WO2016063561A1 - Substrat métallique revêtu - Google Patents

Substrat métallique revêtu Download PDF

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Publication number
WO2016063561A1
WO2016063561A1 PCT/JP2015/064472 JP2015064472W WO2016063561A1 WO 2016063561 A1 WO2016063561 A1 WO 2016063561A1 JP 2015064472 W JP2015064472 W JP 2015064472W WO 2016063561 A1 WO2016063561 A1 WO 2016063561A1
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Prior art keywords
coat layer
ceramic coat
ceramic
coated metal
pores
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PCT/JP2015/064472
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English (en)
Japanese (ja)
Inventor
友好 中村
孝則 河合
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イビデン株式会社
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Priority to JP2016555097A priority Critical patent/JP6581593B2/ja
Publication of WO2016063561A1 publication Critical patent/WO2016063561A1/fr

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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
    • B05D3/02—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
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing

Definitions

  • the present invention relates to a coated metal substrate.
  • Patent Document 1 Conventionally, as a method for achieving heat insulation of an aluminum member, an attempt has been made to form a heat insulating film on a substrate surface (for example, Patent Document 1).
  • JP 2012-072745 A International Publication No. 2012/093697 JP 2014-092035 A
  • Patent Document 1 a porous layer is formed by anodization on the surface of an aluminum alloy base material, and a coating layer containing ZrO 2 or the like having a lower thermal conductivity than the base material is provided on the porous layer.
  • An insulation structure for aluminum products is disclosed.
  • the coating layer described in Patent Document 1 is a thermal spray coating, the coating strength and the adhesion to the substrate are not sufficient, and there is a problem that the coating cracks or peels off.
  • Patent Document 1 discloses that irregularities are also formed on the surface of the coating layer, reflecting the irregularities on the surface of the porous layer. When gas flows through the surface of the coating layer with irregularities, there is a problem that the gas flow is disturbed by the irregularities of the coating layer, and the heat insulation coefficient decreases due to an increase in heat transfer coefficient due to an increase in fluid resistance. there were.
  • Patent Document 2 discloses an exhaust pipe including a surface coating layer in which pores are unevenly distributed in the center portion in the thickness direction of the surface coating layer. According to Patent Document 2, if the pores are unevenly distributed in the central portion in the thickness direction of the surface coating layer, cracks generated in the vicinity of the surface are inhibited from progressing by the pores, and the surface coating layer may be completely destroyed. It is described that it can be prevented. However, in this method, since pores that can improve heat insulation exist only in the center portion of the surface coating layer, the heat insulation performance is applied in places where high heat insulation performance is required, such as engine members. There was a problem that was insufficient.
  • Patent Document 3 discloses an engine in which a heat insulation layer including a silicone resin, magnetic powder, a Si oxide obtained by oxidizing a part of the silicone resin, and hollow particles made of a nonmagnetic material is formed.
  • a heat insulating structure for a combustion chamber member is disclosed.
  • the inventors conducted extensive research to solve the above problems, and as a result, uniformly dispersed pores were formed in the ceramic coat layer, and the surface roughness (Ra) of the ceramic coat layer was suppressed to 8 ⁇ m or less. It has been found that heat insulation can be improved by constituting so that is directly surrounded by the ceramic coat layer, and the present invention has been conceived.
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a coated metal substrate on which a ceramic coat layer having excellent heat insulation properties is formed.
  • the coated metal substrate of the present invention is a coated metal substrate in which a ceramic coat layer made of a ceramic raw material is formed on a substrate made of metal, and the inside of the ceramic coat layer Are characterized in that uniformly dispersed pores are formed, the surface roughness (Ra) of the ceramic coat layer is 8 ⁇ m or less, and the pores are directly surrounded by the ceramic coat layer.
  • the coated metal substrate of the present invention pores that are uniformly dispersed are formed in the ceramic coating layer. Therefore, it becomes a ceramic coat layer excellent in heat insulation. Furthermore, since the surface of the ceramic coat layer has a surface roughness (Ra) of 8 ⁇ m or less, the flow of gas flowing on the surface of the ceramic coat layer is hardly disturbed, and the apparent thermal conductivity can be lowered. In addition, since the pores are directly surrounded by the ceramic coat layer, in other words, there is no shell layer made of hollow particles, so that the generation of cracks originating from the shell layer can be suppressed.
