EP0480727A1 - Rouleau de fourneau revêtu et procédé pour sa fabrication - Google Patents

Rouleau de fourneau revêtu et procédé pour sa fabrication Download PDF

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Publication number
EP0480727A1
EP0480727A1 EP19910309332 EP91309332A EP0480727A1 EP 0480727 A1 EP0480727 A1 EP 0480727A1 EP 19910309332 EP19910309332 EP 19910309332 EP 91309332 A EP91309332 A EP 91309332A EP 0480727 A1 EP0480727 A1 EP 0480727A1
Authority
EP
European Patent Office
Prior art keywords
feed composition
powder feed
coating
zirconia
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19910309332
Other languages
German (de)
English (en)
Other versions
EP0480727B1 (fr
Inventor
Harold Haruhisa Fukubayashi
Masahiko C2-3-12 Nippon Steel Ohwada Apt. Amano
Yukihiro B2-12 Nippon Steel Ohwada Apt. Nakamura
Keiichiro Ohno
Hideo Nitta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Praxair ST Technology Inc
Original Assignee
Union Carbide Coatings Service Technology Corp
Praxair ST Technology Inc
Union Carbide Coatings Service Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide Coatings Service Technology Corp, Praxair ST Technology Inc, Union Carbide Coatings Service Corp filed Critical Union Carbide Coatings Service Technology Corp
Publication of EP0480727A1 publication Critical patent/EP0480727A1/fr
Application granted granted Critical
Publication of EP0480727B1 publication Critical patent/EP0480727B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • 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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides

