , ultrafine alumina of 2 μm or less, and SiC powder having a particle size of 0.1 to 3 mm were prepared. In addition, the artificial electrode was prepared by pulverizing the waste electrode generated when manufacturing molten steel using an electric furnace in the steelmaking field, the characteristics are shown in Table 1.
그리고, Al2O3순도 70%급의 알루미나 시멘트, 실리카 초미분 및 MgO순도가 95% 이상인 마그네시아 클링커를 준비하였다. 상기 원료를 하기 표 2와 같이 배합하고, 인산염 및 알루미늄과 피치의 중량비가 4:6~6:4인 알루미늄-피치 복합체를 하기 표 2와 같이 외삽으로 첨가하였다.Then, magnesia clinker having alumina cement of 70% Al 2 O 3 purity, ultra fine silica and MgO purity of 95% or more was prepared. The raw materials were blended as shown in Table 2 below, and an aluminum-pitch composite having a weight ratio of phosphate, aluminum and pitch of 4: 6 to 6: 4 was added by extrapolation as shown in Table 2 below.
상기한 내화조성물 원료 100중량부에 대하여 6.5중량부의 물을 투입하여 실온에서 혼련기를 이용하여 5분간 혼련하고, 40x40x160mm, 40x40x40mm, 60x60x60mm 크기의 성형틀에 혼련물을 투입한 다음 15초 동안 진동 유입성형하였다. 이후, 성형체를 24시간 양생한 후, 110℃ 건조기에서 24시간 동안 건조하였다.6.5 parts by weight of water was added to 100 parts by weight of the refractory composition, and kneaded at room temperature for 5 minutes using a kneader. The mixture was introduced into a mold having a size of 40x40x160mm, 40x40x40mm, and 60x60x60mm, followed by vibration inlet molding for 15 seconds. It was. Thereafter, the molded body was cured for 24 hours, and then dried in a 110 ° C. dryer for 24 hours.
상기와 같이 제조된 시편의 유동도, 기공율, 상온곡강도, 내스폴링성, 침식지수 및 산화성 지수를 측정하였으며, 그 결과는 하기 표 2와 같다.The flow rate, porosity, room temperature bending strength, spalling resistance, erosion index, and oxidative index of the specimens prepared as described above were measured, and the results are shown in Table 2 below.
상기 유동도는 시편을 유동도 측정 테이블에 올려놓고 15회 타격한 후, 퍼진 길이(mm)를 측정한 것이다.The flow rate is a measure of the spread length (mm) after placing the specimen on the flow measurement table and hitting 15 times.
상기 기공율 및 상온곡강도는 부정형 내화물 물성측정방법에 준하여 측정하였다.The porosity and room temperature bending strength were measured according to the method of measuring the amorphous refractory properties.
상기 내스폴링성은 60x60x60mm크기의 시편을 전기로에 장입하여 1400℃까지 5℃/분의 승온속도로 소성한 후, 1400℃에서 20분 유지한 다음 노에서 꺼내어 물에서 5분 동안 냉각하였다. 이후, 1400℃로 유지된 전기로에 장입하여 20분간 유지하는 실험을 반복하여, 시편이 파괴될 때까지의 반복횟수를 측정한 것이다.The spalling resistance was charged into a 60x60x60mm sized specimen in an electric furnace and calcined at a temperature increase rate of 5 ° C / min to 1400 ° C, held at 1400 ° C for 20 minutes, and then taken out of the furnace and cooled in water for 5 minutes. Thereafter, the experiment was repeated for 20 minutes by charging into an electric furnace maintained at 1400 ° C. to measure the number of repetitions until the specimen was destroyed.
상기 침식지수는 산소-프로판을 열원으로 하는 드럼식 회전침식기에 슬라그(CaO/SiO2=6)를 투입하여 용융시킨 다음 1650℃에서 30분간 반응시킨 후 배출하고, 다시 슬라그를 재투입하여 용융, 반응시키는 것을 5회 반복한 후, 시편의 가운데를 절단하여 침식된 길이를 측정하였다. 상기 측정된 침식길이를 하기 수학식 1에 대입하여 침식지수를 구한 것이며, 하기 수학식 1의 기준시편의 침식길이는 비교재(1)의 침식길이이다.The erosion index was melted by adding slag (CaO / SiO 2 = 6) to a drum type rotary erosion machine using oxygen-propane as a heat source, reacting at 1650 ° C. for 30 minutes, and then discharging the slag again to melt, After the reaction was repeated five times, the middle of the specimen was cut to measure the length of erosion. The erosion index was obtained by substituting the measured erosion length into Equation 1 below, and the erosion length of the reference specimen of Equation 1 below is the erosion length of the comparative material (1).
상기 산화성 지수는 40x40x40mm크기의 시편을 전기로에 장입하여 1500℃까지 5℃/분의 승온속도로 가열하고, 1500℃에서 3시간 유지한 다음 노냉한 후, 높이 방향의 중앙을 절단하여 탈탄길이를 측정하였다. 상기 측정된 탈탄길이를 하기 수학식 2에 대입하여 산화성 지수를 구한 것이며, 하기 수학식 2의 기준시편의 탈탄길이는 비교재(1)의 탈탄길이이다.The oxidative index is inserted into the electric furnace 40x40x40mm size specimen heated to a heating rate of 5 ℃ / min up to 1500 ℃, maintained at 1500 ℃ for 3 hours, after the furnace is cooled, cut the center of the height direction to measure the decarburization length It was. The decarburization length was calculated by substituting the measured decarburization length into Equation 2 below, and the decarburization length of the reference specimen of Equation 2 below is the decarburization length of the comparative material (1).