  • surface roughness (Ra) is arithmetic mean roughness based on JISB0601 (2001), for example, can be measured with a surface roughness measuring machine etc.
  • the cross section of the ceramic coat layer is observed with a scanning electron microscope (hereinafter also referred to as SEM), the state of the pores in the cross section is photographed, and the number of pores having a pore diameter exceeding 0.1 ⁇ m is determined by the following procedure. Count.
  • the imaging magnification is changed as follows for each thickness (also referred to as film thickness) of the ceramic coat layer.
  • the SEM image is taken at five arbitrary locations of the ceramic coat layer which is a target for confirming the dispersion of pores. At this time, photographing is performed so that the entire area of the ceramic coat layer in the thickness direction is included in the SEM image. Subsequently, the photographed SEM image is divided into nine regions of 3 ⁇ 3 in the vertical direction, and the number of pores having a pore diameter of 0.1 ⁇ m or more present in each region is counted.
  • the coated metal substrate of the present invention is 2000 times, 50 ⁇ m or more and less than 100 ⁇ m when the thickness of the ceramic coat layer is 5 ⁇ m or more and less than 50 ⁇ m so that the entire region in the thickness direction of the ceramic coat layer is accommodated.
  • the rectangular areas are randomly selected as 5 rectangular areas, and the rectangular areas are further divided into 9 areas each of 3 ⁇ 3 In case of a split to the total of 45 regions, in all areas of the 45, it can be said that the pore diameter or more pores 0.1 ⁇ m is present more than 10 pieces.
  • the metal is preferably aluminum or an aluminum alloy.
  • the metal is aluminum or an aluminum alloy, it is lightweight, so that it is possible to reduce the weight of the engine and improve the fuel consumption rate.
  • Aluminum or an aluminum alloy can form an alumite layer by subjecting its surface to an alumite treatment or the like.
  • an alumite layer is formed on the surface of a substrate made of aluminum or an aluminum alloy, and the ceramic coat layer is formed on the substrate on which the anodized layer is formed. It is preferable. Since the alumite layer formed on the surface of the base material made of aluminum or an aluminum alloy is obtained by altering a part of the base material, the base material and the alumite layer are integrated. And since an alumite layer has many unevenness
  • the alumite layer is composed of an oxide, it can be chemically bonded to the atoms constituting the ceramic coat layer via oxygen, and the adhesive force between the substrate and the ceramic coat layer is increased. Therefore, the adhesiveness between the substrate and the ceramic coat layer can be improved.
  • the ceramic coating material softened in the firing process spreads over the surface of the metal base material and enters the surface unevenness, thereby canceling the unevenness on the surface of the base material. Therefore, even when unevenness is formed on the surface of the metal substrate, the uneven shape is not reflected on the surface shape of the ceramic coat layer, and the unevenness is not formed on the surface of the ceramic coat layer. Therefore, the surface roughness of the surface of the ceramic coat layer can be reduced while maintaining the adhesive force of the ceramic coat layer.
  • the softening point of the ceramic raw material is preferably 250 to 550 ° C. If the softening point of the ceramic raw material is less than 250 ° C., the softening point is too low, so that the ceramic raw material is difficult to melt during firing, and it may be difficult to form a film having a uniform thickness. On the other hand, if the softening point of the ceramic raw material exceeds 550 ° C., the thermal decomposition of the surfactant may end before the ceramic raw material constituting the ceramic coating raw material softens. In such a case, the decomposition gas generated by the thermal decomposition of the surfactant diffuses into the firing atmosphere and cannot form pores.
  • the ceramic coat layer further contains a crystalline inorganic material.
  • a crystalline inorganic material By including a crystalline inorganic material in the ceramic coat layer, the mechanical strength, heat resistance, adhesiveness, heat insulation and the like of the ceramic coat layer can be improved.
  • the crystalline inorganic material is composed of at least one selected from the group consisting of alumina, zirconia, titania, lanthania, samaria, silica, yttria, calcia, magnesia, ceria, and hafnia. It is preferable. Since these crystalline inorganic materials are excellent in heat resistance, the heat resistance of the ceramic coat layer containing the crystalline inorganic material can be improved.
  • the thickness of the ceramic coat layer is preferably 10 to 1000 ⁇ m.
  • the thickness of the ceramic coat layer is less than 10 ⁇ m, the thickness of the ceramic coat layer is too thin, so that the coated metal substrate cannot exhibit sufficient heat insulation.
