KR20010063698A - Coating method for the roll of high concentration of Zircon - Google Patents
Coating method for the roll of high concentration of Zircon Download PDFInfo
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- KR20010063698A KR20010063698A KR1019990061773A KR19990061773A KR20010063698A KR 20010063698 A KR20010063698 A KR 20010063698A KR 1019990061773 A KR1019990061773 A KR 1019990061773A KR 19990061773 A KR19990061773 A KR 19990061773A KR 20010063698 A KR20010063698 A KR 20010063698A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
- B05B7/22—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc
- B05B7/222—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc
- B05B7/226—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc the material being originally a particulate material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
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- Metallurgy (AREA)
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- Electromagnetism (AREA)
- Coating By Spraying Or Casting (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
Abstract
Description
본 발명은 도금공장의 용융도금욕 내의 포트 롤(Pot Roll)이나, 냉연공장의 연속소둔로 내의 허스 롤(Hearth Roll) 등의 롤 표면에 지르콘 분말을 사용하여 용사코팅하는 지르콘 농도가 높은 롤 코팅방법에 관한 것이다.The present invention is a roll coating having a high zircon concentration coating using a zircon powder on the surface of a roll such as a pot roll in a hot dip bath of a plating plant or a hearth roll in a continuous annealing furnace of a cold rolling mill. It is about a method.
우선 도금공정에 쓰이는 포트 롤 코팅에 대해서 설명한다. 이 코팅은 대표적으로 용융아연도금 공정 중 가장 도금 품질을 좌우하는 공정인 용융도금 욕조 내에 쓰이는 포트 롤(Pot Roll)의 표면에 코팅을 실시하는 것으로, 표면에 드로스(아연산화물)가 잘 부착되지 않도록 하는 것이다. 기존에는 WC계 코팅을 사용하였으나, WC계 코팅의 바인더(Binder)로 쓰이는 각종 금속(Co, CoCr, NiCr)들이 아연에 대해 용식성이 있으므로, 이를 방지하기 위해서 세라믹 코팅이 사용되기도 한다. 세라믹 코팅으로는 알루미나-지르코니아계 등이 사용되었으나, 그 중에 지르콘은 아연과의 젖음성(Wettabilty)이 가장 떨어지고, 또한 반응성이 적기 때문에 좋은 재료로 알려져 있었다.First, the port roll coating used in the plating process will be described. This coating is typically coated on the surface of the pot roll used in the hot dip bath, which is the process that most affects the plating quality of the hot dip galvanizing process, and dross (zinc oxide) does not adhere well to the surface. It is to avoid. Conventionally, WC-based coatings have been used, but various metals (Co, CoCr, NiCr) used as binders of the WC-based coatings are soluble in zinc, so ceramic coatings may be used to prevent them. Alumina-zirconia-based or the like was used as the ceramic coating. Among them, zircon was known as a good material because it has the lowest wettability with zinc and is less reactive.
이에 대한 공지기술로 일본국 공개특허공보 JP 95-126072 호에서는 지르콘 10-85% 와 나머지 질화 규소, 사일론, 질화붕소, 질화나트륨을 포함한 1종 또는 2종의 질화물을 포함하는 코팅발명이 개시되어 있는 데, 두 종의 질화물을 코팅하는 것은 질화물과의 밀착력이 떨어져 효과가 떨어지는 문제점이 있다.As a well-known technique, Japanese Patent Application Laid-Open No. JP 95-126072 discloses a coating invention including 10-85% of zircon and one or two nitrides including remaining silicon nitride, silica, boron nitride, and sodium nitride. In the case of coating two kinds of nitrides, there is a problem in that the adhesion with the nitrides is lowered and the effect is lowered.