상기 표 2에서 비교재(5)의 기공율, 상온곡강도, 내스폴링성은 현장사용 가능 유동도인 140mm를 확보한 후에 측정한 것이다.In Table 2, the porosity, room temperature bending strength, and spalling resistance of the comparative material 5 were measured after securing 140 mm, which is a field useable flow rate.
상기 표 2에 나타난 바와 같이, 산화방지제로 알루미늄-피치 복합체를 본 발명의 범위내로 사용한 발명재(1~6)은 산화방지제를 SiC만 사용한 비교재(1), 산화방지제로 B4C를 사용한 비교재(3~4, 6) 및 알루미늄-피치를 본 발명의 범위보다 많이 첨가한 비교재(5)에 비하여 내식성 및 내산화성이 우수함을 알 수 있다.As shown in Table 2, the inventive materials (1 to 6) using the aluminum-pitch composite as an antioxidant within the scope of the present invention are comparative materials (1) using only SiC as an antioxidant and B 4 C as an antioxidant. It can be seen that the comparative materials (3 to 4, 6) and the aluminum-pitch are superior in the corrosion resistance and the oxidation resistance compared to the comparative material (5) which added more than the range of the present invention.
이에 반하여 비교재(2)는 산화방지제로 Al을 사용한 것으로, 수분과의 수화반응으로 인하여 시편 내부에 미세 기공 및 균열이 발생하였다. 따라서, 기공율이 상당히 증가하여 조직치밀화가 떨어졌으며, 제반 물성도 떨어졌다.On the contrary, the comparative material 2 used Al as an antioxidant, and micropores and cracks were generated in the specimen due to the hydration reaction with moisture. Therefore, the porosity increased considerably, resulting in poor tissue densification and poor physical properties.
또한, 비교재(3~4, 6)는 산화방지제로 고가(Al의 가격 대비 10배 이상)의 B4C를 사용한 것으로, 내산화성은 향상되었으나, B4C 산화 생성물의 낮은 융점으로 인해 내식성 저하를 보였고, 내스폴링성도 떨어졌다.In addition, the comparative materials (3 to 4, 6) used an expensive B 4 C as an antioxidant (more than 10 times the price of Al), and improved oxidation resistance, but corrosion resistance due to the low melting point of the B 4 C oxidation product It showed the fall, and also fell the spalling resistance.
또한, 비교재(5)는 산화방지제로 알루미늄-피치 복합체를 사용하기는 하였으나, 본 발명의 범위를 초과한 4중량부를 첨가한 것으로, 알루미늄-피치 복합체의 첨가량이 너무 많아 유동성이 떨어져 현장 사용 가능 조건인 140mm 이하를 나타내었다. 따라서, 140mm의 유동성 확보를 위해서 소요 수분량이 증가하였고, 그로 인하여 조직 치밀화가 저하되어 내식성이 떨어졌다.In addition, although the comparative material 5 used an aluminum-pitch composite as an antioxidant, it added 4 parts by weight exceeding the range of the present invention, and the addition amount of the aluminum-pitch composite was too high to allow fluidity in the field. The conditions of 140 mm or less were shown. Therefore, the required amount of water was increased to secure the fluidity of 140 mm, thereby reducing tissue densification and deteriorating corrosion resistance.
상술한 바와 같이, 본 발명은 산화방지제로 알루미늄 표면을 피치로 코팅처리한 알루미늄-피치 복합체를 사용함으로써, 카본함유 부정형 내화물의 내산화성 및 내식성을 향상시킬 수 있을 뿐만 아니라 제조비용도 저감되는 효과가 있다.As described above, according to the present invention, by using the aluminum-pitch composite coated with aluminum on the pitch as an antioxidant, not only the oxidation resistance and corrosion resistance of the carbon-containing amorphous refractory can be improved, but also the manufacturing cost is reduced. have.
Claims (5)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101157045B1 (en) * | 2004-12-24 | 2012-06-21 | 주식회사 포스코 | Batch compositions of carbon contained basic castable refractories for ladle slag line |
| WO2013027890A1 (en) * | 2011-08-22 | 2013-02-28 | Korea Institute Of Science And Technology | Spinel-silicon carbide refractory compositions with high corrosion resistivity to coal slag and manufacturing method thereof |
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| KR100734516B1 (en) * | 2005-12-22 | 2007-07-03 | 재단법인 포항산업과학연구원 | Magnesia-spinel-carbon contained basic castable compositions for repairing of converter |
| EP2072482A1 (en) * | 2007-12-17 | 2009-06-24 | Evonik Degussa GmbH | Mixture and fire-resistant moulds made from the mixture or masses with high hydration resistance |
| DE202013011896U1 (en) | 2013-02-04 | 2014-09-16 | Refratechnik Holding Gmbh | Feuerbetonversatz containing a geopolymer binder system and the use of the offset |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101157045B1 (en) * | 2004-12-24 | 2012-06-21 | 주식회사 포스코 | Batch compositions of carbon contained basic castable refractories for ladle slag line |
| WO2013027890A1 (en) * | 2011-08-22 | 2013-02-28 | Korea Institute Of Science And Technology | Spinel-silicon carbide refractory compositions with high corrosion resistivity to coal slag and manufacturing method thereof |
| KR101247691B1 (en) * | 2011-08-22 | 2013-04-01 | 한국과학기술연구원 | Spinel-Silicon Carbide Refractory compositions with High Corrosion Resistivity to Coal Slag and Manufacturing Method thereof |
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