  • the thickness of the ceramic coat layer exceeds 1000 ⁇ m, cracks may easily occur when a thermal shock or the like is applied to the ceramic coat layer.
  • FIG. 1A is a cross-sectional view schematically showing a cross section of a coated metal substrate of the present invention
  • FIG. 1B is a partially enlarged cross-sectional view of a region indicated by a rectangle A in FIG. is there.
  • FIG. 2A schematically shows a procedure for confirming whether pores in the ceramic coat layer are uniformly dispersed
  • FIG. 2B shows a method of dividing an SEM image into nine regions. It is explanatory drawing which showed typically.
  • FIG. 3 is an SEM image obtained by photographing a cross section of the coated metal substrate according to Example 1.
  • the coated metal substrate of the present invention is a coated metal substrate in which a ceramic coat layer made of a ceramic raw material is formed on a substrate made of metal, and the pores dispersed uniformly in the ceramic coat layer
  • the surface roughness (Ra) of the ceramic coat layer is 8 ⁇ m or less, and the pores are directly surrounded by the ceramic coat layer.
  • FIG. 1A is a cross-sectional view schematically showing a cross section of a coated metal substrate of the present invention
  • FIG. 1B is a partially enlarged cross-sectional view of a region indicated by a rectangle A in FIG. is there.
  • a ceramic coat layer 12 is formed on a base material 11 made of metal. Inside the ceramic coat layer 12 are uniformly dispersed pores 13. As shown in FIG. 1 (b), the pores 13 are directly surrounded by the ceramic coat layer 12.
  • the surface roughness (Ra) is 8 ⁇ m or less.
  • the surface roughness (Ra) in this specification is a value measured based on JIS B 0601 (2001).
  • FIG. 2A schematically shows a procedure for confirming whether pores in the ceramic coat layer are uniformly dispersed
  • FIG. 2B shows a method of dividing an SEM image into nine regions. It is explanatory drawing which showed typically.
  • the cross section of the ceramic coat layer for which the pore dispersion is to be confirmed is photographed by SEM.
  • an area indicated by a rectangle B shown in FIG. 2A is an area for capturing an SEM image. As shown in FIG.
  • a magnification in which the entire region of the ceramic coat layer 12 in the thickness direction of the ceramic coat layer 12 falls within the SEM image is selected.
  • the magnification of SEM varies depending on the thickness (film thickness) of the ceramic coating layer.
  • the thickness of the ceramic coating layer is 5 ⁇ m or more and less than 50 ⁇ m, it is 2000 times, when it is 50 ⁇ m or more and less than 100 ⁇ m, it is 1000 times, or 100 ⁇ m or more but less than 300 ⁇ m. Is 500 times, 200 times when 300 ⁇ m or more and less than 500 ⁇ m, 150 times when 500 ⁇ m or more and less than 1000 ⁇ m, and 100 times when 1000 ⁇ m or more and less than 2000 ⁇ m.
  • FIG. 2A is one of SEM images (one of five) taken at random.
  • the photographed SEM image is divided into 9 blocks of 3 ⁇ 3 as shown in FIG.
  • the double-headed arrow c is divided so that the longitudinal direction (the direction indicated by the double-headed arrow c in FIG. 2B) is divided into three equal parts. It is partitioned by double arrows c 1 , c 2 and c 3 which are divided into three equal parts.
  • the length b in the horizontal direction (direction indicated by a double-headed arrow b in FIG. 2B) which is a direction perpendicular to the vertical direction is 1.5 times the thickness c of the ceramic coat layer
  • the double arrows b 1 , b 2, and b 3 that divide this into three are all 1.5 times longer than c 1 , c 2 , and c 3 . That is, the SEM image has a rectangular shape defined by (thickness of the ceramic coat layer) ⁇ (1.5 times the thickness of the ceramic coat layer) in the thickness direction (vertical direction) and the length direction ( It is divided into nine regions by dividing each of them in the horizontal direction.
  • the number of pores having a pore diameter of 0.1 ⁇ m or more present in each of the nine regions is counted. If the number of pores having a pore diameter of 0.1 ⁇ m or more is 10 or more in all 45 regions of 9 regions ⁇ 5 places, it is determined that the pores are uniformly dispersed in the ceramic coat layer.
  • the coated metal substrate of the present invention is 2000 times larger when the thickness of the ceramic coating layer is 5 ⁇ m or more and less than 50 ⁇ m so that the entire region in the thickness direction of the ceramic coating layer is accommodated, and 50 ⁇ m or more and less than 100 ⁇ m.
