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KR100778753B1 - Carbon-containing spray repair - Google Patents

Carbon-containing spray repair Download PDF

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KR100778753B1
KR100778753B1 KR1020010083443A KR20010083443A KR100778753B1 KR 100778753 B1 KR100778753 B1 KR 100778753B1 KR 1020010083443 A KR1020010083443 A KR 1020010083443A KR 20010083443 A KR20010083443 A KR 20010083443A KR 100778753 B1 KR100778753 B1 KR 100778753B1
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carbon
spray repair
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repair material
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KR20030053267A (en
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조문규
이석근
이성영
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주식회사 포스코
재단법인 포항산업과학연구원
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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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/04—Blast furnaces with special refractories
    • C21B7/06—Linings for furnaces
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
    • 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
    • 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63424—Polyacrylates; Polymethacrylates
    • 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; Breaking away linings
    • F27D2001/1605—Repairing linings

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Products (AREA)

Abstract

본 발명은 각종 요로의 내장 내화물의 표면에 도포하여 내화물을 보호하는 탄소함유 분사 보수재에 관한 것으로 그 목적은, 내식성과 내산화성이 우수한 탄소함유 분사 보수재를 제공하는 데 있다. 이를 위해 본 발명에서는, 흑연 분말이 3~15 중량%, 질화알루미늄(AlN)이 1~5 중량%, 잔부는 알루미나, 마그네시아, 지르코니아, 스피넬, 및 탄화규소로 이루어진 군 중에서 선택된 1종 또는 2종 이상이며, 수경성 무기 결합제가 외삽으로 2~10 중량%, 폴리아크릴레이트(polyacrylate), 나프탈렌 설포네이트(naphthalene sulphonate), 및 나트륨 헥사메타포스페이트(sodium hexametaphosphate)로 이루어진 군 중에서 선택된 1종 또는 2종 이상이 외삽으로 0.2~2 중량% 포함된 탄소함유 분사 보수재를 사용한다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon-containing spray repair material for protecting the refractory by applying it to the surface of internal refractories of various urinary tracts, and its object is to provide a carbon-containing spray repair material excellent in corrosion resistance and oxidation resistance. To this end, in the present invention, 3 to 15% by weight of graphite powder, 1 to 5% by weight of aluminum nitride (AlN), the balance is one or two selected from the group consisting of alumina, magnesia, zirconia, spinel, and silicon carbide. Or 2 or 10% by weight of the hydraulic inorganic binder by extrapolation, selected from the group consisting of polyacrylate, poly (phthalate), naphthalene sulphonate, and sodium hexametaphosphate. This extrapolation uses a carbon-containing spray repair containing 0.2 to 2% by weight.

탄소, 흑연분말, 분사 보수재Carbon, Graphite Powder, Spray Repair

Description

탄소함유 분사 보수재 {Wet-type gunning material containing carbon}Wet-type gunning material containing carbon}

본 발명은 탄소를 함유하는 분사 보수재에 관한 것으로, 더욱 상세하게는 철강 설비용 각종 요로의 내장 내화물의 표면에 도포하여 내화물을 보호하는 탄소함유 분사 보수재에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spray repair material containing carbon, and more particularly, to a carbon-containing spray repair material applied to the surface of internal refractories of various urinary furnaces for steel equipment to protect the refractory.

최근 이중 피스톤 방식의 압송장치가 개발되면서 저수분의 치밀질 부정형 내화 조성물을 이송하여 분사 시공하는 습식 분사법(wet-type gunning)이 활발하게 적용되고 있다. 습식 분사법은 치밀질, 저수분의 혼련물을 고압의 피스톤 펌프로 노즐 선단까지 이송한 다음 경화제를 첨가, 혼합하여 고압의 압축공기로 분사함으로써 노체의 손상 부위를 보수하는 방법으로, 기존의 유입 시공체와 유사한 내식성을 나타내기 때문에 활발한 연구가 진행되고 있다.Recently, with the development of a double-piston type pumping device, a wet-type gunning for transporting and spraying a dense amorphous refractory composition of low moisture has been actively applied. The wet spray method repairs damaged parts of the furnace by transferring dense and low moisture kneaded material to the nozzle tip with a high pressure piston pump and then adding and mixing a hardener and spraying it with high pressure compressed air. Active research is being conducted because it shows similar corrosion resistance to the construction body.