다음은 냉연 소둔 공정에 쓰이는 허스 롤 표면 코팅에 대해서 설명한다. 허스 롤이란 연속소둔로 내부에 설치되어 강판의 이송 시 안내 역할을 하는 롤로서, 이 코팅은 강판과의 접촉에서 비롯되는 빌드업(Build-up) 현상을 줄이는 작용을 한다. 연속소둔로 안의 분위기 가스로는 강판의 산화를 방지하기 위하여 N2+(3-5)% H2(Dew Point: -20℃ 이하)가 쓰이고, 그 안의 온도는 약 500-1000℃ 이다. 이 허스 롤의 표면은 높은 표면조도(Ra)를 요구하는 데, 그 이유는 조도가 높아야 강판의 사행(옆으로 미끄러지는 것)을 방지할 수 있기 때문이다. 특히 이 코팅은 높은 고온경도 유지가 필요한 데, 그 이유는 고온경도가 높아야 장시간 작업 후에도 표면조도를 유지할 수 있기 때문이다. 현재 이 코팅의 수명은 표면조도(Ra)가 5㎛ 이하로 떨어지면 일반적으로 교체한다.The following describes the hearth roll surface coating used in the cold rolling annealing process. The hearth roll is a roll which is installed inside the continuous annealing furnace and serves as a guide during the transport of the steel sheet. This coating reduces the build-up phenomenon resulting from contact with the steel sheet. As an atmosphere gas in the continuous annealing furnace, N 2 + (3-5)% H 2 (Dew Point: below -20 ° C) is used to prevent oxidation of the steel sheet, and the temperature therein is about 500-1000 ° C. The surface of the hearth roll requires high surface roughness Ra, because the roughness can be prevented from meandering (sliding to the side) of the steel sheet. In particular, the coating needs to maintain a high temperature hardness, because the high temperature hardness can maintain the surface roughness even after a long time. The life of this coating is now generally replaced when the surface roughness (Ra) drops below 5 μm.
허스 롤 코팅에 관한 연구를 통하여 기술 선진국에서 여러 가지 종류의 코팅을 연구 개발하였다. 이러한 코팅은 폭발용사(Detonation Gun Spraying), 플라즈마 용사(Plasma Spraying) 등을 이용하여 롤의 표면에 코팅을 실시하는 것이다. 공지기술로 일본국 특허공개공보 평7-003426호에는 SiO2를 함유하는 허스 롤 코팅에 관해 기재되어 있고, 평7-003425호에는 ZrO2계통의 코팅에 대해 기재되어 있고, 미국특허 제5,418,015호에는 ZrSiO4계의 코팅에 대해서 기재되어 있다.Through research on the hearth roll coating, various types of coatings have been researched and developed in advanced countries. This coating is to apply a coating on the surface of the roll by using a detonation gun spraying (Plasma Spraying), etc. As a well-known technique, Japanese Patent Laid-Open Publication No. Hei 7-003426 describes a hearth roll coating containing SiO 2 , and Hei 7-003425 describes ZrO 2 -based coatings, and US Patent No. 5,418,015. The ZrSiO 4 -based coating is described.
이와 같이, 도금공정의 포트 롤이나 냉연 소둔공정의 허스 롤의 코팅에는 지르콘을 사용한 코팅이 적합하나, 지르콘을 이용하여 플라즈마 용사를 실시할 때는 지르콘이 분해되어 지르콘의 일부분이 지르코니아(ZrO2) 와 실리카(SiO2)로 분해되어 코팅의 목적을 원활히 달성하지 못하는 문제점이 있다. 도 1에서는 플라즈마 용사 후, 표면의 X 선 회절 결과를 보이고 있다.In this way, suitable for the coating with zirconium coating of the hearth rolls of the port roll or cold-rolled annealing step of the plating process, one, when using a zircon subjected to plasma spraying is zircon decomposition part of a zircon zirconia (ZrO 2) and Decomposition into silica (SiO 2 ) has a problem that does not achieve the purpose of the coating smoothly. 1 shows the X-ray diffraction results of the surface after plasma spraying.
