KR100276254B1 - Repair material with spall resistance for spraying - Google Patents
Repair material with spall resistance for spraying Download PDFInfo
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- KR100276254B1 KR100276254B1 KR1019980056294A KR19980056294A KR100276254B1 KR 100276254 B1 KR100276254 B1 KR 100276254B1 KR 1019980056294 A KR1019980056294 A KR 1019980056294A KR 19980056294 A KR19980056294 A KR 19980056294A KR 100276254 B1 KR100276254 B1 KR 100276254B1
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/14—Hardening accelerators
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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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
Abstract
본 발명은 용융금속을 수강하는 전기로, 전로, 래들 등의 내장내화물의 분무보수재에 관한 것으로, 그 목적은 기존과 같이 분무보수재의 중온강도와 내식성을 개선하기 위해 결합재에 초점을 맞추어 연구하던 것 과는 달리, 원료인 마그네시아의 입도조정으로 중온강도 및 내식성을 현격히 증가시킨 분무보수재를 제공함에 있다.The present invention relates to a spray repair material for internal refractories, such as electric furnaces, converters, ladles, etc., which take molten metal. The purpose of the present invention was to focus on the binder to improve the medium temperature strength and corrosion resistance of the spray repair material. On the contrary, it is to provide a spray repair material that has significantly increased the medium temperature strength and the corrosion resistance by adjusting the particle size of the raw material magnesia.
이와 같은 목적을 갖는 본 발명은, 마그네시아 원료 및 첨가재로 이루어지는 분무 보수재에 있어서, 상기 마그네시아 원료는The present invention having such an object is a spray repair material comprising a magnesia raw material and an additive, wherein the magnesia raw material is
(a) 0.075mm이하의 미분: 32-38중량%(a) Differential below 0.075mm: 32-38% by weight
(b) 1∼0.075mm의 중립입자: 5∼15중량% 및(b) 1 to 0.075 mm neutral particles: 5 to 15% by weight and
(c) 나머지 5∼3mm와 3∼1mm의 조립입자로 이루어지는 내박리성이 우수한 분무보수재에 관한 것을 그 기술적요지로 한다.(c) The technical gist of the spray repairing material which is excellent in peeling resistance which consists of the remaining 5-3 mm and 3-1 mm granulated particles shall be taken as the technical summary.
이러한 본 발명은 종래의 분무보수재 보다 내침식성이 우수하고 중온압축강도가 4배이상 개선되며, 전기로에 직접 적용되는 경우 평균수명이 80%이상 향상되는 효과가 있다.The present invention has better corrosion resistance than the conventional spray repair material and the median compressive strength is improved by more than four times, and when applied directly to the electric furnace has an effect of improving the average life of more than 80%.
Description
본 발명은 용융금속을 수강하는 전기로, 전로, 래들 등의 내장내화물의 분무보수재에 관한 것으로, 상세하게는 보수 시공체의 부분탈락 및 부분침식 억제성이 우수한 분무보수재에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to spray repair materials for internal refractories, such as electric furnaces, converters, ladles, etc., which take molten metal. More particularly, the present invention relates to spray repair materials excellent in suppressing partial dropout and partial erosion of repaired bodies.
일반적으로 용융금속을 수강하는 전기로, 전로, 래들 등의 내장내화물이 침식되면 분무보수재로 보수를 하여 사용수명을 연장하고 있다. 이러한 분무보수재는 마그네시아 원료와 첨가재로 이루어지며, 첨가재로는 결합제와 경화재가 있다.In general, when the internal refractories such as electric furnaces, converters, ladles, etc., which take molten metal, are eroded, they are repaired by spray repair materials to extend their service life. The spray repair material is composed of magnesia raw material and additives, and the additives include a binder and a hardener.