Definitions

  • the present invention relates to a thermal spray powder feed composition. It also relates to such a composition for forming a refractory oxide coating having high thermal shock resistance, increased wear resistance and resistance to spalling in thermal cycling environments and to a process for forming a refractory oxide coating and to an article having a refractory oxide coating.
  • This invention relates particularly to the problem of providing a high wear and thermal shock resistant coating for hearth rolls for annealing steel, stainless steel and silicon steel sheet in a hearth (furnace).
  • the hearth rolls carry the steel sheet through the hearth.
  • the temperature in the hearth may vary from about 816°C (1500°F) to over 1093°C (2000°F) depending upon the type of steel, the travel speed of the sheet steel as it passes through the furnace and the duration of time in the furnace.
  • a major problem encountered in the annealing operation is the transfer or pick-up of material from the steel sheet to the hearth rolls. If pick-up occurs, it will accumulate on the hearth rolls and damage the steel sheet being processed. To avoid this problem frequent roll changes are required with concomitant costs for replacement and lost production. This problem has become more severe in recent years since thinner sheets are being used, along with higher speeds and temperature to increase productivity.
  • the hearth roll To suppress the transfer of material to the hearth roll and to increase wear resistance it is desirable to coat the hearth roll with a coating composition which is substantially chemically inert at elevated temperatures.
  • An undercoating of metal or a ceramic-metal alloy is used to prevent spalling. Spalling may also be prevented using a graded coating in which the composition of the undercoating is gradually varied from 100% alloy to 100% ceramic.
  • the ceramic coatings presently available usually crack in thermal cycling due to a large difference in thermal expansion between the substrate, a heat resistant alloy, and the coating.
  • the alloy undercoat at the interface is oxidized at or above 1000°C in the presence of oxygen leading to spalling of the ceramic layer.
  • the alloy component of the coating When a graded coating is used, the alloy component of the coating is also oxidized which, in turn, increases the volume of the coating. Upon cooling, the coating spalls due to excessive compressive stress created by the shrinkage of the substrate.
  • the powder feed composition of the present invention produces a coating particularly useful to protect a hearth roll in a continuous annealing line for annealing steel, stainless steel or silicon steel sheets.
  • the powder feed composition comprises particles of zirconium silicate in a mixture with particles of zirconia stabilized or partially stabilized with an oxide selected from Y203, CaO, MgO, CeO2 and HfO2.
  • the powder feed composition is applied by a thermal spray technique to produce an as-deposited coating having a composition which by x-ray phase analysis comprises zirconia, silica and zirconium silicate.
  • the major component of the powder composition is partially stabilized zirconia with the zirconium silicate preferably limited to a maximum of 60 wt%.
  • the powder feed composition should comprise at least 65 wt% stabilized zirconia with the remainder substantially zirconium silicate whereas for detonation gun application the powder feed composition should comprise at least 40 wt% stabilized zirconia and up to 60 wt% zirconium silicate.
  • the zirconia may be either fully or partially stabilized although partially stabilized zirconia is preferred.
  • spalling of the coating may be prevented at elevated temperatures exceeding 1150°C by thermally spraying a metallic undercoat.
  • the preferred undercoat in a cobalt based metal matrix comprising Co-Cr-Al-Ta-Y with a dispersion of Al2O3.
  • the present invention is based upon the discovery that a starting powder feed composition consisting essentially of a mixture of zirconium silicate and zirconia with the zirconia being stabilized with a stabilizing oxide such as, for example, yttria, calcia, or magnesia may be thermally sprayed to form a coating processing the characteristic of being resistant to thermal shock and resistant to steel or steel oxide pick-up from a continuous annealing line. Any conventional thermal spray technique may be used to form the coating including detonation gun deposition and plasma spray deposition.
  • the chemical composition of the thermally sprayed coating should consist of a mixture of at least about 40 wt% zirconia (ZrO2), including a stabilizer for the zirconia selected from the group consisting of CaO, Y2O3, MgO, CeO2 and HfO2 with the balance zirconium silicate (ZrSiO4) and/or its decomposition products SiO2 and ZrO2.
  • ZrO2 zirconia
  • the preferred weight percent of the component oxides in the coating is 55 to 85% stabilized ZrO2 and 15 to 45% ZrSiO4 and/or its decomposition products SiO22 and ZrO22.
  • the optimum weight percent of the component oxides in the coating is 70 to 85% stabilized ZrO2 and 15 to 30% ZrSiO4 and/or its decomposition products.
  • the stabilizer should be between 2 and 20 wt% of the zirconia component.
  • the coatings are preferably applied by detonation gun deposition or plasma spray deposition.
  • a typical detonation gun consists essentially of a water-cooled barrel which is some metres (several feet) long with an inside diameter of about 2.5mm (1 inch).
  • a mixture of oxygen and a fuel gas e.g., acetylene, in a specified ratio (usually about 1:1) is fed into the barrel along with a charge of coating material in powder form. Gas is then ignited and the detonation wave accelerates the powder to about 730 m/sec, (2400 ft./sec) while heating the powder close to or above its melting point.
  • a pulse of nitrogen purges the barrel and readies the system for the next detonation. The cycle is then repeated many times a second.
  • the detonation gum deposits a circle of coating on the substrate with each detonation.
  • the circles of coating are about 25mm (1 inch) in diameter and several microns (a few ten thousandths of an inch) thick.
  • Each circle of coating is composed of many overlapping microscopic thin lenticular particles or splats corresponding to the individual powder particles. The overlapping splats interlock and bond to each other and the substrate without automatically alloying at the interface thereof.
  • the placement of the circles in the coating deposition are closely controlled to build-up a smooth coating of uniform thickness and to minimize substrate heating.
