TW201609538A - 包含可磨塗層之輥 - Google Patents

包含可磨塗層之輥 Download PDF

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TW201609538A
TW201609538A TW104121828A TW104121828A TW201609538A TW 201609538 A TW201609538 A TW 201609538A TW 104121828 A TW104121828 A TW 104121828A TW 104121828 A TW104121828 A TW 104121828A TW 201609538 A TW201609538 A TW 201609538A
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Taiwan
Prior art keywords
roll
particles
coating
weight
composition
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TW104121828A
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English (en)
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TWI663126B (zh
Inventor
珍丹尼斯 尼古拉斯
吉柏特 朗庫爾
克里斯汀 貝里
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維蘇威法國公司
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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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • 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
    • 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
    • B05D3/02—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 by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
    • B21B27/02—Shape or construction of rolls
    • B21B27/03—Sleeved rolls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B39/00—Arrangements for moving, supporting, or positioning work, or controlling its movement, combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B39/008—Rollers for roller conveyors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
    • B65G39/00—Rollers, e.g. drive rollers, or arrangements thereof incorporated in roller-ways or other types of mechanical conveyors 
    • B65G39/02—Adaptations of individual rollers and supports therefor
    • B65G39/07—Other adaptations of sleeves
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/225—Nitrides
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/56—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 carbides or oxycarbides
    • C04B35/565—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 carbides or oxycarbides based on silicon carbide
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    • 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
    • C04B35/584—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 silicon nitride
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    • 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
    • C04B35/597—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 silicon oxynitride, e.g. SIALONS
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    • 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
    • C04B35/62222—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic coatings
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B41/5059—Silicon carbide
    • C—CHEMISTRY; METALLURGY
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    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5062—Borides, Nitrides or Silicides
    • C04B41/5066—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5062—Borides, Nitrides or Silicides
    • C04B41/5067—Silicon oxynitrides, e.g. SIALON
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C13/00—Rolls, drums, discs, or the like; Bearings or mountings therefor
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/14—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment
    • F27B9/20—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace
    • F27B9/24—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace being carried by a conveyor
    • F27B9/2407—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace being carried by a conveyor the conveyor being constituted by rollers (roller hearth furnace)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/02—Skids or tracks for heavy objects
    • F27D3/026—Skids or tracks for heavy objects transport or conveyor rolls for furnaces; roller rails
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
    • C—CHEMISTRY; METALLURGY
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
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Abstract

本申請案係有關應用於輥上之保護性及可磨塗層組成物，且更具體地係有關用於高溫應用之包含可磨塗層之運送機輥、製造此類輥之方法、及其用途。鋁熔體造成之腐蝕係減少，且藉摩擦移除沉積物。輥之壽命從而增加。

