KR100265003B1 - Refractory material of magnesia-spinel type - Google Patents
Refractory material of magnesia-spinel type Download PDFInfo
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- KR100265003B1 KR100265003B1 KR1019960062230A KR19960062230A KR100265003B1 KR 100265003 B1 KR100265003 B1 KR 100265003B1 KR 1019960062230 A KR1019960062230 A KR 1019960062230A KR 19960062230 A KR19960062230 A KR 19960062230A KR 100265003 B1 KR100265003 B1 KR 100265003B1
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- magnesia
- spinnel
- refractory
- spinel
- aluminum titanate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped 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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped 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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/043—Refractories from grain sized mixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped 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 aluminates
- C04B35/443—Magnesium aluminate spinel
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/16—Making or repairing linings increasing the durability of linings or breaking away linings
Abstract
Description
본 발명은 턴디쉬용 내장내화물로 사용되는 마그네시아-스핀넬질 내화재에 관한 것으로, 보다 상세하게는 고온에서의 용적안정성이 우수한 마그네시아-스핀넬질 내화재에 관한 것이다.The present invention relates to a magnesia-spinnel refractories used as internal refractories for tundish, and more particularly to a magnesia-spinnel refractories having excellent volume stability at high temperatures.
마그네시아-스핀넬질 내화재(벽돌)는 주로 시멘트 로타리 길른(Cement Rotary Kiln)용 내장내화물로 사용되어온 마그네시아-크로미아질 내화벽돌의 문제를 해결하기 위한 수단으로 개발되었다. 즉, 마그네시아-크로미아질 내화벽돌중에 함유되어 있는 크롬성분의 사용중 용출에 의한 환경문제를 해결하기 위한 대체재질로서 개발된 것이다. 이러한 대체재질 개발의 대표적인 것으로는 일본특허 공개공보 평6-100357호, 평6-l16014호, 평7-187756호 및 평7-61857호 등을 들 수 있다. 이와 같은 많은 연구로 현재에는 마그네시아-스핀넬질 내화벽돌이 시멘트 로타리 킬른용 내장내화물의 주류를 이루고 있다.Magnesia-spinnel refractories (bricks) have been developed as a means to solve the problem of magnesia-chromia refractories, which have been mainly used as interior refractories for cement rotary kilns. In other words, it was developed as an alternative material to solve the environmental problems caused by elution of the chromium component contained in the magnesia-chromiatrile firebrick. Representative examples of such alternative material development include Japanese Patent Application Laid-Open No. Hei 6-100357, Hei 6-l16014, Hei 7-187756 and Hei 7-61857. Much of this research has led to the mainstream of magnesia-spinnel refractory bricks for internal refractories for cement rotary kilns.
그러나, 상기 마그네시아-스핀넬질 내화벽돌은 염기성 내화물의 특성과 유사하여 강중에 함유되는 알루미나 등의 개재물을 최소화할 수 있음에도 불구하고 고온에서의 열간선팽창율이 커서 산중성 내화물에 비하여 용적안정성이 저하되므로, 마그네시아-스핀넬질 내화벽돌을 제강이나 턴디쉬용 내장내화물로 사용하기에는 부적합하다. 따라서, 마그네시아-스핀넬질 내화벽돌을 제강 및 턴디쉬용 내화물로서 활용하기 위해서는 마그네시아-스핀넬질 내화벽돌의 용적안정성의 향상이 필수불가결한 요소이다.However, the magnesia-spinnel refractory brick is similar to that of the basic refractory material, and although the inclusion of alumina and the like contained in the steel can be minimized, the coefficient of volume expansion at high temperature is high, so that the volume stability is lowered compared to the acid neutral refractory material. Magnesia-spinnel refractory bricks are not suitable for use as internal refractories for steelmaking or tundish. Therefore, in order to utilize the magnesia-spinnel refractory brick as a refractory for steelmaking and tundish, the improvement of the volume stability of the magnesia-spinnel refractory brick is indispensable.
이에 본 발명자들은 마그네시아-스핀넬질 내화재를 턴디쉬에 적용하기 위해 연구와 실험을 거듭하고 그 결과에 근거하여 본 발명을 제안하게 된 것으로, 본 발명은 마그네시아와 마그네시아 잉여 스핀넬(MgO-rich Spinel)로 이루어진 내화재료에 알루미늄티타네이트(A12Ti05) 분말을 첨가하여 내식성은 저하시키지 않으면서 고온에서의 용적안정성을 향상시킨 마그네시아-스핀넬질 내화재를 제공하고자 하는데, 그 목적이 있다.The present inventors have repeatedly studied and experimented to apply the magnesia-spinnel refractories to tundish, and the present invention was proposed based on the results, and the present invention is magnesia and magnesia surplus spinel (MgO-rich Spinel). The purpose of the present invention is to provide a magnesia-spinnel refractories having improved volume stability at high temperature without deteriorating corrosion resistance by adding aluminum titanate (A1 2 Ti0 5 ) powder to the refractory material.