  • the coated metal substrate of the present invention has excellent heat insulating performance because there are uniformly dispersed pores.
  • the ceramic coating layer constituting the coated metal substrate of the present invention has pores, but the pores are directly surrounded by the ceramic coating layer.
  • Examples of the case where the pores are not directly surrounded by the ceramic coat layer include a case where the pores are formed of a structure different from the ceramic coat layer, for example, hollow particles. In such a case, the pores are surrounded by the ceramic coat layer via the hollow particles (also referred to as a shell layer).
  • the ceramic coat layer and the shell layer are different materials, cracks may occur in the ceramic coat layer due to the difference in thermal expansion coefficient.
  • the ceramic coat layer constituting the coated metal substrate of the present invention since the pores are directly surrounded by the ceramic coat layer and there is no shell layer, the above problem does not occur.
  • the thermal conductivity at room temperature of the ceramic coating layer constituting the coated metal substrate of the present invention is preferably 0.1 to 3 W / m ⁇ K. If the thermal conductivity is less than 0.1 W / m ⁇ K, the porosity required to achieve the above thermal conductivity is increased, so that the mechanical strength of the formed ceramic coat layer may be excessively lowered. is there. On the other hand, if the thermal conductivity exceeds 3 W / m ⁇ K, there is a problem that a sufficient heat insulating effect cannot be obtained. In order to obtain a desired heat insulation effect, it is necessary to increase the thickness of the ceramic coat layer. Therefore, when applying the coated metal substrate of the present invention to an engine member or the like, it is difficult to secure a space in the design. There is a problem. The thermal conductivity is measured based on JIS R 1611 (2010) using a laser flash device (thermal constant measuring device: NETZSCH LFA457 Microflash).
  • the average pore diameter of the pores formed in the ceramic coat layer is not particularly limited, but is preferably 0.1 to 80 ⁇ m, preferably 0.5 to 50 ⁇ m, and 1 to 50 ⁇ m. Is more preferable. When the average pore diameter is less than 0.1 ⁇ m, the heat insulating effect obtained by the pores is small, and a sufficient heat insulating effect may not be obtained. On the other hand, when the average pore diameter exceeds 80 ⁇ m, the pore size is too large, and the mechanical strength of the ceramic coat layer may be lowered.
  • the average pore diameter of the pores can be obtained using an image similar to the SEM image used for determining whether or not the pores described above are uniformly dispersed.
  • the average pore diameter can be obtained by measuring the pore diameter of all the pores present in the nine divided areas and obtaining the average value.
  • the diameter of the pores is the diameter corresponding to the projected area circle (Haywood diameter).
  • the porosity of the ceramic coat layer constituting the coated metal substrate of the present invention is preferably 5 to 75%, more preferably 10 to 60%, and even more preferably 20 to 45%.
  • the porosity of the ceramic coat layer is less than 5%, the heat insulating performance of the ceramic coat layer may not be sufficient.
  • the porosity of the ceramic coat layer exceeds 75%, the porosity is too high, the mechanical strength of the ceramic coat layer is lowered, and cracks are likely to occur.
  • the porosity of the ceramic coat layer can be obtained using an image similar to the SEM image used for determining whether or not the above-described pores are uniformly dispersed. Specifically, the total value of the area occupied by all the pores existing in the nine divided areas is obtained and divided by the total area of the nine areas, and this value is measured at five locations. The average value of the five locations is taken as the porosity of the ceramic coat layer.
  • the surface of the ceramic coat layer (the surface not in contact with the substrate) has a surface roughness (Ra) of 8 ⁇ m or less, preferably 4 ⁇ m or less, and more preferably 2 ⁇ m or less.
  • the lower limit of the surface roughness (Ra) is not particularly limited, but is preferably 1 ⁇ m from the viewpoint of product yield.
  • each member which comprises the coated metal base material of this invention is demonstrated one by one.
  • the base material constituting the coated metal base material of the present invention will be described.
  • the base material made of metal include stainless steel, heat resistant steel (SUH), aluminum, aluminum alloy, iron, inconel, hastelloy, and invar.
  • various cast products for example, cast iron, cast steel, carbon steel, etc.
  • the heat resistant steel (SUH) include martensitic heat resistant steel (SUH3, SUH11, etc.), austenitic heat resistant steel (SUH35, etc.), ferritic heat resistant steel (SUH446, etc.) and the like.