일본특허공보 평8-217550에서는 흑연 또는 탄소 함유 내화물의 분말과 입도 250 메쉬 이하의 내화성 미분을 물유리의 희박 수용액과 혼합, 건조한 것에 의하여 흑연 표면에 내화물의 미분을 부착시킨 분말 또는 골재를 준비하고, 이것과 다른 내화물 분말 또는 골재를 배합하여 제조한 탄소함유 분사 보수재를 보고하였다. Japanese Patent Application Laid-Open No. Hei 8-217550 prepares a powder or aggregate obtained by adhering fine powder of a refractory to a graphite surface by mixing and drying a powder of graphite or carbon-containing refractory powder and a refractory fine powder having a particle size of 250 mesh or less with a lean aqueous solution of water glass. A carbon containing spray repair material prepared by combining this with other refractory powders or aggregates was reported.

또한, 일본특허공보 평8-239274에서는 내화재료 100 중량부에 대하여 고정 탄소 65~90 중량％, 연화점 150~350℃의 피치(pitch)를 1~15 중량%, 평균 분자량이 2000 이상의 열경화성 페놀 수지를 2~10 중량%, 탄소 섬유를 0.01~0.5 중량% 함유한 탄소함유 분사 보수재를 제시하였다. In addition, Japanese Patent Application Laid-Open No. Hei 8-239274 discloses a thermosetting phenol resin having 65 to 90% by weight of fixed carbon, 1 to 15% by weight of a softening point of 150 to 350 ° C, and an average molecular weight of 2000 or more, based on 100 parts by weight of the refractory material. To 2 to 10% by weight, carbon-containing spray repair material containing 0.01 to 0.5% by weight was presented.

한국 공개특허 97-702832에서는 내화재료 100 중량부에 대하여, 65 중량% 내지 90중량%의 고정탄소를 가지며, 연화점이 250℃ 내지 350℃인 피치를 1 내지 30 중량부 포함하는 부정형내화물을 이용한 분사 보수재를 보고한 바 있다.Korean Patent Laid-Open Publication No. 97-702832 has a fixed carbon of 65% by weight to 90% by weight with respect to 100 parts by weight of a refractory material, and sprays using an amorphous refractory including 1 to 30 parts by weight of a pitch having a softening point of 250 ° C to 350 ° C. I have reported the conservatives.

그러나 상기 방법들은 내산화성이 낮은 비정질의 탄소 원료를 사용하거나, 탄소 원료의 고온산화를 방지하기 위한 산화방지제를 사용하지 않아서 실제 적용시 탄소 원료의 첨가 효과가 지속되지 못하는 문제점이 있었다.However, these methods do not use an amorphous carbon raw material having low oxidation resistance or do not use an antioxidant for preventing high temperature oxidation of the carbon raw material, so that the effect of adding the carbon raw material may not be sustained in actual application.

본 발명은 상기한 바와 같은 문제점을 해결하기 위하여 안출된 것으로서, 그 목적은, 내식성과 내산화성이 우수한 탄소함유 분사 보수재를 제공하는 데 있다.The present invention has been made to solve the above problems, the object is to provide a carbon-containing injection repair material excellent in corrosion resistance and oxidation resistance.

상기의 목적을 달성하기 위해 본 발명에서는, 흑연 분말이 3~15 중량%, 질화알루미늄(AlN)이 1~5 중량%, 잔부는 알루미나, 마그네시아, 지르코니아, 스피넬, 및 탄화규소로 이루어진 군 중에서 선택된 1종 또는 2종 이상이며, 수경성 무기 결합제가 외삽으로 2~10 중량%, 폴리아크릴레이트(polyacrylate), 나프탈렌 설포네이트(naphthalene sulphonate), 및 나트륨 헥사메타포스페이트(sodium hexametaphosphate)로 이루어진 군 중에서 선택된 1종 또는 2종 이상이 외삽으로 0.2~2 중량% 포함된 탄소함유 분사 보수재를 사용한다. In order to achieve the above object, in the present invention, 3 to 15% by weight of graphite powder, 1 to 5% by weight of aluminum nitride (AlN), the balance is selected from the group consisting of alumina, magnesia, zirconia, spinel, and silicon carbide. 1 type, or 2 or more types, wherein the hydraulic inorganic binder is extrapolated from 2 to 10% by weight, selected from the group consisting of polyacrylate, polyacrylate, naphthalene sulphonate, and sodium hexametaphosphate Use a carbon-containing spray repair containing 0.2 to 2 percent by weight of species or two or more by extrapolation.                     