본 발명은 마그네시아-스펀넬질 내화재에 있어서, 마그네시아 잉여 스핀넬과 마그네시아의 중량비가 35:65-40:60으로 이루어진 내화재료; 및 상기 내화재료 대비 5-15중량%의 알루미늄티타네이트 분말로 조성되고, 상기 마그네시아 잉여 스핀넬은 마그네시아와 알루미나의 중량비가 50:50-70:30으로 이루어지고, 그리고 상기 알루미늄티타네이트 분말의 입자크기가 1.0mm 이하인 것을 특징으로 하는 용적안정성이 우수한 마그네시아-스핀넬질 내화재에 관한 것이다.The present invention relates to a magnesia-spunnel fireproof material comprising: a fireproof material having a weight ratio of magnesia surplus spinnel to magnesia being 35: 65-40: 60; And 5-15% by weight of aluminum titanate powder relative to the refractory material, and the magnesia surplus spinel has a weight ratio of magnesia and alumina of 50: 50-70: 30, and particles of the aluminum titanate powder. It relates to a magnesia-spinnel refractories with excellent volumetric stability, characterized in that the size is 1.0mm or less.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
일반적으로 마그네시아 잉여 스핀넬 클링커는 마그네시아로 이루어진 결정립(grain)의 주위에 정스핀넬(stoichimetry spinel, 마그네시아:알루미나의 비는 중량비로 28:72)이 분포되어 있으며, 열팽창율의 차이 때문에 마그네시아와 정스핀넬사이에는 매우 미세한 틈(gap)이 발생되어 있는 미세구조를 나타낸다. 이러한 특징 때문에 염기성질 내화물에 마그네시아 잉여 스핀넬 클링커를 사용하면 내스폴링성의 저하를 방지할 수 있다.In general, the magnesia surplus spinel clinker has a spinichimetry spinel (magnesia: alumina ratio of 28:72) by weight around a grain of magnesia, and due to the difference in thermal expansion rate, It shows a microstructure in which very fine gaps are formed between spinnels. Due to these characteristics, the use of magnesia surplus spinel clinker for basic refractory can prevent deterioration of spalling resistance.
이러한 이유로 본 발명에서는 연속주조 턴디쉬 등에 사용되는 마그네시아-스핀넬질 내화재에 마그네시아 잉여 스핀넬을 적용하는데, 마그네시아와 알루미나의 비가 중량비로 50:50-70:30이어야 한다.For this reason, the present invention applies a magnesia surplus spinel to the magnesia-spinnel refractories used in continuous casting tundish, etc., the ratio of magnesia and alumina should be 50: 50-70: 30 in weight ratio.
이는 마그네시아 잉여 스핀넬의 조성에 있어서 마그네시아의 함유량이 50이하가 되면 알루미나의 성분이 과다하여 슬래그중의 CaO와의 반응성이 증대되므로 마그네시아-스핀넬질 내화재의 내식성의 향상이 미약하기 때문이다. 또한, 마그네시아의 함유량이 70 이상이 되면 내침윤성이 취약한 마그네시아 고유의 특성에 근접하여 마그네시아 잉여 스핀넬의 사용효과가 발휘되지 않기 때문이다.This is because when the magnesia content in the composition of the magnesia surplus spinel is 50 or less, the alumina component is excessive and the reactivity with CaO in the slag is increased, so that the improvement of the corrosion resistance of the magnesia-spinnel fireproof material is weak. In addition, when the content of magnesia is 70 or more, the use effect of the magnesia surplus spinel is not exerted close to the intrinsic characteristics of magnesia, which is poor in infiltration resistance.
본 발명에서는 상기와 같이 한정되는 마그네시아 잉여 스핀넬과 마그네시아의 함유량을 중량비로 35:65-40:60으로 한정한다.In the present invention, the content of magnesia surplus spinnel and magnesia defined as above is limited to 35: 65-40: 60 by weight ratio.
이는 마그네시아 잉여 스핀넬의 함유량이 중량비 35 이하가 되면 내침윤성이 취약한 마그네시아 고유의 특성에 근접하여 마그네시아 잉여 스핀넬의 사용효과가 발휘되지 않기 때문이고, 또한, 마그네시아 잉여 스핀넬의 함유량이 중량비로 40 이상이 되면 알루미나의 성분이 과다하여 슬래그중의 CaO와의 반응성이 증대되어 마그네시아-스핀넬질 내화벽돌의 내식성 향상효과가 미약하기 때문이다.This is because when the content of magnesia surplus spinnel is 35 or less by weight, the use effect of magnesia surplus spinnel is not exerted close to the intrinsic property of magnesia, which is weak in infiltration resistance, and the content of magnesia surplus spinnel is 40 by weight. This is because when the alumina component is excessive, the reactivity with CaO in the slag is increased, and the effect of improving the corrosion resistance of the magnesia-spinnel-fired brick is weak.