분무보수재의 마그네시아 원료는 조립으로 5-3mm:5-20중량%와 3-1mm:20-40중량%, 중립으로 1-0.075mm: 20-30중량% 미분으로 0.075mm 이하:20-30중량%로 입도를 조합하여 사용하고 있다. 이러한 입도조합은 일본 공개특허공보 평 7-127978호, 동공보 평 6-227869호에서 찾아 볼 수 있다. 그러나, 이러한 분무보수재로 각종 로체를 보수하는 경우 시공체가 사용중에 균일하게 침식되지 않고 부분적으로 침식되어 부분 보수를 자주 하게 되는 문제점이 있다.Magnesia raw material of spray refining material is 5-3mm: 5-20% by weight and 3-1mm: 20-40% by weight, 1-0.075mm by neutral: 0.0-30mm or less by 20-30% by weight fine powder: 20-30% by weight A combination of particle sizes is used. Such particle size combinations can be found in Japanese Patent Laid-Open Nos. 7-127978 and 6-227869. However, in the case of repairing various furnaces with such spray repair materials, there is a problem in that the repaired bodies are not eroded uniformly during use, but are partially eroded, so that partial repairs are frequently performed.
부분적으로 침식되는 것은 (1) 분무체에 있어 소결층과 미소결층의 강도차와 (2) 분무체로 슬라그가 침투하는 두 가지 원인으로 파악할 수 있다.Partial erosion can be attributed to two reasons: (1) the difference in strength between the sintered layer and the unbonded layer in the spray and (2) the penetration of slag into the spray.
(1)각종 로체의 내화물에 보수된 분무체는, 사용중에 용강이나 슬라그(Slag)와 접촉하는 가동면과 배면으로 나누어진다. 가동면은 슬라그의 침투에 의하여 조직이 치밀하고 강도가 높은 층으로 변하게 되는 반면, 배면은 소결이 되지 않는 강도가 약한 미소결 층이 존재하게 되어 그 경계면의 강도차에 의한 내부 크랙(Crack)이 발생되고, 이에 따라 사용중에 시공체가 부분적으로 탈락하는 것이다. 이는 분무재 사용후 시공체를 채취하여 단면을 관찰해 보면 내부 미소결된 원질층에 크랙(Crack)이 발생되어 있는 것을 확인할 수 있으며, 이는 분무체의 중온(1,000℃)의 강도가 약하기 때문이다. (2) 또한, 종래의 분무재를 내압이 높은 밀폐형 회전침식기로 회전침식을 하면 시편 내부로 슬라그가 침투되어 시편이 부풀어 오르면서 나중에는 탈락되는 현상이 나타난다.(1) Sprays repaired in refractory materials of various furnace bodies are divided into movable surfaces and rear surfaces which are in contact with molten steel or slag during use. The surface of the movable surface is changed into a dense and high-strength layer by the penetration of slag, while the back surface has a weak layer of weak strength that cannot be sintered. And, thus, the construction body partially falls off during use. This can be confirmed that the cracks are generated in the internally sintered raw material layer when observing the cross-section after using the sprayed material after use of the spraying material, because the strength of the sprayed medium is weak (1,000 ° C). . (2) In addition, when the conventional spraying material is subjected to rotary erosion with a high internal pressure sealed rotary immersion, slag penetrates into the specimen and the specimen swells, resulting in a phenomenon of dropping later.
본 발명자는 종래의 분무보수재의 이러한 문제점를 개선하기 위해 주원료와 첨가재에 대해 다양한 검토와 연구한 결과, 무엇 보다 주원료의 입도별 함량에 문제가 있다는 것을 인식하고 실험을 통해 최적의 입도별 함량을 도출하고 본 발명을 제안하게 이르렀다.The present inventors have conducted various studies and studies on the main raw materials and additives to improve these problems of the conventional spray repair materials, recognizing that there is a problem in the content of the main raw materials by particle size, and deriving the optimum content by the particle size through experiments. It has come to propose the present invention.
본 발명은 분무보수재의 유동성을 확보하면서 반응표면적이 넓은 미분의 마그네시아 원료를 최적화되록 마그네시아 원료의 입도를 조정함으로써, 침투하는 초기 스라그와의 반응성을 높여 스라그가 더 이상 시공체 내부를 침식하지 못하게 하면서 반응표면적의 확대로 중온에서 소결력이 높아 중온강도가 개선되는 분무보수재를 제공함에 있다.According to the present invention, the particle size of the magnesia raw material is adjusted to optimize the magnesia raw material having a wide reaction surface while ensuring the fluidity of the spray repair material, thereby increasing the reactivity with the initial slag infiltrating so that the slag no longer erodes the interior of the construction body. It is to provide a spray repair material that improves the mesophilic strength by increasing the reaction surface area and increasing the sintering power at the mid temperature.