  • an electric arc is established between a non-consumable electrode and a second non-consumable electrode spaced therefrom. Gas is passed in contact with the non-consumable electrode such that it contains the arc.
  • the arc-containing gas is constricted by a nozzle and results in a high thermal content effluent.
  • the powders used to produce the coatings are injected into the effluent nozzle and are deposited onto the surfaces to be coated. This process, which is described in US-A-2 858 411, produces a deposited coating which is sound, dense and adherent to the substrate.
  • the applied coating also consists of irregularly shaped microscopic splats or leaves which are interlocked and bonded to one another and also the substrate.
  • the coating composition for the plasma arc spray process will be substantially equivalent to its corresponding starting material composition.
  • the detonation gun to apply the starting material evaporation of the components may result in a significantly different ratio of constituents in the as deposited coating.
  • some change in chemistry may occur during deposition, using any thermally sprayed process. Such changes can be compensated for by adjusting the powder composition or deposition parameters.
  • the solidifying ZrSiO4 powder particles may contain ZrSiO4 as a crystallographic phase and/or ZrO2 + SiO2 as the decomposition products of the molten ZrSiO4 in separate crystallographic phases within individual splats.
  • ZrO2 and SiO2 are intimately associated within each splat which had previously been ZrSiO4 in the powder form.
  • ⁇ associated ⁇ is meant the extremely fine and intermixed crystalline structure of SiO2, ZrO2 and/or ZrSiO4 crystallites within the splat.
  • the coatings of the present invention are preferably applied by detonation or plasma spray deposition, it is possible to employ other thermal spray techniques such as, for example, high velocity combustion spray (including hypersonic jet spray), flame spray and so called high velocity plasma spray methods (including low pressure or vacuum spray methods). Other techniques can be employed for depositing the coatings of the present invention as will readily occur to those skilled in the art.
  • the thermal spray coating may be applied directly to the metal substrate.
  • an undercoat compatible with the substrate and resistant to oxidation is preferred.
  • An undercoat of a ceramic-metal alloy mixture having a cobalt based metal matrix containing alumina is preferred.
  • Optimum coatings are a cobalt based alloy with alumina dispersions described in US-A- 4 124 737. The refractory oxide coating reacts with the preferred undercoat to produce an impervious thin layer of aluminium and/or zirconium oxide phases at the interface which prevents oxidation of the undercoat as well as to provide good bonding between the undercoat and the ceramic layer.
  • the impervious layer may be less than 0.005mm (5 microns) and is produced as a result of interdiffusion or oxidation in an environment at an elevated temperature in the presence of oxygen.
  • a similar layer may form in an inert atmosphere as a result of reaction between the oxide overcoat and the metallic undercoat.
  • various powder mixtures containing a yttria stabilized zirconia (ZrO2 ⁇ 8% Y2O3) and zirconium silicate (ZrSiO4) were mechanically blended into the blend ratios identified in Table I and fed to a plasma torch in a conventional manner to produce a coating on a 304 stainless steel bar.
  • the ceramic coating was applied on one face of the 304 stainless steel bar 6.99x1.91x1.27cm (2 3/4 ⁇ x 3/4 x 1/2 ⁇ height) which was first coated with a detonation gun with an undercoat of 0.05 to 0.075mm (50 to 75 microns) of a cobalt-based coating undercoating of 90 (Co-25Cr-7.5A1-0.8Y-10Ta) + 10% A12O3. Then the ceramic coating was ground to a 100 micrometre thickness before heat cycling.
  • the coating specimens were heated in air to 1150°C to 1200°C and held for a minimum of six (6) hours followed by air cooling. After five (5) cycles, the specimens were water quenched on the sixth cycle. If no spalling or partial spalling occurred, the coating was described as acceptable. The results are shown below in Table I.
  • Examples 3, 4 and 5 Additional tests as set forth in Examples 3, 4 and 5 were conducted to substantiate the superiority of a detonation gun coating formed from a thermal spray powder feed composition comprising zirconium silicate and partially stabilized zirconia (ZrO2 ⁇ 5CaO) on a hearth roll based on its anti-pickup characteristics compared to detonation gun coatings of a conventional composition of (Co-25Cr-7.5A1-.8Y-10Ta) + 10% A12O3, a coating from a feed composition of ZrSiO4, and bare steel.
  • a thermal spray powder feed composition comprising zirconium silicate and partially stabilized zirconia (ZrO2 ⁇ 5CaO) on a hearth roll based on its anti-pickup characteristics compared to detonation gun coatings of a conventional composition of (Co-25Cr-7.5A1-.8Y-10Ta) + 10% A12O3, a coating from a feed composition of ZrSiO4, and bare steel
  • Anti-Pickup Index is determined by the sum of the anti-pickup points (AP) for faces A, B and C based on the following Table III.
  • the normalized wear rate is calculated by the following procedure.
  • Heat shock Test 1000°C - 15 minute heating from ambient to 1000°C, water quench for 15 minutes - 1 cycle.
  • the sample substrate material had a thick plate shape with a dimension of 50x50x10 mm, one 50x50 side coated.
  • the sample substrate was 304 stainless steel.
  • Thermal shock resistance is evaluated by counting how many cycles the coating can survive without spalling off.
  • the as-deposited coating should preferably have at least about 40 wt% stabilized zirconia and up to 60 wt% zirconium silicate.
  • the preferred concentration of the component oxides in the coating independent of crystalline structure should be between about 55 to about 85 wt% stabilized Zr02 and 15 to 45% ZrSi04 and/or its decomposition products Si02 and Zr02 with 70 to 85 wt% stabilized Zr02 being optimum.
  • the concentration of stabilizer in the as-deposited coating composition should preferably be between 2 to 20 wt% of the zirconia component.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Reduction Rolling/Reduction Stand/Operation Of Reduction Machine (AREA)
  • Rolls And Other Rotary Bodies (AREA)
  • Tunnel Furnaces (AREA)
  • Paints Or Removers (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
EP91309332A 1990-10-11 1991-10-10 Rouleau de fourneau revêtu et procédé pour sa fabrication Expired - Lifetime EP0480727B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59609690A 1990-10-11 1990-10-11
US596096 1990-10-11