본 발명에 사용되어지는 마그네시아와 마그네시아 잉여 스핀넬용 내화재료는 특별히 한정하는 것은 없으나, 불순물의 영향을 최소화하기 때문에 순도 95% 이상인 것이 바람직하다.The refractory material for magnesia and magnesia surplus spinnel used in the present invention is not particularly limited, but is preferably at least 95% pure because it minimizes the influence of impurities.
본 발명에서는 상기 마그네시아 잉여 스핀넬과 마그네시아로 이루어진 내화재료에 입자크기가 1.0mm 이하인 알루미늄티타네이트 분말을 상기 내화재료 대비 5-15중량% 첨가한다.In the present invention, 5-15% by weight of aluminum titanate powder having a particle size of 1.0 mm or less is added to the refractory material including the magnesia surplus spinel and magnesia.
상기 알루미늄티타네이트는 코디어라이트(2MgO·2A12O3·2SiO2)와 β-스포듀민(Li2O3·Al2O3·4SiO2)과 더불어 세라믹중에서 열팽계수가 가장 적은 재료중의 하나로써, 코디어라이트와 β-스포듀민의 융점이 각각 1470℃와 1430℃로 낮은 반면에 알루미늄티타네이트의 융점은 1860℃로 높기 때문에 제강 및 턴디쉬 조업의 온도가 1500-1700℃임을 감안하면 알루미늄티타네이트는 내화물의 내화도를 저하시키지 않는 장점이 있다. 한편, 알루미늄티타네이트는 900-1200℃ 부근에서 분해반응이 일어나는 단점이 있기는 하나, 이러한 분해반응은 본 발명의 마그네시아-스핀넬질 내화재중에 함유되어 있는 마그네시아에 의하여 억제된다.The aluminum titanate, together with cordierite (2MgO · 2A1 2 O 3 · 2SiO 2 ) and β-spodumene (Li 2 O 3 · Al 2 O 3 · 4SiO 2 ), has the lowest coefficient of thermal expansion in ceramics. For example, considering that the melting point of cordierite and β-spodumene is low at 1470 ° C and 1430 ° C, while the melting point of aluminum titanate is high at 1860 ° C, the temperature of steelmaking and tundish operations is 1500-1700 ° C. Aluminum titanate has the advantage of not lowering the fire resistance of the refractory. On the other hand, aluminum titanate has a disadvantage that the decomposition reaction occurs in the vicinity of 900-1200 ℃, this decomposition reaction is suppressed by the magnesia contained in the magnesia-spinnel refractories of the present invention.
상기 알루미늄티타네이트 분말은 그 입자크기가 1.Omm 이하로 제한되는데, 그 이유는 입자크기가 1.Omm를 초과하면 열팽창율의 이방성을 나타내는 알루미늄 티타네이트 고유의 특성에 의해 내화재중에 기공율이 증가되어 마그네시아-스핀넬질 내화재의 내식성이 저하되기 때문이다.The aluminum titanate powder is limited to a particle size of 1.Omm or less, because the porosity is increased in the refractory material due to the inherent properties of aluminum titanate exhibiting anisotropy of thermal expansion rate when the particle size exceeds 1.Omm. This is because the corrosion resistance of the magnesia-spinnel refractories is lowered.
또한, 상기 알루미늄티타네이트 분말을 5-15중량%로 제한하여 첨가한다. 그 이유는 알루미늄티타네이트 분말의 첨가량이 5중량% 미만일 경우에는 첨가량이 적어서 마그네시아-스핀넬질 내화벽돌의 용적안정성의 향상이 미약하며, 알루미늄티타네이트 분말의 첨가량이 15중량% 이상일 경우에는 마그네시아-스핀넬질 내화벽돌의 기공율이 증가되어 내식성이 저하되기 때문이다.In addition, the aluminum titanate powder is limited to 5-15% by weight. The reason is that when the addition amount of aluminum titanate powder is less than 5% by weight, the addition amount is small, so that the volume stability of magnesia-spinnel refractory brick is poor, and when the addition amount of aluminum titanate powder is 15% by weight or more, magnesia-spinning This is because the porosity of the nelly refractory brick increases, which lowers the corrosion resistance.