상기 목적을 달성하기 위한 본 발명의 분무보수재는, 마그네시아 원료가Spray repair material of the present invention for achieving the above object, the magnesia raw material is
(a) 0.075mm이하의 미분: 32-38 중량%(a) Differential below 0.075mm: 32-38% by weight
(b) 1∼0.075mm의 중립입자: 5∼15중량% 및(b) 1 to 0.075 mm neutral particles: 5 to 15% by weight and
(c) 나머지 5∼3mm와 3∼1mm의 조립입자로 구성되는 것을 포함하여 구성된다.(c) It is comprised including what consists of remainder of 5-3 mm and 3-1 mm granulated particles.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 중온강도와 내식성을 개선하기 위해 분무보수재의 결합재에 초점을 맞추어 연구하던 종래의 기술과는 달리, 원료인 마그네시아의 입도조정으로 중온강도 및 내식성을 현격히 증가시키는데, 그 특징이 있다.The present invention, unlike the prior art, focusing on the binding material of the spray repair material to improve the mesophilic strength and corrosion resistance, significantly increases the mesophilic strength and corrosion resistance by adjusting the particle size of magnesia as a raw material.
본 발명자는 기존의 분무보수재에 대한 다양한 연구와 실험결과, 기존의 마그네시아 원료는 중립(1-0.075mm)의 함량이 높고 미분의 함량이 낮아서 슬라그 층의 SiO2성분이 침투되면 MgO와 반응하여 융점이 높은 포스테라이트(MgO·SiO2)의 형성속도가 늦어 시공체 내부 깊게 슬라그 침투가 일어나서 팽창되어 시편이 부풀어 오른 다는 것을 확인하였다. 이러한 문제분석결과, 중온강도를 높이고 슬라그(Slag) 침투를 억제하여 내식성을 증가하기 위해서는 미분의 사용량이 증가할 필요가 있다는 것을 인식하게 되었다.As a result of various studies and experiments on conventional spray repair materials, the present magnesia raw material has a high content of neutrality (1-0.075mm) and a low content of fine powder, and reacts with MgO when the SiO 2 component of the slag layer penetrates. It was confirmed that the formation rate of forsterite (MgO · SiO 2 ) with high melting point was slow and the slag penetrated deeply inside the structure, causing the specimen to swell. As a result of the problem analysis, it was recognized that the amount of fine powder needed to be increased to increase the medium temperature strength and to suppress the slag penetration and increase the corrosion resistance.
이러한 관점에 근거하여 본 발명에서는 분무보수재의 마그네시아 원료를, (a) 0.075mm이하의 미분: 32-38 중량%, (b) 1∼0.075mm의 중립입자: 5∼15중량% 및 (c) 나머지 5∼3mm와 3∼1mm의 조립입자로 입도조정하는데, 이를 구분하여 설명한다.Based on this aspect, in the present invention, the magnesia raw material of the spray repair material is (a) fine powder of 0.075mm or less: 32-38% by weight, (b) 1 ~ 0.075mm neutral particle: 5-15% by weight and (c) The particle size is adjusted to the remaining 5 to 3 mm and 3 to 1 mm granulated particles, it will be described separately.
(a) 먼저, 미분은 위에서 언급한 바와 같이, 기존 보다 함유량을 증가함으로써 슬라그중의 SiO2성분과 MgO의 반응속도가 빨라서 초기에 고융점의 포스테라이트가 가동면 표면에서 생성되어 점도가 높아지기 때문에 계속적인 SiO2성분의 침투가 억제되도록 한다. 또한, 표면적이 넓은 미분함량이 높으면 1000℃ 소결온도에서 결합재와 소결력이 증가되어 소결강도가 증가된다. 이를 위해 미분은 32%이상 함유되나, 미분사용량이 38%를 넘으면 분말 유동성이 나빠져 재료 탱크내에서 분말의 토출이 잘되지 않아 액동현상이 나타나고, 재료탱크 내부에 커다란 공극(Bridge) 현상이 생겨 나중에는 재료가 토출되지 않는 현상이 나타난다.(a) First, as described above, the fine powder has a higher content than the existing one, so that the reaction rate of SiO 2 component and MgO in the slag is faster, so that a high melting point of forsterite is initially formed on the surface of the movable surface, resulting in a higher viscosity. This allows continuous penetration of the SiO 2 component to be suppressed. In addition, when the fine powder content having a large surface area is high, the binder and the sintering force are increased at the sintering temperature of 1000 ° C., thereby increasing the sintering strength. To this end, more than 32% of the fine powder is contained, but if the amount of fine powder exceeds 38%, the powder fluidity deteriorates, so that the powder is not discharged well in the material tank, resulting in liquid phenomena, and a large bridge inside the material tank. The phenomenon is that the material is not discharged.