이하, 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 탄소함유 분사 보수재는 흑연 분말 3~15 중량%와, 질화 알루미늄 1~5 중량%, 그리고 알루미나, 마그네시아, 지르코니아, 스피넬, 탄화규소 중의 1종 또는 2종 이상으로 이루어진 잔부로 구성되며, 여기에 수경성 무기 결합제가 외삽으로 2~10 중량 첨가되고, polyacrylate, naphthalene sulphonate, sodium hexametaphosphate 중의 1종 또는 2종 이상이 외삽으로 0.2~2 중량% 첨가된 조성이다.The carbon-containing spray repair material according to the present invention comprises 3 to 15% by weight of graphite powder, 1 to 5% by weight of aluminum nitride, and the balance consisting of one or two or more of alumina, magnesia, zirconia, spinel, and silicon carbide. 2 to 10 wt% of the inorganic inorganic binder is extrapolated, and one or two or more of polyacrylate, naphthalene sulphonate, and sodium hexametaphosphate are extrapolated by 0.2 to 2 wt%.

본 발명에 따른 분사 보수재의 원료 중 흑연 분말은 폐 전극봉이나 폐 흑연질 도가니 등을 분쇄한 후 체가름하여 얻은 것을 사용하면, 가격이 저렴하므로 제조비용을 절감할 수 있다.The graphite powder in the raw material of the spray repair material according to the present invention is obtained by pulverizing waste electrode rods, waste graphite crucibles, or the like, and then sieving it.

폐 전극봉이나 흑연질 도가니 등의 흑연계 폐기물은 탄소함량이 99% 이상이며 고온에서 소성함으로써 흑연화율이 99% 이상이다. 산화 혹은 이물질의 침투로 인하여 변질된 부위를 제거한 나머지를 분쇄기로 파쇄한 다음 체가름함으로써 내화물의 원료로 사용 가능한 저가 원료를 얻을 수 있다. Graphite wastes such as waste electrodes and graphite crucibles have a carbon content of 99% or more and a graphitization rate of 99% or more by firing at a high temperature. It is possible to obtain a low-cost raw material that can be used as a raw material of the refractory material by crushing the remaining parts removed by the crusher by oxidizing or infiltration of foreign matter and then sieving.

이와 같이 탄소계 폐기물로부터 얻은 흑연 분말의 함량은 3~15 중량%인데, 이는, 흑연 분말의 함량이 3 중량% 보다 적으면 보수재의 내침윤성이 저하하며, 15 중량% 보다 많으면 보수재의 내침식성이 낮아 바람직하지 않기 때문이다. As such, the graphite powder obtained from the carbonaceous waste is 3 to 15% by weight, which is less than 3% by weight of graphite powder, and the infiltration resistance of the repair material is lowered. This is because it is not preferable.

한편, 분사 보수재의 원료 중 AlN은 탄소 원료의 고온 산화를 방지하기 위한 산화방지제로서 사용한 것이다. 기존에 산화방지제로서 사용한 Al, Si 등의 금속 분말은 수용매 중에 분산이 용이하지 않고, 또한 알루미나 시멘트, 마그네시아 미 분 등을 사용하는 캐스타블(castable)에 첨가할 경우 수용매에 의한 금속분말의 수화 반응이 빠르게 진행되어 금속 수화물과 수소기체로 변화하므로 고온에서는 탄소의 산화방지제로써 기능을 할 수 없다. 반면에 본 발명에서 사용한 AlN은 수용매 중에 분산이 용이하고, 고온에서 산화 분위기에 노출되었을 때 주위에 존재하는 탄소 입자보다 우선적으로 열분해한 다음 산화성 기체와 반응하여 Al2O3로 변화함으로써 탄소의 산화를 억제한다.On the other hand, AlN in the raw material of the injection repair material is used as an antioxidant for preventing the high temperature oxidation of the carbon raw material. Metal powders such as Al and Si, which are conventionally used as antioxidants, are not easily dispersed in a solvent, and when added to castables using alumina cement, magnesia fine powder, etc. The hydration reaction of is rapidly progressing to metal hydrate and hydrogen gas, so it cannot function as an antioxidant of carbon at high temperature. On the other hand, AlN used in the present invention is easy to disperse in an aqueous solvent, and when exposed to an oxidizing atmosphere at a high temperature, preferentially pyrolyzes over carbon particles present in the surroundings, and then reacts with an oxidizing gas to change to Al 2 O 3 . Inhibits oxidation