본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위하여 발명된 것으로서, 지르콘 플라즈마 용사 후에 열처리를 실시하여 분해가 되었던 지르코니아와 실리카를 지르콘으로 재 형성시키도록 하고, 지르콘 분말에 소량의 Fe 또는 Mn을 첨가하여 열처리 시에 지르콘의 합성을 도울 수 있도록 하는 지르콘 농도가 높은 롤 코팅방법을 제공함을 그 목적으로 한다.The present invention has been invented to solve the problems of the prior art as described above, to perform a heat treatment after the zircon plasma spray to re-decompose zirconia and silica into zircon, and a small amount of Fe or Mn in the zircon powder It is an object of the present invention to provide a roll coating method having a high zircon concentration that can be added to help the synthesis of zircon during heat treatment.
도 1은 지르콘 플라즈마 용사 후, 표면의 X 선 회절 결과를 나타낸 그래프.1 is a graph showing the X-ray diffraction results of the surface after the zircon plasma spraying.
상기의 목적을 달성하기 위한 본 발명의 지르콘 농도가 높은 롤 코팅방법은, 도금욕조내의 포트 롤 또는 냉연 허스 롤 등의 롤 표면을 코팅하는 방법에 있어서, 내열강의 표면에 본드 코팅을 실시하고, 그 위에 Fe 또는 Mn을 0.25 내지 0.5 wt.% 이내로 함유하고 있는 지르콘 분말을 이용하여 플라즈마 용사 코팅을 실시한 후, 1150 내지 1200℃의 온도범위에서 1 내지 1.5 시간 동안 열처리하는 것을 특징으로한다.In the roll coating method having a high zircon concentration of the present invention for achieving the above object, in the method of coating a roll surface such as a pot roll or a cold rolled hearth roll in a plating bath, the surface of the heat resistant steel is subjected to a bond coating. After the plasma spray coating using the zircon powder containing Fe or Mn within 0.25 to 0.5 wt.%, Characterized in that the heat treatment for 1 to 1.5 hours at a temperature range of 1150 to 1200 ℃.
또한, 본 발명에서는 상기 지르콘 분말에 Fe 및 Mn을 각각 0.25 내지 0.5 wt.% 이내로 첨가할 수 도 있다.In addition, in the present invention, Fe and Mn may be added to the zircon powder within 0.25 to 0.5 wt.%, Respectively.
이하에서는 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 연속 용융도금공정의 용융도금욕조내의 포트 롤 또는 냉연 소둔공정의 허스 롤 등의 롤을 그 대상으로 한다.The present invention is directed to a roll such as a pot roll in a hot dip bath of a continuous hot dip plating process or a hearth roll of a cold rolling annealing process.
먼저 SCH22(고 Ni, Cr, C 강) 등의 일반적인 내열강의 표면에 본드코팅을 실시하고, 그 위에 플라즈마 용사방법을 사용하여 코팅을 실시한다.First, a bond coating is applied to the surface of general heat resistant steel such as SCH22 (high Ni, Cr, C steel), and the coating is applied thereon using a plasma spraying method.
상기 플라즈마 용사코팅의 재료로는 Fe 및 Mn을 각각 0.25 내지 0.5 wt.% 이내로 함유하고 있거나, Fe 또는 Mn 어느 하나를 0.25 내지 0.5 wt.% 이내로 함유하고 있는 지르콘 분말을 이용한다.As the material of the plasma spray coating, zircon powder containing Fe and Mn within 0.25 to 0.5 wt.% Or either Fe or Mn within 0.25 to 0.5 wt.% Is used.
상기와 같이 Fe 또는 Mn을 지르콘 분말에 첨가하여 사용하는 이유는 후공정의 열처리시에 지르콘의 합성을 도와주도록 하기 위한 것이며, 그 첨가량을 0.25 내지 0.5 wt.% 이내로 제한하는 이유는, 범위 이하에서는 첨가효과가 미약하고, 범위 이상에서는 Fe 또는 Mn의 산화에 의한 Fe 산화물 또는 Mn 산화물의 양이 많아져서 오히려 지르콘의 비 반응성의 영향을 방해할 수 있기 때문이다.The reason why Fe or Mn is added to the zircon powder and used as described above is to assist in the synthesis of zircon during the heat treatment of the post process, and the reason for limiting the addition amount to within 0.25 to 0.5 wt.% Is below the range. This is because the addition effect is insignificant, and in the above range, the amount of Fe oxide or Mn oxide due to the oxidation of Fe or Mn increases, which may hinder the influence of the zircon's non-reactivity.
