KR20020052828A - Refractory composition - Google Patents
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- KR20020052828A KR20020052828A KR1020000082292A KR20000082292A KR20020052828A KR 20020052828 A KR20020052828 A KR 20020052828A KR 1020000082292 A KR1020000082292 A KR 1020000082292A KR 20000082292 A KR20000082292 A KR 20000082292A KR 20020052828 A KR20020052828 A KR 20020052828A
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Abstract
Description
본 발명은 내화물 조성물에 관한 것으로, 보다 상세하게는 향상된 강도 및 내산화성을 갖으며, 높은 내스폴링 특성을 갖는 내화물을 제조할 수 있는 내화물 조성물에 관한 것이다.The present invention relates to a refractory composition, and more particularly, to a refractory composition capable of producing a refractory having improved strength and oxidation resistance and having high spalling properties.
[종래 기술][Prior art]
Al2O3-C계 내화물은 제철소의 제강 공정 및 연속 주조 공정에서 슬라이드 게이트(Slide gate), 래들 슈라우드(Ladle Shroud), 상부 노즐(Upper Nozzle), 하부 노즐(Lower Nozzle), 침지 노즐의 몸체부 등, 주로 노즐류에 사용되는 중성 내화 벽돌이다. 상기 내화물은 1600℃ 부근, 고비중의 용강에 사용되기 때문에, 상온 강도 및 고온 강도 등의 기계적 성질뿐만 아니라, 탄소의 산화에 의하여 내화물이 열화되지 않도록 내산화성을 갖아야 하고, 용강에 의해 젖음성(wettability)을 나타내지 않으며 갑작스런 열충격에 의해 내화물이 파손되는 스폴링(spalling)에 대한 저항성이 우수해야 하는 등의 특성이 요구된다.Al 2 O 3 -C-based refractory is the body of the slide gate, ladle shroud, upper nozzle, lower nozzle, immersion nozzle in steelmaking and continuous casting process of steel mill It is a neutral refractory brick mainly used for nozzles. Since the refractory material is used in high specific gravity molten steel near 1600 ° C, not only mechanical properties such as room temperature strength and high temperature strength, but also have oxidation resistance so that refractory is not degraded by oxidation of carbon, and wettability by molten steel ( It does not show wettability and requires excellent resistance to spalling in which refractory is broken by sudden thermal shock.
이러한 특성 중, 고온 특성을 향상시키기 위하여, Al2O3클린커(clinker) 및탄소원으로 인상(flake) 흑연을 혼합하고, 이들 골재 성분의 혼합물을 성형하여 성형체를 제조한 후, 이 성형체를 소성하여 Al2O3-C계 내화물을 제조하는 방법이 시도되었다. 또한 상기 Al2O3와 인상 흑연만 사용하여 성형체를 제조하면 성형체 제조가 어렵고, 또한, 제조된 성형체의 강도가 약한 문제가 있어서, 수지를 성형 조제인 결합재로 사용하여 성형체를 제조하는 방법이 일반적으로 실시되고 있다(G.I.Antonov, Refractory and Industrial Ceramics, 39(9-10) 329 (1998), E.V.Krivokorytov et.al., Glass and Ceramics, 55(5-6) 144 (1998), W. Sinclair, Materials Forum 20 193 (1996)).Among these characteristics, in order to improve high temperature characteristics, flake graphite is mixed with an Al 2 O 3 clinker and a carbon source, a mixture of these aggregate components is molded to prepare a molded body, and then the molded body is fired. A method of preparing an Al 2 O 3 -C system refractory has been attempted. In addition, when a molded article is manufactured using only Al 2 O 3 and impression graphite, it is difficult to manufacture a molded article, and there is a problem in that the strength of the manufactured molded article is weak. Thus, a method of manufacturing a molded article using a resin as a binder for molding is generally used. (GIAntonov, Refractory and Industrial Ceramics, 39 (9-10) 329 (1998), EVKrivokorytov et.al., Glass and Ceramics, 55 (5-6) 144 (1998), W. Sinclair, Materials Forum 20 193 (1996)).