Description

包含可磨塗層之輥
本申請案係有關應用於輥上之保護性及可磨塗層組成物，且更具體地係有關用於高溫應用之包含可磨塗層之運送機輥、生產此類塗層之組成物、製造此類輥之方法、及其用途。
經運送之金屬片常以鋁或含鋁之鋅合金處理以抗腐蝕。眾所皆知由包含熔融矽石、富鋁紅柱石、矽線石、礬土、SiC基質、或金屬(如耐火鋼)之材料製成之輥於高溫度下之極佳特性，如其高耐火性(refractoriness)及低熱膨脹性，及其對於熔融金屬之相對惰性。其廣泛用於輥膛爐(roller hearth furnace)。儘管含二氧化矽之輥係較佳，其存在缺點：雖於爐內進行，經塗布之金屬片之鋁開始熔化。部分熔化之鋁與源自陶瓷輥體之SiO2或矽酸鹽反應，導致鋁氧化(Al=>Al2O3)且矽酸鹽還原為金屬形式(主要為Si)，從而由於腐蝕而大幅減少輥之壽命。
已知欲防止腐蝕，輥可以SiAlON或以經燒結之氮化矽或碳化矽塗布。塗層可進一步包含鈦酸鋁粒子。所有該些材料係確實已知對於熔融鋁具非潤濕特性。
即使減少腐蝕，一些沉積現象仍持續。藉使用硬或持久性氮化矽塗層，Si3N4於表面緩慢氧化，致使形成二氧化矽。次要相(如源自氮化矽氧化之二氧化矽)係與鋁反應，產生Al2O3與Si，其聚積於經塗布之輥表面。
揭示於US-A1-2007/089642中的硬塗層包含氮化矽粒子及黏合劑，其含有在有機溶劑中之表面改質之奈米尺度固體粒子。該塗層係描述為硬質，係因氮化物塗層對基材之強黏著性。有機溶劑係用於避免氮化矽粒子之任何水解。此硬塗層通常應用於太陽能坩堝(solar crucible)，亦可應用於鋁冶金之上升管，以防鋁腐蝕。
US-A1-2009160108揭示無塗層之熔融矽石輥，其中表面多孔性(surface porosity)係利用有機溶劑填入氮化矽。此係某種程度上防止表面沉積。由於熔融矽石仍為表面上之主要相，當接觸鋁時，仍觀察到腐蝕。
本發明之目的係提供耐鋁腐蝕之輥，此外其解決沉積問題。輥之表面係經塗布，但與US-A1-2007/0089642相反的是，塗層非硬質。於本發明中，塗層係可磨的，且藉磨耗而與沉積物一起部分移除，產生一乾淨表面，同時維持良好耐鋁腐蝕性。
本發明係有關具至少一層可磨塗層之輥，其包含：a)83-98重量%之聚集體，其包含Si3N4、SiC、或SiAlON粒子或其混合物， b)2-17重量之Al2O3或SiO2、ZrO2、CeO2、Y2O3超微米粒子或其混合物。
超微米粒子之平均粒徑係高於100nm但低於1000nm。
聚集體可進一步包含Al2TiO5粒子。
此類輥係主要用於輥膛爐，其使用之溫度係高於800℃。當金屬或金屬氧化物(如部分氧化之鋁或礬土)之沉積物聚積於輥表面上時，輥塗層之Si3N4粒子傾向於藉由在輥上的經運送之金屬片的摩擦而脫落。Si3N4粒子/Si3N4粒子間之鍵，以及Si3N4粒子/基材間之鍵確實係弱的。於高溫下特定時間後(於用戶之爐中可達數週)，氮化矽粒子與黏合劑粒子間之內聚力增加，且塗層緻密化但維持其可磨性質。儘管如此，沉積物仍剝落，係因經緻密化塗層之部分最終於摩擦作用下剝落。此亦係輥表面上之金屬片之摩擦及輥與緻密化塗層間之界面之黏著性之結果，輥與緻密化塗層間之界面之黏著性比沉積物與緻密化塗層間之界面之黏著性弱。根據超微米粒子之濃度或本質，其與基材之黏著性及內聚力係進一步經改進，且儘管有摩擦力，沉積物未剝落且仍位於輥上。然而，視需求，該些沉積物仍可藉外部作用而機械性剝落。於此情況，輥必須拆除，從而藉施加足夠之摩擦力以清潔沉積物。另一選項係完全移除塗層，且重新施加一新塗層至輥。
術語「可磨」係用以描述於經運送之金屬片之摩擦下或藉施加一外部作用(如研磨步驟)而被磨耗的 塗層。其結果為，塗層表面係自我再生(self-regenerated)，且輥之壽命增加。
塗層任選地包含暫時性黏合劑，如有機黏合劑。有機黏合劑可為丙烯酸系或環氧聚合物、澱粉、聚乙烯醇等。有機黏合劑之優勢為，在暫時性基礎上增加例如輸送及/或安裝輥而不損壞所需之機械性質。一旦輥用於爐中，有機黏合劑由於高溫而消失，留下輥與其可磨塗層。
氮化物粒子之比表面積係小於或等於8m2/g，且較佳地介於0.5與5m2/g之間。若比表面積高於8m2/g，因塗層乾燥期間產生之壓力而觀察到裂縫。舉例而言，實現包含具比表面積10m2/g之粒子之塗層，且裂縫數目極高，其程度使得經塗布之物件不可使用。
使用數種顯示不同比表面積之粒子，允許在組成物施加至基材時藉由優化粉末堆積而適配塗層密度及性質。
本發明進一步提供一輥，其中可磨塗層係由複數個組成物層製成，其包含：a)83-98重量%之Si3N4、SiC、或SiAlON粒子或其混合物之聚集體，b)2-17重量%之Al2O3或SiO2、ZrO2、CeO2、Y2O3超微米粒子或其混合物。
聚集體可進一步包含Al2TiO5粒子。
由於塗層係於摩擦下移除，可根據製造塗層所用之條件訂製輥之使用壽命。
為了使輥可輸送，經塗布之輥係較佳地於至少800℃下加熱至少3小時。
塗層之平均厚度為至少150μm係有利的。
可磨塗層可藉使用下述之組成物製成。本發明之目的亦係用於生產在輥上之可磨塗層之組成物，其包含：a)50-75重量之Si3N4、SiC、或SiAlON粒子或其混合物之聚集體，b)1.5-10重量%，較佳地1.5-5重量%，之Al2O3或SiO2、ZrO2、CeO2、Y2O3超微米粒子或其混合物，c)15-48.5重量%之H2O，其特徵為該Si3N4、SiC、或SiAlON粒子具比表面積(BET)小於或等於8m2/g，且較佳地包含介於0.5與5m2/g之間。