  • Ni-based heat-resistant alloys such as Inconel (NCF751 etc.) are also included.
  • Aluminum alloys include pure aluminum (1000s), Al-Cu alloys (2000s), Al-Mn alloys (3000s), Al-Si alloys (4000s), Al-Mg alloys ( 5000 series), Al-Mg-Si based alloys (6000 series), Al-Zn-Mg based alloys (7000 series), and the like.
  • the composition of the alloy is not particularly limited.
  • the shape of the substrate is not particularly limited, and for example, the shape can be arbitrarily set according to the shape of a member used as a gas flow member, etc., but at least in the portion where the gas flows, A ceramic coat layer is preferably formed.
  • the gas distribution member include engine members such as an intake port, an exhaust port, an engine valve, and a piston.
  • the substrate may be a plate-like body such as a flat plate, a curved plate, a bent plate, or a cone such as an umbrella type or a mushroom type.
  • the surface of the substrate is preferably subjected to a roughening treatment. This is because the surface area is increased by the roughening treatment, and the adhesion between the substrate and the ceramic coat layer is increased.
  • the surface roughness (Ra) of the roughened substrate is preferably 0.05 to 10 ⁇ m. When the surface roughness (Ra) is less than 0.05 ⁇ m, an increase in the surface area of the substrate does not contribute much to an increase in adhesion. On the other hand, when the surface roughness (Ra) exceeds 10 ⁇ m, air is likely to intervene between the ceramic coat layer formed on the substrate surface and the substrate surface, and the adhesion with the ceramic coat layer is reduced. .
  • the method for forming the alumite layer on the base material is not particularly limited, and a conventionally known method can be used.
  • the base material is used as an anode and an electric current is supplied in an electrolytic bath.
  • a method of forming an alumite layer by [alumite treatment (also referred to as anodizing treatment)] can be applied.
  • alumite treatment also referred to as anodizing treatment
  • the thickness of the alumite layer is preferably 0.2 to 100 ⁇ m. If the thickness of the alumite layer is less than 0.2 ⁇ m, the thickness of the alumite layer is too thin, and the effect of improving the adhesion with the ceramic coat layer may be hardly obtained. On the other hand, if the thickness of the alumite layer exceeds 100 ⁇ m, it takes too much time to form the alumite layer, which is uneconomical.
  • the thickness of the alumite layer is more preferably 10 to 50 ⁇ m. In addition, the thickness of an alumite layer can be measured by observing the cross section of a coat metal base material using SEM etc.
  • An alumite layer is a layer of a composite oxide of aluminum oxide or aluminum oxide and another metal oxide formed by oxidation of a metal substrate made of aluminum or an aluminum alloy.
  • the base material and the alumite layer are in close contact with each other because they are chemically bonded via oxygen.
  • the ceramic coat layer is made of a ceramic raw material, and examples of the ceramic raw material include amorphous inorganic materials.
  • the amorphous inorganic material is preferably made of glass, and more preferably made of low softening point glass having a softening point of 250 to 550 ° C.
  • Examples of the low softening point glass having a softening point of 250 to 550 ° C. include SiO 2 —TiO 2 glass, SiO 2 —PbO glass, SiO 2 —PbO—B 2 O 3 glass, and B 2 O 3 —PbO glass.
  • the softening point is measured using, for example, a glass automatic softening point / strain point measuring device (SSPM-31) manufactured by Opt Corporation, based on the method specified in JIS R 3103-1 (2001). be able to.
  • SSPM-31 glass automatic softening point / strain point measuring device
  • the ceramic coat layer may further contain a crystalline inorganic material in addition to the ceramic raw material described above.
  • the crystalline inorganic material is preferably made of at least one selected from the group consisting of alumina, zirconia, titania, lanthania, samaria, silica, yttria, calcia, magnesia, ceria, and hafnia.
  • the thickness of the ceramic coat layer is preferably 10 to 1000 ⁇ m, more preferably 10 to 600 ⁇ m, and even more preferably 10 to 200 ⁇ m. If the thickness of the ceramic coat layer is less than 10 ⁇ m, the thickness of the ceramic coat layer is too thin, so that the coated metal substrate cannot exhibit sufficient heat insulation. On the other hand, if the thickness of the ceramic coat layer exceeds 1000 ⁇ m, cracks may easily occur when a thermal shock or the like is applied to the ceramic coat layer.