본 발명에서 사용되는 알루미늄티타네이트 분말로서는 특별히 한정하는 것은 없으나, 불순물의 영향을 최소화하기위해 순도 95% 이상인 것이 바람직하다.The aluminum titanate powder used in the present invention is not particularly limited, but is preferably 95% or more in order to minimize the influence of impurities.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예]EXAMPLE
하기 표 1에 나타낸 조성이 되도록 칭량 한 후, 결합제로서 페놀수지를 2.5중량% 첨가하여 900kg/cm2의 압력으로 성형하였다. 이들 성형체를 1750℃에서 8시간 동안 소성하여 발명예(1-3) 및 비교예(1-8)의 내화재를 얻었다. 얻어진 내화재들의 기공율, 1500℃에서의 선팽창율, 침식지수 및 침윤지수를 구하여 그 결과를 하기 표 1에 나타내었다.After weighing the composition shown in Table 1 below, 2.5 wt% of the phenol resin was added as a binder and molded at a pressure of 900 kg / cm 2 . These molded bodies were baked at 1750 ° C. for 8 hours to obtain fireproof materials of Inventive Example (1-3) and Comparative Example (1-8). The porosity, linear expansion at 1500 ° C., erosion index and infiltration index of the obtained refractory materials were obtained, and the results are shown in Table 1 below.
이때, 선팽창율은 열간 선팽창율로서 용적안정성을 평가(열간선팽창율이 작을수록 용적안정성이 우수)하였고, 침식지수 및 침윤지수는 침식제로서 염기도의 비가 2.0인 슬래그와 용강을 중량비로 60:40이 되도록하여 1550℃×1시간×침식제배제×4회반복의 조건하에서 회전침식시험을 행한 후, 비교예(8)을 1로 하였을 때의 상대값으로 구한 것이다.At this time, the linear expansion rate was the hot linear expansion rate to evaluate the volume stability (the smaller the hot linear expansion rate is, the better the volume stability), and the erosion index and the infiltration index are the erosion agents. After the rotary erosion test was carried out under the conditions of 1550 ° C. × 1 hour × erosion eliminator × 4 repetitions, the relative value obtained when Comparative Example (8) was 1 was obtained.
상기 표 1에서 알 수 있는 바와같이, 마그네시아와 알루미나의 비가 중량비로 50:50-70:30으로 이루어진 마그네시아 잉여 스핀넬과 마그네시아와의 비가 중량비로 35:65-40:60인 내화재료에 입자크기가 1.Omm 이하인 알루미늄티타네이트 분말이 5-15중량% 첨가된 발명예(1-3)은 본 발명의 목적이 달성되었으나, 본 발명의 범위를 벗어난 비교예(1-8)은 용적안정성, 내식성 및 내침윤성의 향상이 미약하거나 저하되었다.As can be seen in Table 1, the ratio of magnesia surplus spinel and magnesia in the ratio of magnesia and alumina is 50: 50-70: 30, and the particle size of the refractory material is 35: 65-40: 60 in weight ratio. Inventive Example (1-3) in which 5-15% by weight of aluminum titanate powder having a thickness of 1.Omm or less was achieved, but Comparative Example (1-8), which is outside the scope of the present invention, has volumetric stability, The improvement in corrosion resistance and invasion resistance was weak or decreased.
상술한 바와같이, 본 발명에 의하여 제조되는 마그네시아-스핀넬질 내화벽돌은 내식성은 저하되지 않으면서 고온에서의 용적안정성이 우수한 특성을 지니고 있다. 또한, 본 발명에 의하여 제조되는 마그네시아-스핀넬질 내화벽돌은 염기성이므로, 용강과 내화물이 직접 접촉하더라도 강중으로 내화물성 개재물이 거의 함유되지 않는다. 따라서, 내화물에 의한 용강의 오염을 방지하기 위하여 턴디쉬에 통상적으로 사용되는 마그네시아질 코팅(coating)재를 사용할 필요가 없으므로, 턴디쉬용 내화물에 적용할 경우 비용을 대폭적으로 감소시킬 수 있다.As described above, the magnesia-spinnel fireproof brick produced by the present invention has excellent volume stability at high temperature without deteriorating corrosion resistance. In addition, the magnesia-spinnel refractory brick produced by the present invention is basic, so that even if the molten steel and the refractory are in direct contact with each other, the refractory inclusions are hardly contained in the steel. Therefore, there is no need to use the magnesia coating material commonly used in tundish in order to prevent contamination of molten steel by refractory, so that the cost can be greatly reduced when applied to the tundish refractory.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019960062230A KR100265003B1 (en) | 1996-12-06 | 1996-12-06 | Refractory material of magnesia-spinel type |
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| KR1019960062230A KR100265003B1 (en) | 1996-12-06 | 1996-12-06 | Refractory material of magnesia-spinel type |
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| CN117430439B (en) * | 2023-12-20 | 2024-03-12 | 中钢洛耐科技股份有限公司 | Composite refractory material for melting furnace top and upper part and preparation method and application thereof |
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