Publications (2)

Publication Number Publication Date
EP0480727A1 true EP0480727A1 (fr) 1992-04-15
EP0480727B1 EP0480727B1 (fr) 1995-07-26

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EP91309332A Expired - Lifetime EP0480727B1 (fr) 1990-10-11 1991-10-10 Rouleau de fourneau revêtu et procédé pour sa fabrication

Country Status (8)

Country Link
EP (1) EP0480727B1 (fr)
JP (1) JPH0718405A (fr)
KR (1) KR960008146B1 (fr)
AT (1) ATE125577T1 (fr)
AU (1) AU658833B2 (fr)
CA (1) CA2053188C (fr)
DE (1) DE69111552T2 (fr)
ES (1) ES2075364T3 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0595451A1 (fr) * 1992-10-28 1994-05-04 Praxair S.T. Technology, Inc. Composition en poudre pour former des revêtements d'oxides réfractoires; procédé utilisé pour produire ce revêtement et article ainsi produit
WO1997015720A1 (fr) * 1995-10-23 1997-05-01 Pulp And Paper Research Institute Of Canada Application de revetements de protection thermique a des cylindres secheurs de machine a papier pour eviter le sursechage des bords du papier
WO2000064836A1 (fr) * 1999-04-26 2000-11-02 General Electric Company Ceramique muni d'un revetement a base de zircon
SG150380A1 (en) * 2002-08-21 2009-03-30 United Technologies Corp Thermal barrier coatings with low thermal conductivity
EP2767609A1 (fr) * 2013-02-14 2014-08-20 Praxair S.T. Technology, Inc. Oxydation sélective d'une composition chargée de MCrAIY modifié avec des niveaux élevés de céramique agissant comme une barrière pour des formations d'oxyde spécifiques
CN115584461A (zh) * 2022-08-26 2023-01-10 武汉钢铁有限公司 一种防止炭套辊芯渗碳的方法、隔离涂层及炉底辊
WO2024022653A1 (fr) * 2022-07-29 2024-02-01 Endress+Hauser Flowtec Ag Produit en acier inoxydable revêtu d'émail, procédé de production et débitmètre

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009536984A (ja) * 2006-05-12 2009-10-22 フンダシオン イナスメット セラミックコーティングを得る方法および得られたセラミックコーティング
JP5112361B2 (ja) 2009-02-27 2013-01-09 三菱重工業株式会社 航空機構造体製造装置
CN105483695B (zh) * 2015-12-04 2018-03-30 武汉钢铁重工集团有限公司 一种炉底辊的制作方法
DE102017004944A1 (de) 2017-05-23 2018-11-29 Vdeh-Betriebsforschungsinstitut Gmbh Ofenrolle für einen Wärmebehandlungsprozess eines Werkstücks, Verfahren zum Herstellen derselben, Transporteinrichtung für einen Ofen, Thermoprozessanlage und Verwendung einer Ofenrolle in einer Thermoprozessanlage mit einem Ofen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1536493A (fr) * 1966-07-22 1968-08-16 Montedison Spa Enduits protecteurs de grande résistance et procédé correspondant pour leur application sur des surfaces intérieurs de réacteurs de craquage d'hydrocarbure
FR2186852A5 (en) * 1972-06-02 1974-01-11 Vysoka Skola Chem Tech Plasma-spraying of zircon - from water-stabilised burners eliminating volume changes with temp
EP0230554A1 (fr) * 1985-12-12 1987-08-05 Asea Brown Boveri Aktiengesellschaft Couche de protection aux hautes températures et son procédé de fabrication