聚集體可進一步包含Al2TiO5粒子，其具比表面積(BET)小於或等於8m2/g，且較佳地介於0.5與5m2/g之間。
基於粉末比表面積之顆粒分佈優化，容許訂製具有高塗層密度之組成物流動性。輥係從而易於塗布。
由於氮化矽粒子係懸浮或溶解於水中，觀察到表面粒子水解。此確實係何以US-A1-2007/0089642主張必須不存在水以取得硬塗層之原因。然而，發明人意外發現，此水解使得顆粒表面對黏合劑產生優化之化學親和力，其明顯減少黏合劑之需求，達到塗層與基材之最小黏著性。
超微米粒子如Al2O3或SiO2之平均粒徑係高於100nm。其常於水性膠體溶液形式下使用。水性膠體溶液係操作上容易且安全。
本發明之另一目的係製造輥之方法，其包含之步驟為：a)提供包含熔融矽石、富鋁紅柱石、矽線石、礬土、SiC基質、或金屬(如耐火鋼)之輥，其具核心及表面；b)對該物件之至少一表面之至少一部分施加以上述之組成物；c)乾燥該輥；d)任選地，於800℃下加熱該輥至少3小時。
塗層係藉噴塗、浸漬、氾流(flooding)、或電漿噴塗該組成物而施加至輥。
上述之輥可優勢地用於輸送以鋁處理之鋼片。
1‧‧‧輥
2‧‧‧撐體
3‧‧‧金屬板
4‧‧‧塗層
5‧‧‧軸
6‧‧‧軸
7‧‧‧螺栓
8a‧‧‧支架
8b‧‧‧支架
(a)‧‧‧軸(6)與板(3)/經塗布之輥的接觸點間之距離
(b)‧‧‧板(3)/經塗布之輥的接觸點與板(3)最靠近撐體(2)之末端間之距離
(c)‧‧‧支架(8a,8b)之尺寸
圖1係描繪測試條件之側視圖。
本發明現將藉本發明之實施例及比較例之方式說明。
可磨性質係藉耐磨耗性測試(wear resistance test)及抗刮性評估。為了操控輥而無損毀，需要最小抗刮性。此外，耐磨耗性不應太低，以確保塗層之最小壽命，且不能太高，以使沉積物藉摩擦移除。發明人注意到，可磨性質係二抗性數值結合之結果。
耐磨耗性係根據下列步驟測定。圖1係描繪測試條件之側視圖。將50mm長度且50mm直徑之熔融矽石輥(1)秤重，之後提供以欲評估之組成物之200μm塗層(4)。一旦塗層(4)經乾燥(60℃下2小時)，再次將經塗布之輥秤重，並測定塗層重量。
輥(1)係安裝於軸(5)上，且水平固定在二個位於垂直安裝於撐體(2)之軸(6)上的20(c)x 60mm支架(8a,8b)之間的金屬板(3)(200 x 100 x 1mm之USIBOR1500鋼片，150g)係經排列以正切接觸經塗布之輥。二軸(5)與(6)係平行。板(3)係藉螺栓(7)固定於支架(8a,8b)之間，以免因輥旋轉而移位。在塗層磨耗時，板於軸(6)上逐漸傾斜。軸(6)與板(3)/經塗布之輥的接觸點間之距離(a)係設定為150mm。板(3)/經塗布之輥的接觸點與板(3)最靠近撐體(2)之末端間之距離(b)係設定為125mm。
輥係以220rpm旋轉。旋轉係週期性中斷，且測定殘留之塗層重量。重複該操作，直到磨損30重量%之塗層為止。
若30重量%之塗層係在小於250分鐘內磨耗，則該塗層標記為(--)。若磨耗30重量%之塗層需要大於500分鐘，則塗層標記為(++)。若30重量%之塗層係在包含於250與500分鐘間之時間內磨耗，則塗層標記為(+-)。
耐磨耗性代表塗層組分間之鍵結強度。
抗刮性代表與基材之黏著強度。其係刮劃經塗布表面所需之負載(以牛頓計)。意外地發現，抗刮性可為相當高，而耐磨耗性低。
於數值1N以下時，黏著強度太弱。當輥係經輸送或操控時，塗層損毀。
當抗刮性高於7N時，塗層視為具強黏著性。然而，塗層仍可磨損。
作為實施例，藉由混合氮化矽粉末與SiO2或Al2O3膠體溶液及水而製造三種組成物(用於產生實施例1至9之組成物1至3)。從而將輥浸漬於組成物溶液中，且隨後於60℃下乾燥2小時。
塗層組成物之實施例係顯示於表1
隨即以三種不同條件評估該等輥(實施例1至9)。
首先(實施例1至3)，輥不受高於乾燥溫度之進一步熱處理。
其次(實施例4至6)，以2重量%之濃度將有機黏合劑加入塗層組成物。輥係浸漬於塗層溶液中，之後乾燥及測試。
再者(實施例7至9)，使用包含有機黏合劑之組成物塗布之輥係於800℃下加熱3小時。
作為比較例(實施例10)，輥係以US-A1-2008-260608揭示之組成物塗布。由於Si3N4粒子之粒度分析(顆粒主要1微米)，塗層係藉噴塗形成。於乾燥步驟後，輥係於1000℃下加熱3小時。組成物如下：
實施例取得下列結果(表2)。
如可由表2觀察，未經燃燒之實施例(1-3)具低耐磨耗及抗刮性。該些經塗布者係耐鋁腐蝕，但輥無法輸送。
將有機黏合劑添加至組成物會增加所有組成物之抗刮性及耐磨耗性(實施例4至6)。
當輥於800℃下加熱至少3小時(實施例7至9)，有機黏合劑消失而不損毀氮化矽層。相較於未經加熱之輥，耐磨耗性係輕微改進。由於弱磨耗性(--)，當受到摩擦時，沉積物將傾向連同氮化矽粒子脫落。增加耐磨耗性(+/-)及抗刮性，沉積物將傾向連同隔離之氮化矽粒子脫落，但亦與其形成一部分塗層。較高之抗刮性值可導致更黏之沉積物，從而需要進一步之強度以將其移除。
高抗刮性容許替換輥時毋須降低爐溫度，其在保養或替換輥時可能需要。
儘管加熱，比較樣本之耐磨耗性與抗刮性數值皆低(實施例10)。此塗層之特性係完全不同。其原因為，氮化物粒子之粒徑低於1μm。儘管塗層於1000℃下加熱， 具此塗層之輥無法用於此工業應用，係因低耐磨耗性導致高度可磨的塗層。於短時間後，輥表面上不留塗層，誘導沉積物出現及輥體腐蝕。