결합재를 사용하여 상기 주성분인 골재 성분과 결합재를 혼합하여, 성형하고 소성하면, 결합재가 중합되면서 상기 골재 성분들이 결합되어, 우수한 강도를 갖는 성형체가 제조될 수 있다. 일반적으로 결합재로서는 액상 또는 고상(혹은 이들 복합)의 페놀 수지가 사용되고 있으나, 수지의 가격이 고가이며, 수지를 사용하여 제조된 내화물을 실제 제강 조업 중에 사용할 때, 이 수지가 흑연으로 결정화되기 어려운 난흑연화성 탄소로 되어, 제조된 내화물이 취성을 가지므로 내스폴링성이 저하되는 결점이 있다. 따라서 최근에는 가능한 결합재의 양을 최소로 하면서 성형시의 결합력을 부여하기 위하여 결합재 수지의 점도를 조절하거나 유기 용매로 변성시킨 수지를 사용하는 등의 연구가 진행되어 왔으나, 수지의 변성에 의해서 결합재의 가격은 더욱 상승하였고, 기대만큼의 특성 개선은 이루어지지 않고 있는 실정이다. 또한, 내산화성을 향상시키기 위하여, Si, Al, Mg 등의 금속 산화방지제를첨가하는 방법이 연구되었으며, 내스폴링성을 향상시키기 위한 연구도 진행되었으나, 만족할만한 효과를 얻을 수 없었다.When the aggregate is mixed with the main component and the binder using a binder, molded and fired, the aggregate is bonded while the binder is polymerized, thereby forming a molded article having excellent strength. Generally, phenolic resins in liquid or solid phase (or these complexes) are used as binders, but the resins are expensive and difficult to crystallize into graphite when the refractory manufactured using the resins is used during actual steelmaking operations. Graphitized carbon is used, and the produced refractory has brittleness, and thus has a disadvantage in that spalling resistance is lowered. Therefore, in recent years, studies have been conducted to control the viscosity of the binder resin or to use a resin modified with an organic solvent in order to give the bonding force during molding while minimizing the amount of the binder possible. Prices have risen further, and characteristics are not improving as much as expected. In addition, in order to improve oxidation resistance, a method of adding metal antioxidants such as Si, Al, Mg, and the like has been studied, and studies to improve spalling resistance have been conducted, but satisfactory effects have not been obtained.
본 발명은 상술한 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 강도가 높은 내화물을 제조할 수 있는 내화물 조성물을 제공하는 것이다.The present invention has been made to solve the above problems, and an object of the present invention is to provide a refractory composition capable of producing a high strength refractory.
본 발명의 다른 목적은 우수한 내산화성 및 높은 내스폴링성을 갖는 내화물을 제조할 수 있는 내화물 조성물을 제공하는 것이다.Another object of the present invention is to provide a refractory composition which can produce a refractory having excellent oxidation resistance and high spalling resistance.
상기 목적을 달성하기 위하여, 본 발명은 Al2O3클린커 및 인상 흑연을 포함는 주성분 100 중량부; 액상 수지 결합재 2 내지 5 중량부; 및 고상 결합재를 포함하는 Al2O3계 내화물 조성물을 제공한다. 상기 고상 결합재로는 상기 주성분 100 중량부에 대하여 1 내지 3 중량부의 고상 페놀 수지를 사용할 수 도 있고, 1 내지 5 중량부의 석탄계 또는 석유계 핏치 분말을 사용할 수 도 있다. 또한, 상기 Al2O3계 내화물 조성물은 산화방지제 및 결합재의 중/축합 촉매 역할을 하는 붕산을 상기 주성분 100 중량부에 대하여 1 내지 5 중량부의 양으로 더욱 포함할 수 도 있다.In order to achieve the above object, the present invention comprises 100 parts by weight of a main component including Al 2 O 3 clinker and the impression graphite; 2 to 5 parts by weight of the liquid resin binder; And it provides an Al 2 O 3 system refractory composition comprising a solid binder. As the solid binder, 1 to 3 parts by weight of a solid phenol resin may be used with respect to 100 parts by weight of the main component, or 1 to 5 parts by weight of coal-based or petroleum-based pitch powder may be used. In addition, the Al 2 O 3 system refractory composition may further include boric acid, which serves as a poly / condensation catalyst of the antioxidant and the binder in an amount of 1 to 5 parts by weight based on 100 parts by weight of the main component.