이러한 AlN의 함량은 1~5 중량%인데, 이는, AlN의 함량이 1 중량% 보다 적으면 산화억제 효과가 없고 5 중량% 보다 많으면 산화억제 효과는 동등하지만 필요 이상의 첨가량으로 인하여 보수재 원가가 상승하는 요인이 되기 때문이다. The content of AlN is 1 to 5% by weight, which means that if the content of AlN is less than 1% by weight, there is no oxidation inhibitory effect. It is a factor.

본 발명의 분사 보수재에서 외삽으로 첨가되는 수경성 무기 결합제로는 알루미나 시멘트, 수경성 알루미나 초미분 등을 사용하면 되며 특별히 한정하지 않는다. 무기 결합제의 함량이 외삽으로 2 중량% 보다 적으면 보수재의 기계적 강도가 낮고 10 중량% 보다 많으면 내화성 골재에 비하여 내식성이 낮은 결합제의 함량이 과다하여 보수재의 내식성이 낮아지므로 바람직하지 않다. The hydraulic inorganic binder to be extrapolated from the spray repair material of the present invention may be used by using alumina cement, hydraulic alumina ultrafine powder, and the like. When the content of the inorganic binder is extrapolated to less than 2% by weight, the mechanical strength of the repair material is low, and when the content of the inorganic binder is more than 10% by weight, it is not preferable because the corrosion resistance of the repair material is low because the content of the binder having low corrosion resistance is higher than that of the fire resistant aggregate.

또한, 본 발명의 분사 보수재에서 외삽으로 첨가되는 polyacrylate, naphthalene sulphonate, sodium hexametaphosphate 중 1종 또는 2종 이상은 분산제로서 첨가되는 것이며, 그 첨가량이 0.2 중량%보다 작으면 분산효과가 없어 보수재의 유동성이 낮고 2 중량%보다 많으면 분산성은 유사하면서 필요 이상 첨가한 것이므로 바람직하지 않다. In addition, one or two or more of polyacrylate, naphthalene sulphonate, and sodium hexametaphosphate added by extrapolation in the spray repair material of the present invention are added as a dispersant, and when the addition amount is less than 0.2% by weight, the fluidity of the repair material is ineffective. If it is low and more than 2 weight%, dispersibility is similar, and since it is added more than necessary, it is unpreferable.                     

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다, 그러나, 하기의 실시예는 본 발명의 이해를 돕기 위하여 제시되는 것일 뿐 본 발명이 하기하는 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention. However, the following examples are provided only to aid the understanding of the present invention, and the present invention is not limited to the following examples.

실시예 1 및 2Examples 1 and 2

실시예 1 및 2에서는 표 1에 나타낸 바와 같이, 폐 전극봉, 폐 흑연질 도가니 등에서 변질된 부분을 제거한 후 분쇄기로 파쇄하고, 분쇄물을 0.075 mm 이하의 공업용 체를 이용하여 체가름하여 얻은 흑연 분말을 각각 11 및 10 중량%, 자전고온반응합성법(SHS)으로 제조한 순도 95%, 입도 0.075 mm 이하의 AlN 분말을 4 중량%, 잔부로서 순도 99%, 입도 6 mm 이하의 알루미나 및 마그네시아 내화 골재를 혼합하고, 외삽으로, Al2O3 함량 80%의 알루미나 시멘트 4 및 5 중량%, sodium hexametaphosphate(표 1에서 S로 표시)와 naphthalene sulphonate(표 1에서 N으로 표시)를 각각 0.3 및 0.5 중량%, 수분 5~10 중량%를 추가로 첨가하여 5 분간 혼합하였다. In Examples 1 and 2, as shown in Table 1, the graphite powder obtained by removing the deteriorated part from the waste electrode rod, the waste graphite crucible, etc., and then crushing it with a pulverizer, and sieving the pulverized product using an industrial sieve of 0.075 mm or less 11 and 10% by weight respectively, 95% purity prepared by SHS, 4% by weight of AlN powder with a particle size of 0.075 mm or less, 99% purity as remainder, alumina and magnesia refractory aggregate with a particle size of 6 mm or less And extrapolated 0.3% and 0.5% by weight of 4% and 5% by weight of alumina cement with 80% Al 2 O 3 content, sodium hexametaphosphate (indicated by S in Table 1) and naphthalene sulphonate (indicated by N in Table 1), respectively. %, Moisture 5-10% by weight were further added and mixed for 5 minutes.