Claims (14)

  1. 一種輥，其有具至少一層於800℃下3小時後可磨之塗層，該輥包含：a)83-98重量%之聚集體，其包含Si3N4、SiC、或SiAlON粒子或其混合物，b)2-17重量%之Al2O3、SiO2、ZrO2、CeO2、Y2O3超微米粒子或其混合物。
  2. 如請求項1之輥，其中該聚集體更包含Al2TiO5粒子。
  3. 如前述請求項中任一項之輥，其中該聚集體粒子之比表面積(specific surface area；BET)係小於或等於8m2/g，且較佳地介於0.5與5m2/g之間。
  4. 如前述請求項中任一項之輥，其中該粒子之聚集體包含具不同比表面積之粒子。
  5. 如前述請求項中任一項之輥，其中該塗層係由複數個如請求項1所述之層製成。
  6. 如前述請求項中任一項之輥，其中該塗層之平均厚度係至少150μm。
  7. 如前述請求項中任一項之輥，其中該輥係由熔融矽石、富鋁紅柱石、矽線石、礬土、SiC基質、或金屬製成，該金屬如耐火鋼。
  8. 如前述請求項中任一項之輥，其中該塗層包含暫時性黏合劑，如丙烯酸系或環氧聚合物或聚乙烯醇。
  9. 一種組成物，其包含：a)50-75重量%之Si3N4、SiC、或SiAlON粒子或其混合物之聚集體， b)1.5-10重量%，較佳地1.5-5重量%之Al2O3或SiO2、ZrO2、CeO2、Y2O3超微米粒子或其混合物，c)15-48.5重量%之H2O，其特徵為該Si3N4、SiC、或SiAlON粒子具比表面積(BET)小於或等於8m2/g，且較佳地包含介於0.5與5m2/g之間。
  10. 如請求項9之組成物，其中該聚集體進一步包含Al2TiO5粒子，其具比表面積(BET)小於或等於8m2/g，且較佳地包含介於0.5與5m2/g之間。
  11. 一種製造如請求項1至8中任一項之輥之方法，其包含之步驟為：a)提供由熔融矽石、富鋁紅柱石、矽線石、礬土、SiC基質、或金屬製成之輥，其具核心及表面，該金屬如耐火鋼；b)將請求項9之組成物施加於該輥之表面之至少一部分；c)乾燥該輥。
  12. 如請求項11之方法，其中該組成物係藉噴塗、浸漬、氾流(flooding)、或電漿噴塗而塗布。
  13. 如請求項11之方法，其更包含於溫度至少800℃下加熱該輥至少3小時之步驟。
  14. 如請求項1至8中任一項之輥之用途，用於輸送以鋁處理之鋼片。
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