이하 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 Al2O3-C계 내화물 조성물은 주성분으로 골재 성분인 Al2O3클린커와 인상 흑연을 포함한다. Al2O3클린커와 인상 흑연의 혼합 비율은 70 내지 90 : 10 내지 30 중량%이다. 상기 인상 흑연의 사용량이 10 중량% 미만일 경우에는 인상 흑연을 사용함에 따른 효과를 얻을 수 없으며, 30 중량%를 초과하는 경우에는 용강 중에 탄소가 용해되어 용강을 오염시킬 수 있고, 내화물의 강도가 취약해질 수 있어 바람직하지 않다.The Al 2 O 3 -C system refractory composition of the present invention contains Al 2 O 3 clinker and impression graphite, which are aggregate components, as main components. The mixing ratio of Al 2 O 3 clinker and impression graphite is 70 to 90: 10 to 30% by weight. When the amount of the graphite used is less than 10% by weight, the effect of using the graphite is not obtained, and when the amount of the graphite used exceeds 30% by weight, carbon may be dissolved in the molten steel to contaminate the molten steel, and the strength of the refractory is weak. It is not desirable to be able to.
본 발명의 내화물 조성물은 상기 주성분과 함께, 성형 조제로서, 결합재를 더욱 포함한다. 아울러, 산화방지제 뿐만 아니라, 결합재의 중합 촉매 작용을 하는 붕산(H2BO3)을 더욱 포함할 수 도 있다.The refractory composition of this invention contains a binder as a shaping | molding adjuvant with the said main component further. In addition, as well as antioxidants, it may further include boric acid (H 2 BO 3 ) which serves as a polymerization catalyst of the binder.
일반적으로 상기 골재 성분 사이에는 결합재 수지로부터 유도된 탄소 재료가 분포하게 되므로, 내화물의 특성은 결합재 수지로부터 유도된 탄소 재료의 특성에 크게 의존하게 된다. 본 발명에서는 결합재 수지로부터 유도된 탄소 재료의 특성을 향상시키기 위하여, 붕산을 더욱 사용하였으며, 붕산은 내화물 제조 공정 중 소성 공정에서 하기 반응식 1과 같이 분해되어 보론 산화물로 전환되어, 결합재 수지를 둘러싸게 되므로 결합재 수지의 산화를 방지할 수 있다.In general, since the carbon material derived from the binder resin is distributed between the aggregate components, the properties of the refractory material are highly dependent on the properties of the carbon material derived from the binder resin. In the present invention, in order to improve the properties of the carbon material derived from the binder resin, boric acid was further used, and the boric acid was decomposed to boron oxide in the firing process during the refractory manufacturing process and converted to boron oxide to surround the binder resin. Therefore, oxidation of the binder resin can be prevented.
[반응식 1]Scheme 1
2H2BO3→B2O3+ 3H2O2H 2 BO 3 → B 2 O 3 + 3H 2 O
아울러, 붕산은 약산성을 나타냄에 따라 결합재의 중/축합 촉매 작용을 하게 되고, 이에 따라 결합재 수지의 중/축합 반응이 활발하게 일어나서, 골재 성분들을 더욱 견고하게 결합시킬 수 있다.In addition, the boric acid exhibits a weak acidity, thereby acting as a poly / condensation catalyst of the binder, and thus, a poly / condensation reaction of the binder resin occurs actively, thereby more tightly binding the aggregate components.