  • the coated metal substrate of the present invention includes, for example, a substrate preparation step for preparing a substrate made of metal, and a ceramic coat layer formed by applying a ceramic coat material made of a ceramic material and a surfactant on the substrate. It can be produced by a coating layer forming step for forming a coating layer for forming and a firing step in which the substrate on which the coating layer is formed is fired at a predetermined temperature to form a ceramic coat layer.
  • Substrate preparation step In the substrate preparation step, a substrate made of metal is prepared.
  • the base material preparation step it is preferable to perform a cleaning process to remove impurities on the surface of the base material.
  • the cleaning treatment is not particularly limited, and a conventionally known cleaning treatment method can be used. Specifically, for example, a method of performing ultrasonic cleaning in an alcohol solvent can be used.
  • a roughening treatment may be applied to the portion where the ceramic coat layer is formed.
  • the roughening treatment include sand blast treatment, etching treatment, high temperature oxidation treatment, and alkali treatment. These may be used alone or in combination of two or more. You may perform a washing process after this roughening process. In addition, it is preferable to perform a roughening process ahead of the coating layer formation process mentioned later.
  • the substrate surface is preferably subjected to an alumite treatment.
  • an alumite layer can be formed on the surface of the substrate, and the adhesion between the substrate and the ceramic coat layer can be further improved.
  • alumite treatment is performed on a part of the substrate, it is preferable to protect it by attaching a masking tape or the like to a portion where the alumite treatment is not performed.
  • an alkaline bath or a non-aqueous bath such as formamide and boric acid can be used in addition to the acidic bath.
  • Acid baths include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfosalicylic acid, pyrophosphoric acid, sulfamic acid, phosphomolybdic acid, boric acid, malonic acid, succinic acid, maleic acid, citric acid, tartaric acid, phthalic acid, itacone
  • An aqueous solution in which one or two or more acids, malic acid, glycolic acid and the like are dissolved can be used.
  • dissolved 1 type, or 2 or more types of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium phosphate, ammonia water etc. can be used as an alkaline bath.
  • an alumite treatment an alumite layer having a thickness of 0.2 to 100 ⁇ m is formed on the surface of the substrate.
  • a ceramic coating material is obtained by mixing the ceramic material and the surfactant.
  • the surfactant that is mixed with the ceramic raw material to constitute the ceramic coating raw material may be a liquid or a solid.
  • the ceramic raw material is the same as that described in the description of the coated metal substrate of the present invention, the description thereof is omitted here.
  • the ceramic coating raw material can be obtained, for example, by mixing a ceramic raw material, a surfactant, and water and wet-mixing with a ball mill or the like.
  • the order and combination of mixing the three components are not particularly limited.
  • the ceramic raw material and water may be mixed first, and a surfactant may be further added. May be added, or the ceramic raw material, surfactant and water may be mixed at once.
  • the surfactant is a general term for substances having a hydrophilic group and a hydrophobic group in the molecule, and the kind thereof is not particularly limited, and may be a liquid or a solid.
  • the surfactant contained in the ceramic coat raw material undergoes thermal decomposition in the subsequent firing step to form pores. That is, the surfactant functions as a pore forming agent.
  • the mixing ratio of the ceramic raw material and water is not particularly limited, but about 100 parts by weight of water is preferable with respect to 100 parts by weight of the ceramic raw material. This is because when the ceramic raw material and water are mixed in such a weight ratio, a viscosity suitable for application to a metal substrate is likely to be obtained. Moreover, you may mix
  • the dispersion medium for example, water or an organic solvent such as methanol, ethanol, or acetone can be used.
  • the content of the dispersion medium in the ceramic coating raw material is not particularly limited.
  • the dispersion medium is preferably 50 to 150 parts by weight with respect to 100 parts by weight of the ceramic raw material. This is because, by blending the dispersion medium in such a ratio, the viscosity of the ceramic coat raw material becomes a viscosity suitable for application to the substrate.
  • the organic binder include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and the like. These may be used alone or in combination of two or more. Further, a dispersion medium and an organic binder may be used in combination.
  • the content of the surfactant in the ceramic coating raw material is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight in terms of solid content, based on the total amount of the ceramic coating raw material. Preferably, it is 0.5 to 3% by weight.
  • the content of the surfactant is less than 0.1% by weight, a sufficient amount of pores may not be formed in the ceramic coat layer.