(b) 1∼0.075mm의 중립과 (c) 5∼3mm와 3∼1mm의 조립입자는, 미분함량의 증가로 인해 분말상태의 유동성의 확보차원에서 그 함량을 조정한 것으로 본 발명에서는 중립의 함량을 기존 대비 대폭 하향화하면서 조립의 함량을 미분과 함께 증가시켰다. 구체적으로 1∼0.075mm의 중립입자: 5∼15중량%로 하고, 나머지를 5∼3mm와 3∼1mm의 조립입자로 한다.(b) 1 to 0.075 mm neutral and (c) 5 to 3 mm and 3 to 1 mm granulated particles were adjusted in order to secure the fluidity in the powder state due to the increase in the fine powder. The content of the granules increased with the fine powder while lowering the content significantly. Specifically, 1 to 0.075 mm of neutral particles: 5 to 15% by weight, and the remainder to 5 to 3 mm and 3 to 1 mm of granulated particles.
이러한 입도조정은, 분무보수재의 천연마그네시아의 원료가 분말상태의 유동성이 나빠지지 않도록 하는 것을 기본으로 하여 조정한 것이다. 분말 상태의 유동성이 나쁘면 분무 시공기기 내에서 분말이 유동이 잘되지 않아 시공기기의 재료 토출상태가 불안하게 되어 시공체의 조직이 불균일해진다. 미분함량만 증가되면 분말 유동성이 나빠지므로 분말의 유동성이 저해되지 않도록 5-3mm와 3-1mm의 조립과 1-0.075mm의 중립의 사용량을 동시에 상기와 같이 조정한 것이다. 각각 입자의 유동성을 관찰하면 입자의 크기가 큰 쪽이 유동성이 높다. 즉, 5∼3mm 입도가 유동성이 가장 크고 3∼1mm, 1∼0.075mm, 0.075mm이하의 순으로 유동성이 크게 나타난다. 유동성이 크다고 하여 5∼3mm, 3∼1mm의 조립만 사용할 경우 부착이 되지 않아 시공체가 형성되지 않으므로 본 발명에서는 이를 고려해 상기와 같이 조립과 중립을 입도조정한 것이다.The particle size adjustment is based on the fact that the raw material of the natural magnesia of the spray repair material does not deteriorate the fluidity of the powder state. If the fluidity of the powder is poor, the powder does not flow well in the spraying equipment, and the material discharge state of the construction equipment becomes unstable, resulting in uneven structure of the construction body. If only the fine content is increased, the powder fluidity is deteriorated, so that the granularity of 5-3mm and 3-1mm and the amount of neutrality of 1-0.075mm are adjusted simultaneously as described above so that the fluidity of the powder is not impaired. When the fluidity of each particle is observed, the larger the particle size, the higher the fluidity. That is, 5-3 mm particle size has the largest fluidity, and fluidity is large in order of 3-1 mm, 1-0.075 mm, 0.075 mm or less. When only 5 to 3mm, 3 to 1mm assembly is used because of the high fluidity is not attached because the construction is not formed in the present invention is to adjust the granulation and granulation as described above in consideration of this.
본 발명에서 5∼3mm와 3∼1mm의 조립입자는 통상의 방법대로 그 비율을 조정하여 사용하면 되며, 그 일례는 후술하는 실시예에 제시한다.In the present invention, the granulated particles of 5 to 3 mm and 3 to 1 mm may be used by adjusting their ratios according to a conventional method, and an example thereof is shown in Examples described later.