본 발명의 내화물 조성물에 포함되는 붕산의 양은, 상기 주성분 100 중량부에 대하여 1 내지 5 중량부가 바람직하다. 붕산의 양이 1 중량부미만일 경우에는, 중/축합 촉매로서의 작용은 가능할 것이나, 내화물 사용시 기대되는, 붕산의 분해반응(2H3BO3→ B2O3+ 3H2O)에 의해 생성되는 보론 산화물에 의한 산화방지 효과가 미흡하다. 또한 5 중량부를 초과하여 사용할 경우에는, 중/축합 촉매로서의 역할 및 사용중의 산화방지제로서의 역할은 기대할 수 있으나, 분해 반응시의 물의 증발에 기인한 기공의 형성으로 산화방지 효과가 결여될 가능성이 있으며, 동시에 높은 기공율을 나타낼 것이므로 저강도를 나타내게 된다.As for the amount of boric acid contained in the refractory composition of this invention, 1-5 weight part is preferable with respect to 100 weight part of said main components. When the amount of boric acid is less than 1 part by weight, it may be possible to act as a poly / condensation catalyst, but boron produced by the decomposition reaction of boric acid (2H 3 BO 3 → B 2 O 3 + 3H 2 O), which is expected when using a refractory. The antioxidation effect by oxide is inadequate. In addition, when used in an amount exceeding 5 parts by weight, the role as a poly / condensation catalyst and the antioxidant in use can be expected, but there is a possibility that the formation of pores due to the evaporation of water during the decomposition reaction may lack the antioxidant effect. At the same time, it will show high porosity and therefore low strength.
상기 결합재로는 액상 페놀계 수지와 함께, 고상 페놀계 수지 또는 석탄계 또는 석유계 핏치를 사용할 수 있다. 또한, 상기 석탄계 또는 석유계 핏치로는 연화점이 80 내지 250℃인 핏치를 사용하는 것이 바람직하다. 연화점이 80℃ 미만일 경우에는 탄화 수율이 저하되어 바람직하지 않고, 연화점이 250℃보다 높을 경우에는 유동성이 결여되어, 내화물 핏치의 탄화 반응중 용융된 용융 핏치가 주성분 사이로 흘러들어가기 어렵고, 이로 인해서, 내화물의 특성이 열화될 수 있다.In addition to the liquid phenolic resin, the binder may be a solid phenolic resin or a coal or petroleum pitch. In addition, as the coal-based or petroleum-based pitch, it is preferable to use a pitch having a softening point of 80 to 250 ° C. If the softening point is lower than 80 ° C., the carbonization yield is lowered, which is not preferable. If the softening point is higher than 250 ° C., the fluidity is insufficient, and the molten melt pitch hardly flows between the main components during the carbonization reaction of the refractory pitch. The characteristics of may deteriorate.
본 발명의 내화물 조성물에 포함되는 결합재의 양은 페놀 수지를 사용할 경우에는 상기 주성분 100 중량부당 1 내지 3 중량부, 핏치를 사용할 경우에는 1내지 5 중량부가 바람직하다. 상기 페놀 수지의 양이 1 중량부미만일 경우에는 결합재 역할이 미미하며, 3 중량부를 초과하는 경우에는 성형 및 열처리 중 외부로 배출되어 내화물 전체의 성능이 열화될 수 있다. 또한, 상기 핏치의 양이 1 중량부 미만일 경우에는 핏치가 결합재의 역할을 충분히 만족시킬 수 없을 것이며, 5 중량부를 초과할 경우에는 열처리중 점도가 낮은 용융 핏치가 외부로 배출되어 내화물 전체의 성능이 열화될 수 있다.The amount of the binder included in the refractory composition of the present invention is preferably 1 to 3 parts by weight per 100 parts by weight of the main component when using a phenol resin, 1 to 5 parts by weight when using a pitch. When the amount of the phenol resin is less than 1 part by weight, the role of the binder is insignificant, and when the amount of the phenol resin is greater than 3 parts by weight, the performance of the entire refractory may be deteriorated by being discharged to the outside during molding and heat treatment. In addition, when the amount of the pitch is less than 1 part by weight, the pitch may not sufficiently satisfy the role of the binder, and when the amount is more than 5 parts by weight, the molten pitch having a low viscosity during heat treatment is discharged to the outside to improve the performance of the entire refractory. May deteriorate.