이와 같이 지르콘의 용사코팅이 완료되면, 1150 내지 1200℃의 온도범위에서 1 내지 1.5 시간 동안 열처리한다.When the thermal spray coating of zircon is completed, heat treatment for 1 to 1.5 hours at a temperature range of 1150 to 1200 ℃.
열처리의 목적은 용사코팅층의 조성을 지르콘이 분해되는 것을 방지하여 대부분 지르콘으로 유지하기 위한 것이다. 열처리 온도범위 및 시간범위를 이와 같이한정한 이유는, 그 범위 이상에서는 모재 자체가 심하게 열처리되어 지르콘의 농도는 증가할 지라도 경도가 저하되는 별개의 문제가 발생하고, 그 범위 이하에서는 열처리 효과가 미약하기 때문이다.The purpose of the heat treatment is to maintain the composition of the thermal spray coating layer is mostly zircon to prevent the decomposition of zircon. The reason for limiting the heat treatment temperature range and the time range in this way is that the above-mentioned range causes the heat treatment of the base material itself to cause a separate problem of deterioration in hardness even though the concentration of zircon increases. Because.
이하에서는 구체적인 실시예 및 비교예를 통하여 본 발명에 대하여 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples.
SCH22(고 Ni, Cr, C 강) 등의 내열강 위에 우선 블라스팅(Blasting)을 알루미나 입자가 약 85-100㎛ 인 것을 이용하여 공기압이 5 Kg/㎠ 이상으로 표면을 거칠게 한다. 그때 표면조도(Ra)가 약 12-15㎛ 인지를 확인한다.First, blasting (blasting) on heat-resistant steel such as SCH22 (high Ni, Cr, C steel) to roughen the surface with air pressure of 5 Kg / cm 2 or more using alumina particles of about 85-100 탆. At that time, confirm that the surface roughness Ra is about 12-15 μm.
본드 코팅은 CoCrNiAlTaY 본드 코팅을 30 ㎛ 실시한다. 코팅실시 후에 표면조도(Ra)가 6-8㎛ 가 되도록 하기 위하여 연마(Buffing)를 실시한다. 연마재는 다이아몬드를 함유한 연마천으로 실시한다.Bond coating carries out 30 micrometers of CoCrNiAlTaY bond coatings. After coating is carried out, buffing is performed to make the surface roughness Ra be 6-8 μm. The abrasive is carried out with an abrasive cloth containing diamond.
분말입자의 크기가 30-150㎛ 인 지르콘 분말에 다음의 표 1에 나타낸 바와 같은 첨가량의 첨가물을 각각 첨가한 분말을 사용하여 플라즈마 용사코팅을 약 100 ㎛ 실시한다. 코팅은 Sulzer Metco 사의 PT-M1000 으로 Ar, He 가스를 이용하여 실시하였다(Primary Gas: Ar gas, 80 SLPM (standard liter per minute) at 5 kg/㎠, Secondary Gas: He gas, 17 SLPM (standard liter per minute) at 5 kg/㎠, Gun Volts: 60 V, Gun Ampere: 650 A).Plasma spray coating is performed by using a powder in which zircon powder having a particle size of 30-150 µm is added to each of the additives as shown in Table 1 below. Coating was performed using Sul, Metco's PT-M1000 using Ar, He gas (Primary Gas: Ar gas, 80 SLPM (standard liter per minute) at 5 kg / ㎠, Secondary Gas: He gas, 17 SLPM (standard liter) per minute) at 5 kg / cm 2, Gun Volts: 60 V, Gun Ampere: 650 A).