  • the content of the surfactant exceeds 10% by weight, the amount of the surfactant to be added is too large, and a large amount of pores may be formed and connected to each other. Such pores do not become pores uniformly dispersed in the ceramic coat layer, and there is a possibility that the heat insulation performance and the mechanical strength are lowered.
  • the surfactant is preferably a water-soluble surfactant.
  • the surfactant is water-soluble, it is excellent in self-dispersibility in the softened ceramic raw material, and it becomes easy to form uniform pores. Therefore, a ceramic coat layer having high heat insulation performance can be obtained.
  • the type of the surfactant is not particularly limited, and any anionic, cationic or nonionic surfactant may be used, but self-dispersibility and formation of uniform pores in the ceramic raw material. From the viewpoint, it is more preferable to use an anionic surfactant.
  • anionic surfactant examples include polycarboxylic acid and / or salt thereof, naphthalene sulfonate formalin condensate and / or salt thereof, polyacrylic acid and / or salt thereof, polymethacrylic acid and / or salt thereof, polyvinyl Examples thereof include sulfonic acid and / or a salt thereof.
  • the water-soluble surfactant is one having an HLB value of 8.0 or more in the Griffin method.
  • the thermal decomposition temperature of the surfactant is preferably 200 to 600 ° C. When the thermal decomposition temperature of the surfactant is within the above range, pores uniformly dispersed in the ceramic coat layer are easily formed. If the thermal decomposition temperature is lower than 200 ° C., the thermal decomposition of the surfactant may be completed before the ceramic raw material constituting the ceramic coating raw material is softened in the initial stage of the firing process. In such a case, the decomposition gas generated by the thermal decomposition of the surfactant diffuses into the firing atmosphere and cannot form pores. On the other hand, it is technically difficult to set the thermal decomposition temperature to a value exceeding 600 ° C.
  • the thermal decomposition temperature of the surfactant is a temperature at which the weight of the surfactant is decreased by 5% by weight as measured by thermogravimetric analysis (TGA).
  • a crystalline inorganic material may be further added to the ceramic coat raw material.
  • the timing of adding the crystalline inorganic material is not particularly limited. For example, before mixing the ceramic raw material, the surfactant, and water, the ceramic raw material and the crystalline material are mixed. You may have the process of mixing an inorganic material. Since the crystalline inorganic material is the same as that described in the description of the coated metal substrate of the present invention, the description thereof is omitted here.
  • adding a crystalline inorganic material further as a ceramic coat raw material you may have the process of mixing a ceramic raw material and a crystalline inorganic material, before mixing a ceramic raw material, surfactant, and water mentioned above. .
  • a coating layer for forming a ceramic coating layer is formed by coating a ceramic coating material for forming a ceramic coating layer on a substrate.
  • the thickness of the coating layer is not particularly limited, but is preferably 10 to 1000 ⁇ m, and is preferably thick enough to form a ceramic coat layer having a thickness of 10 to 200 ⁇ m.
  • the thickness of the coating layer is less than 10 ⁇ m, the thickness of the formed ceramic coating layer is too thin, and the coated metal substrate may not be able to exhibit sufficient heat insulation.
  • the thickness of the coating layer exceeds 1000 ⁇ m, the thickness of the formed ceramic coat layer becomes too thick, and cracks may easily occur when a thermal shock is applied to the ceramic coat layer.
  • Examples of the method for forming the coating layer on the substrate include spray coating, electrostatic coating, inkjet, transfer using a stamp or roller, brush coating, and the like.
  • (C) Firing step the substrate on which the coating layer is formed is fired at 300 to 600 ° C. to form a ceramic coat layer on the surface of the substrate.
  • the firing temperature is preferably equal to or higher than the softening point of the amorphous inorganic material.
  • the applied amorphous inorganic material is softened and melted, and the formed ceramic coat layer and the substrate are firmly adhered.
  • the surfactant contained in the ceramic coat raw material is dispersed in the softened ceramic raw material, and pores are formed by causing thermal decomposition.
  • the surfactant Since the surfactant has self-dispersibility, it can be widely dispersed in the softened ceramic raw material to form uniformly dispersed pores in the ceramic coat layer. Furthermore, since the pores formed by the decomposition of the surfactant are directly surrounded by the ceramic coat layer, the generation of foreign matters can be suppressed, and the deterioration of heat insulation performance and the generation of cracks can be suppressed. Further, when pores are exposed on the surface of the ceramic coat layer during firing, the ceramic raw material forming the ceramic coat layer is softened, so that the exposed portions of the pores can be closed quickly. Therefore, pores are not exposed on the surface of the fired ceramic coat layer, and a ceramic coat layer with high flatness (low surface roughness) can be obtained.