결합재로는 페놀 수지보다 석탄계 또는 석유계 핏치를 사용하는 것이 저렴하므로 바람직하다.As the binder, it is preferable to use a coal or petroleum pitch than the phenol resin.
이와 같은 조성의 본 발명의 내화물 조성물은, 기존의 Al2O3-C 내화물에 비해 생산원가가 저가이면서, 높은 고온 강도를 나타내고, 산화저항성도 우수하며 동시에 높은 내스폴링성을 갖는 고기능의 내화물을 제조할 수 있다.The refractory composition of the present invention having such a composition has a low cost of production compared to the existing Al 2 O 3 -C refractory material, exhibits high temperature strength, excellent oxidation resistance and at the same time high performance refractory having high spalling resistance. It can manufacture.
이하 본 발명의 바람직한 실시예 및 비교에를 기재한다. 그러나 하기한 실시예는 본 발명의 바람직한 일 실시예일 뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparisons of the present invention are described. However, the following examples are only one preferred embodiment of the present invention and the present invention is not limited to the following examples.
실시예 1Example 1
Al2O3클링커 85 중량%와, 인상흑연 20 중량%을 혼합하였다. 이 혼합물 100 중량부에 대하여, 연화점이 200℃인 고상 핏치 2 중량부 및 액상 페놀 수지를 3 중량부를 상기 혼합물에 첨가하여 Al2O3-C계 내화물 조성물을 제조하였다. 이 조성물을 성형하여 성형체를 제조한 후, 이 성형체를 1000℃에서 소성처리하여 내화물을 제조하였다.And the Al 2 O 3 85% by weight of clinker, graphite impression 20% by weight were mixed. To 100 parts by weight of this mixture, 2 parts by weight of a solid pitch having a softening point of 200 ° C. and 3 parts by weight of a liquid phenol resin were added to the mixture to prepare an Al 2 O 3 -C type refractory composition. After molding the composition to produce a molded article, the molded article was calcined at 1000 占 폚 to produce a refractory.
(비교예 1)(Comparative Example 1)
Al2O3클링커 85 중량%와, 인상흑연 20 중량%를 혼합하였다. 이 혼합물 100중량부에 대하여 고상 페놀수지 2 중량부 및 액상 페놀수지 3 중량부를 상기 혼합물에 첨가하여 Al2O3-C계 내화물 조성물을 제조하였다. 이 내화물 조성물을 성형하여 성형체를 제조한 후, 이 성형체를 1000℃에서 소성하여 내화물을 제조하였다.85% by weight of Al 2 O 3 clinker and 20% by weight of impression graphite were mixed. 2 parts by weight of a solid phenol resin and 3 parts by weight of a liquid phenol resin were added to the mixture with respect to 100 parts by weight of the mixture to prepare an Al 2 O 3 -C system refractory composition. After molding the refractory composition to produce a molded article, the molded article was fired at 1000 占 폚 to produce a refractory.