지르콘 분말의 공급양은 15 g/min 로 하였고, 용사거리는 120 mm 로 하였다.The supply amount of zircon powder was 15 g / min, and the spraying distance was 120 mm.
지르콘 분말이 용사코팅 후에는 다음 표 1에 나타낸 바와 같이 열처리하고, X선 회절 시험을 실시하여 지르콘분율을 계산하여 나타내었다.After the zircon powder was thermally coated, it was heat-treated as shown in Table 1 below, and the zircon fraction was calculated by X-ray diffraction test.
상기 표 1에서 알 수 있듯이, 비교재 8, 9와 같이 열처리를 하지 않는 경우에는 지르콘분율이 매우 낮음을 알 수 있고, 비교재 2 내지 비교재 4와 같이 Fe 또는 Mn 첨가량이 작은 경우 및 비교재 5 내지 비교재 7과 같이 열처리온도가 낮은 경우 등의 본 발명의 범위 밖일 경우에도 지르콘분율은 본 발명의 발명재 1 내지 발명재 8과 비교할 때 상당히 낮음을 알 수 있다.As can be seen in Table 1, when the heat treatment is not performed as in Comparative Materials 8 and 9, it can be seen that the zircon fraction is very low, and when the amount of Fe or Mn added is small as in Comparative Materials 2 to 4 and Comparative Materials It can be seen that the zircon fraction is considerably lower than that of Inventive Materials 1 to 8 of the present invention even when outside the scope of the present invention, such as when the heat treatment temperature is low, such as 5 to Comparative Material 7.
또한, 비교재 1의 경우에는 열처리온도가 1200℃로서 너무 높은 경우에는 지르콘분율은 상당히 높으나, 모재의 경도 저하가 많아서 부적합함을 알 수 있다(경도가 HRC로 58에서 52로 감소).In addition, in the case of Comparative Material 1, if the heat treatment temperature is too high, such as 1200 ℃, the zircon fraction is considerably high, but the hardness of the base material is largely unsuitable (hardness is reduced from 58 to 52 in HRC).
이상에서 상세히 설명한 바와 같이 본 발명의 지르콘 농도가 높은 롤 코팅방법을 사용하면, 지르콘 플라즈마 용사코팅 후에 지르콘이 지르코니아와 실리카로 분해되는 것을 방지할 수 있어 지르콘 코팅의 목적을 원활히 달성할 수 있는 효과가 있다.As described in detail above, by using the roll coating method having a high zircon concentration of the present invention, it is possible to prevent zircon from being decomposed into zirconia and silica after zircon plasma spray coating, so that the purpose of the zircon coating can be smoothly achieved. have.
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| KR1019990061773A KR20010063698A (en) | 1999-12-24 | 1999-12-24 | Coating method for the roll of high concentration of Zircon |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63282249A (en) * | 1987-05-13 | 1988-11-18 | Nippon Steel Corp | Thermal spray coated casting metal mold and thermal spraying method thereof |
| JPH062101A (en) * | 1992-06-15 | 1994-01-11 | Kurosaki Refract Co Ltd | Alumina-zircon thermal spraying material containing metal powder |
| JPH06135768A (en) * | 1992-10-28 | 1994-05-17 | Praxair St Technol Inc | Powdery composition for forming fire resisting oxide film, method for use thereof and article |
-
1999
- 1999-12-24 KR KR1019990061773A patent/KR20010063698A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63282249A (en) * | 1987-05-13 | 1988-11-18 | Nippon Steel Corp | Thermal spray coated casting metal mold and thermal spraying method thereof |
| JPH062101A (en) * | 1992-06-15 | 1994-01-11 | Kurosaki Refract Co Ltd | Alumina-zircon thermal spraying material containing metal powder |
| JPH06135768A (en) * | 1992-10-28 | 1994-05-17 | Praxair St Technol Inc | Powdery composition for forming fire resisting oxide film, method for use thereof and article |
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