혼합물의 유동성 평가를 위해 플로우 테이블(flow table)을 이용하여 15 회 타격한 후 시편의 퍼짐성(flow 값)을 측정하였다. The flowability of the specimens was measured after 15 blows using a flow table to evaluate the flowability of the mixture.

상온강도 측정을 위해 4040160mm 크기의 시편, 침식시험을 위해 110(길이)40(높이)88(윗변) 116(아래변)mm 횡제리형 시편, 산화시험을 위해 606060mm 시편을 성형하였으며, 실온에서 12 시간 양생한 후 110 ℃에서 24 시간 건조하였다. JIS 규격에 근거하여 꺾임강도를 측정하였다. 4040 160mm specimens for measuring room temperature strength, 110 (length) 40 (height) 88 (upper side) 116 (lower side) mm cross-section specimens for erosion test, 606060mm specimens for oxidation test, 12 hours at room temperature After curing, the mixture was dried at 110 ° C. for 24 hours. The bending strength was measured based on the JIS standard.                     

가스 소성로를 이용하여 1500℃에서 3시간 소성한 다음 시편의 중앙을 절단하여 산화층의 면적을 구하여 전체 면적에 대한 비를 구하여 산화지수를 나타내었다. After firing at 1500 ° C. for 3 hours using a gas firing furnace, the center of the specimen was cut to obtain the area of the oxide layer, and the ratio to the total area was obtained to show the oxidation index.

제강 레이들에서 채취한 슬래그를 이용하여 1650 ℃에서 3시간 회전침식시험을 수행하였으며, 시험 후 시편의 중앙을 절단하여 침식 및 침윤 두께를 측정하여 침식지수 및 침윤지수를 나타내었다. The erosion test was carried out at 1650 ° C. for 3 hours using slag collected from steelmaking ladles. After the test, the center of the specimen was cut to measure the erosion and infiltration thicknesses.

상기한 바와 같은 방법으로 측정된 flow 값, 침윤지수, 침식지수, 상온강도, 및 산화지수를 표 1에 나타내었다.The flow values, infiltration index, erosion index, room temperature strength, and oxidation index measured by the method as described above are shown in Table 1.

한편, 비교예 1 내지 9에서는 사용되는 각 원료를 본 발명에서 제시한 함량 범위를 벗어난 조건으로 분사 보수재를 제조한 후, 실시예와 동일한 방법으로 flow 값, 침윤지수, 침식지수, 상온강도, 및 산화지수를 측정하고, 그 결과를 표 1에 함께 나타내었다. 이 때 flow 값이 130 mm 이하로 낮은 시편에 대해서는 다른 시험을 수행하지 않았다.On the other hand, in Comparative Examples 1 to 9 after the injection repair material is manufactured under the conditions outside the content range suggested in the present invention, the flow value, infiltration index, erosion index, room temperature strength, and The oxidation index was measured and the results are shown in Table 1 together. No other tests were performed on specimens with flow values as low as 130 mm.

또한, 침윤지수, 침식지수 및 산화지수는 비교예 1을 기준시편으로 하여 비교예 1의 측정값을 100으로 하여 이에 대한 백분율로써 지수화하여 나타내었다.In addition, the infiltration index, the erosion index and the oxidation index was expressed as a percentage of the value of Comparative Example 1 to the measured value of Comparative Example 1 to 100 as a reference sample.