이하, 본 발명을 실시예를 통하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예 1]Example 1
천연 마그네시아 원료를 아래 표 1과 같이 입도 조합하고 이 원료 100중량%에 결합재로 마이크로 실리카 2중량%, 난용성 규산염 1중량%, 용해서 규산염 1중량%를 배합외로 첨가하고, 이 시료 일정량을 채취하여 물을 12중량% 첨가하여 혼련한 슬러리를 회전침식시편 성형틀에 주입하여 회전침식시편을 제조하고 110℃로 건조하였다. 건조된 회전침식시편을 드럼형 회전침식기에 종래품과 같이 장착하여 1650℃ 로 가열하고 여기에 철과 슬라그를 투입하여 1시간 반응시킨 후 배출하고 다시 철과 슬라그를 투입하여 1시간 반응시키는 순으로 5회를 반복하였다. 사용된 슬라그의 CaO/SiO2비는 2.0 인 것으로 전기로에서 채취된 슬라그를 분쇄하여 사용하였다.Natural magnesia raw materials are combined in particle size as shown in Table 1 below, and 100% by weight of this raw material is added with 2% by weight of micro silica, 1% by weight of poorly soluble silicate, and 1% by weight of silicate as a binder, and a predetermined amount of this sample is collected. The slurry was kneaded by adding 12% by weight of water to the rotary erosion specimen mold to prepare a rotary erosion specimen, and dried at 110 ° C. The dried rotary erosion specimen was mounted in a drum-type rotary erosion machine as in the prior art, and heated to 1650 ° C., in which iron and slag were added and reacted for 1 hour, and then discharged. Then, iron and slag were added and reacted for 1 hour. Repeat five times. The slag CaO / SiO 2 ratio was 2.0, and the slag collected from the electric furnace was ground and used.
표 1에서 알 수 있듯이, 발명예(1,2,3)은 분말의 유동성이 양호하고 중온의 강도가 종래재에 비하여 4배 이상 증가하였으며, 내식성도 종래재에 비하여 우수하게 나타났다.As can be seen from Table 1, the inventive examples (1, 2, 3) has good flowability of the powder and the strength of the medium temperature increased more than four times compared to the conventional material, the corrosion resistance was also superior to the conventional material.
비교예 1은 조립의 함량을 40중량% 이하로 하고 중립과 미분의 함량을 증가한 것으로 중온의 강도가 높고 회전침식시 표면의 부품현상이 나타나지 않았지만 탱크내 브릿지 현상이 발생하여 분말의 유동성이 나쁜 것으로 나타났다.In Comparative Example 1, the content of granules was 40 wt% or less, and the content of neutral and fine powder was increased. The strength of the medium temperature was high, and the surface phenomena did not appear during rotational erosion. appear.
한편, 본 발명에 따라 입도조정된 분무보수재 30ton을 100ton의 전기로에 적용한 결과 분말상태의 유동성이 우수하여 재료토출이 일정하게 되고, 부착율이 95% 이상으로 되어 부착성이 우수한 결과를 확인할 수 있었다.On the other hand, according to the present invention was applied to 30 tons of spray-repair material adjusted to the size of 100 tons of electric furnace results in excellent powder fluidity, the material discharge is constant, the adhesion rate is more than 95% was confirmed that the excellent adhesion properties .
또한 종래재는 사용 2-3 회째부터 시공체가 부분적으로 탈락되고 침식이 빠르게 되어 5회 사용후에 다시 보수를 하였지만 본 발명품은 2-3회째 부분침식 현상이 나타나지 않으며, 7회째 부분침식이 나타나고, 9회 사용후 보수를 하는 것으로 나타나 평균수명이 80% 이상 증가된 것으로 나타났다.In addition, the conventional materials are partially removed from the use 2-3 times and the erosion is rapidly accelerated and repaired again after 5 times of use, but the present invention does not show the 2-3 times partial erosion phenomenon, the seventh partial erosion, 9 times Repairs were made after use, indicating an increase in life expectancy above 80%.
상술한 바와 같이, 본 발명은 종래의 분무보수재 보다 중온압축강도가 4배이상 커지고 내식성도 개선되는 분무보수재를 제공할 수 있으며, 이러한 분무보수재는 전기로에 직접 적용되는 경우 평균수명이 80%이상 향상되는 효과가 있다.As described above, the present invention can provide a spray repair material 4 times larger than the conventional spray repair material and the corrosion resistance is improved corrosion resistance, this spray repair material is improved by more than 80% average life when applied directly to the electric furnace It is effective.
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