상기 실시예 1 및 비교예 1의 방법으로 제조된 Al2O3-C계 내화물에 대해 7초 내에 소정의 온도에 도달하는 급속 승온에 의해 내부에 균열이 발생하는 온도를 측정하는 스폴링 특성을 측정하였다. 그 결과, 실시예 1의 내화물은 1750℃에서 파괴가 일어난 반면에, 비교예 1의 내화물은 1530℃의 온도에서 파괴가 일어나, 실시예 1의 내화물의 내스폴링 특성이 크게 개선되었음을 알 수 있다.The spalling characteristics of the Al 2 O 3 -C-based refractory prepared by the method of Example 1 and Comparative Example 1 to measure the temperature at which the crack is generated by rapid temperature rising to reach a predetermined temperature within 7 seconds Measured. As a result, the refractory material of Example 1 was broken at 1750 ° C, whereas the refractory material of Comparative Example 1 was broken at a temperature of 1530 ° C, indicating that the spalling properties of the refractory material of Example 1 were greatly improved.
상술한 바와 같이, 본 발명의 내화물 조성물은 향상된 강도 및 내산화성을 갖고, 높은 내스폴링 특성을 갖는다.As mentioned above, the refractory compositions of the present invention have improved strength and oxidation resistance and have high spalling properties.
Claims (5)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100908704B1 (en) * | 2002-12-24 | 2009-07-22 | 주식회사 포스코 | Carbon-containing acid neutral refractory composition |
| CN103880322A (en) * | 2014-02-09 | 2014-06-25 | 黄小仙 | Method for preparing constructional composite mineral admixture |
| CN104773966A (en) * | 2014-02-09 | 2015-07-15 | 黄小仙 | Preparation method of binding material mix |
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|---|---|---|---|---|
| JPH01286950A (en) * | 1988-05-12 | 1989-11-17 | Kawasaki Refract Co Ltd | Carbon-containing refractory |
| KR910000569A (en) * | 1989-06-08 | 1991-01-29 | 박태준 | Oxidation Resistance Graphite Refractory and Manufacturing Method Thereof |
| KR930702249A (en) * | 1990-10-24 | 1993-09-08 | 미첼 웰터 | Refractory material combined with sialon matrix and preparation method thereof |
| KR20000040775A (en) * | 1998-12-19 | 2000-07-05 | 신현준 | Carbon-containing amorphous refractory composition |
| KR20000041153A (en) * | 1998-12-21 | 2000-07-15 | 신승근 | Carbonaceous amorphous refractory for a steel-making container |
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2000
- 2000-12-26 KR KR1020000082292A patent/KR20020052828A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01286950A (en) * | 1988-05-12 | 1989-11-17 | Kawasaki Refract Co Ltd | Carbon-containing refractory |
| KR910000569A (en) * | 1989-06-08 | 1991-01-29 | 박태준 | Oxidation Resistance Graphite Refractory and Manufacturing Method Thereof |
| KR930702249A (en) * | 1990-10-24 | 1993-09-08 | 미첼 웰터 | Refractory material combined with sialon matrix and preparation method thereof |
| KR20000040775A (en) * | 1998-12-19 | 2000-07-05 | 신현준 | Carbon-containing amorphous refractory composition |
| KR20000041153A (en) * | 1998-12-21 | 2000-07-15 | 신승근 | Carbonaceous amorphous refractory for a steel-making container |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100908704B1 (en) * | 2002-12-24 | 2009-07-22 | 주식회사 포스코 | Carbon-containing acid neutral refractory composition |
| CN103880322A (en) * | 2014-02-09 | 2014-06-25 | 黄小仙 | Method for preparing constructional composite mineral admixture |
| CN104773966A (en) * | 2014-02-09 | 2015-07-15 | 黄小仙 | Preparation method of binding material mix |
| CN104773969A (en) * | 2014-02-09 | 2015-07-15 | 黄小仙 | Method for preparing complex mineral admixture for building |
| CN104773966B (en) * | 2014-02-09 | 2017-02-22 | 南通科达建材股份有限公司 | Preparation method of binding material mix |
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