흑연분말함량 (중량%)Graphite powder content (% by weight) AlN함량 (중량%)AlN content (wt%) 결합제 함량 (중량%)Binder Content (% by weight) 분산제 함량 (중량%)Dispersant Content (wt%) Flow 값(mm)Flow value (mm) 침윤지수Infiltration Index 침식지수Erosion Index 상온강도(kg/cm2)Room temperature strength (kg / cm 2 ) 산화지수Oxidation index 실시예Example 1One 1111 44 44 0.3(S)0.3 (S) 157157 8585 100100 5959 101101 22 1010 44 55 0.5(N)0.5 (N) 159159 8585 9999 6060 100100 비교예Comparative example 1One 1One 44 55 1(N)1 (N) 160160 100100 100100 6565 100100 22 2020 44 55 0.5(N)0.5 (N) 145145 8080 150150 4545 110110 33 1010 0.50.5 55 0.3(S)0.3 (S) 155155 120120 120120 6363 190190 44 1010 1010 55 1(N)1 (N) 157157 8787 100100 5151 9898 55 1010 55 1One 0.2(S)0.2 (S) 154154 8787 105105 3535 100100 66 1010 55 2020 0.5(N)0.5 (N) 155155 140140 160160 7070 100100 77 1212 44 44 0.05(S)0.05 (S) 120120 -- -- -- -- 88 1010 33 55 3(N)3 (N) 160160 8787 101101 6161 101101

표 1에 나타낸 바와 같이, 본 발명의 범위를 벗어난 조건으로 제조한 비교예 1~8의 경우 유동도, 기계적 강도, 내침식성, 그리고 내침윤성 등이 낮음을 알 수 있었다. 반면에 본 발명의 조건 범위로 제조된 실시예 1 및 2의 경우 각종 특성이 우수함을 알 수 있었다.As shown in Table 1, in Comparative Examples 1 to 8 manufactured under conditions outside the scope of the present invention, it was found that the fluidity, mechanical strength, corrosion resistance, and infiltration resistance were low. On the other hand, in the case of Examples 1 and 2 manufactured under the condition range of the present invention, it was found that various characteristics were excellent.

상기한 바와 같이, 본 발명에 따른 분사 보수재는 고온에서 장시간 사용시 우수한 내식성과 내산화성을 나타내기 때문에 노체의 손상부위 보수에 적용시 사용 수명이 향상되고, 따라서 원가가 절감되는 효과가 있다.As described above, since the spray repair material according to the present invention exhibits excellent corrosion resistance and oxidation resistance when used at a high temperature for a long time, the service life is improved when applied to repairing damaged parts of the furnace, thus reducing the cost.

또한, 본 발명에서는 탄소계 폐기물로부터 얻은 저가의 흑연 분말을 탄소 원료로 사용하기 때문에 제조 비용이 절감되는 효과가 있다.
In addition, in the present invention, since the inexpensive graphite powder obtained from the carbon-based waste is used as the carbon raw material, the manufacturing cost is reduced.

Claims (2)

흑연 분말이 3~15 중량%, 질화알루미늄(AlN)이 1~5 중량%, 잔부는 알루미나, 마그네시아, 지르코니아, 스피넬, 및 탄화규소로 이루어진 군 중에서 선택된 1종 또는 2종 이상이며, 수경성 무기 결합제가 외삽으로 2~10 중량%, 폴리아크릴레이트(polyacrylate), 나프탈렌 설포네이트(naphthalene sulphonate), 및 나트륨 헥사메타포스페이트(sodium hexametaphosphate)로 이루어진 군 중에서 선택된 1종 또는 2종 이상이 외삽으로 0.2~2 중량% 포함된 탄소함유 분사 보수재.3 to 15% by weight of graphite powder, 1 to 5% by weight of aluminum nitride (AlN), the balance is one or two or more selected from the group consisting of alumina, magnesia, zirconia, spinel, and silicon carbide; One or two or more selected from the group consisting of 2 to 10% by weight of extrapolation, polyacrylate, naphthalene sulphonate, and sodium hexametaphosphate are extrapolated from 0.2 to 2 Carbon-containing spray repair material by weight. 제 1 항에 있어서,The method of claim 1, 상기 흑연 분말은 탄소계 폐기물을 분쇄하고 상기 분쇄물을 체가름하여 얻어진 것인 탄소함유 분사 보수재.The graphite powder is obtained by pulverizing the carbon-based waste and sieving the pulverized product.
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JPH11310474A (en) * 1998-04-28 1999-11-09 Okayama Ceramics Gijutsu Shinko Zaidan Surface-treated graphite and carbon-containing amorphous refractories using it
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