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6709949A (fr) * 1966-07-22 1968-01-23
AU603692B2 (en) * 1983-06-20 1990-11-22 Norton Company A powder for the production of sintered stabilized zirconia
JPS60194056A (ja) * 1984-03-14 1985-10-02 Hitachi Ltd セラミツク被覆層を有する耐熱部材

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1536493A (fr) * 1966-07-22 1968-08-16 Montedison Spa Enduits protecteurs de grande résistance et procédé correspondant pour leur application sur des surfaces intérieurs de réacteurs de craquage d'hydrocarbure
FR2186852A5 (en) * 1972-06-02 1974-01-11 Vysoka Skola Chem Tech Plasma-spraying of zircon - from water-stabilised burners eliminating volume changes with temp
EP0230554A1 (fr) * 1985-12-12 1987-08-05 Asea Brown Boveri Aktiengesellschaft Couche de protection aux hautes températures et son procédé de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 7, no. 118 (C-167)(1263) 21 May 1983 & JP-A-58 037 171 ( SUMITOMO DENKI KOGYO K.K. ) 4 March 1983 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0595451A1 (fr) * 1992-10-28 1994-05-04 Praxair S.T. Technology, Inc. Composition en poudre pour former des revêtements d'oxides réfractoires; procédé utilisé pour produire ce revêtement et article ainsi produit
CN1070897C (zh) * 1992-10-28 2001-09-12 普拉塞尔·S·T·技术有限公司 制备耐火氧化物涂层的粉末料组合物、用法和涂覆的物体
WO1997015720A1 (fr) * 1995-10-23 1997-05-01 Pulp And Paper Research Institute Of Canada Application de revetements de protection thermique a des cylindres secheurs de machine a papier pour eviter le sursechage des bords du papier
WO2000064836A1 (fr) * 1999-04-26 2000-11-02 General Electric Company Ceramique muni d'un revetement a base de zircon
US6517960B1 (en) 1999-04-26 2003-02-11 General Electric Company Ceramic with zircon coating
SG150380A1 (en) * 2002-08-21 2009-03-30 United Technologies Corp Thermal barrier coatings with low thermal conductivity
SG150382A1 (en) * 2002-08-21 2009-03-30 United Technologies Corp Thermal barrier coatings with low thermal conductivity
SG151095A1 (en) * 2002-08-21 2009-04-30 United Technologies Corp Thermal barrier coatings with low thermal conductivity
EP2767609A1 (fr) * 2013-02-14 2014-08-20 Praxair S.T. Technology, Inc. Oxydation sélective d'une composition chargée de MCrAIY modifié avec des niveaux élevés de céramique agissant comme une barrière pour des formations d'oxyde spécifiques
WO2024022653A1 (fr) * 2022-07-29 2024-02-01 Endress+Hauser Flowtec Ag Produit en acier inoxydable revêtu d'émail, procédé de production et débitmètre
CN115584461A (zh) * 2022-08-26 2023-01-10 武汉钢铁有限公司 一种防止炭套辊芯渗碳的方法、隔离涂层及炉底辊

Also Published As

Publication number Publication date
JPH0718405A (ja) 1995-01-20
KR960008146B1 (ko) 1996-06-20
DE69111552T2 (de) 1996-02-29
CA2053188A1 (fr) 1992-04-12
ATE125577T1 (de) 1995-08-15
ES2075364T3 (es) 1995-10-01
DE69111552D1 (de) 1995-08-31
EP0480727B1 (fr) 1995-07-26
CA2053188C (fr) 1997-12-16
AU8578491A (en) 1992-04-16
KR920008209A (ko) 1992-05-27
AU658833B2 (en) 1995-05-04

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Inventor name: FUKUBAYASHI, HAROLD HARUHISA

Inventor name: AMANO, MASAHIKO, C2-3-12 NIPPON STEEL OHWADA APT.

Inventor name: NAKAMURA, YUKIHIRO, B2-12 NIPPON STEEL OHWADA APT

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