  • the ceramic coat layer and the alumite layer are in close contact with each other, and the ceramic coat layer penetrates into the irregularities such as cracks formed in the alumite layer, It adheres more firmly to the base material and alumite layer.
  • the coated metal substrate of the present invention The effects of the coated metal substrate of the present invention are listed below. (1) In the coated metal substrate of the present invention, pores are uniformly dispersed in the ceramic coat layer formed on the substrate. Therefore, it is excellent in heat insulation performance and thermal shock resistance.
  • Example 1 Substrate preparation step A plate (150 mm ⁇ 70 mm ⁇ 0.5 mmt) made of aluminum (A1050) is prepared as a substrate, and ultrasonic cleaning is performed in an alcohol solvent, followed by sand blasting. The surface (both sides) of the material was roughened. The sand blasting process was performed for 60 minutes using Al 2 O 3 abrasive grains. Thereby, the surface roughness (Ra) measured based on JIS B 0601 (2001) on the surface of the substrate was 1.0 ⁇ m.
  • (B) Coating layer forming step (b-1) Ceramic coat raw material preparing step SiO 2 —TiO 2 glass (softening point 400 ° C.) was prepared as a powder of an amorphous inorganic material. Methylcellulose was prepared as an organic binder. A polycarboxylic acid type surfactant was prepared as the surfactant. In the preparation of the raw material mixture, 2 parts by weight of a surfactant is added to 100 parts by weight of the amorphous inorganic material powder, 100 parts by weight of water is further added, and a slurry is prepared by wet mixing with a ball mill. The raw material was obtained.
  • (B-2) Coating process A ceramic coating material was coated on the surface of a flat substrate by spray coating. The coating time was adjusted so that the fired ceramic coating layer had a thickness of 330 ⁇ m, and the coating was dried in a dryer at 100 ° C. for 60 minutes.
  • (C) Firing Step After the above step, a ceramic coat layer was formed by heating in a heating furnace at 520 ° C. for 10 minutes in the air to obtain a coated metal substrate according to Example 1. Thereafter, the surface of the coated metal substrate was cut vertically, and the cross section thereof was photographed by SEM. The obtained photograph is shown in FIG. Note that the chipping of the ceramic coat layer seen in the upper left part of FIG. 3 is missing when the ceramic coat layer is cut in order to take an SEM image.
  • Example 2 A coated metal substrate according to Example 2 was obtained in the same manner as in Example 1 except that heating was performed at 560 ° C. for 60 minutes in the firing step.
  • Comparative Example 1 (C) In the firing step, a coated metal substrate according to Comparative Example 1 was obtained in the same manner as in Example 1 except that heating was performed at 610 ° C. for 10 minutes.
  • the surface roughness Ra of the ceramic coat layer was measured using a surface roughness measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., Handy Surf E-35B). The results are shown in Table 1.
  • test pieces for measuring thermal conductivity according to Example 1, Example 2, and Comparative Example 1 were prepared.
  • the film thickness of the test piece for measuring thermal conductivity was 330 ⁇ m for the test piece according to Example 1, and 700 ⁇ m for the test piece according to Example 2 and the test piece according to Comparative Example 1.
  • JISR1611 (2010) using the laser flash apparatus thermal constant measuring apparatus: NETZSCH LFA457 Microflash
  • measured the heat conductivity of the thickness direction of the ceramic coat layer The results are shown in Table 1.
  • the test piece according to Comparative Example 1 was brittle and cracked when installed in the laser flash device, and the thermal conductivity could not be measured.
  • the coated metal substrate of the present invention was excellent in heat insulating properties because the pores were uniformly dispersed in the ceramic coat layer.

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Abstract

L'invention concerne un substrat métallique revêtu comportant une couche de revêtement céramique contenant un matériau de départ céramique formé sur un substrat contenant un métal. Le substrat métallique revêtu selon l'invention se caractérise en ce que l'intérieur de la couche de revêtement céramique contient des pores dispersés uniformément, en ce que la rugosité de surface (Ra) de la couche de revêtement céramique est de 8 µm ou inférieure et en ce que les pores sont directement entourés par la couche de revêtement céramique.
PCT/JP2015/064472 2014-10-24 2015-05-20 Substrat métallique revêtu WO2016063561A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04147985A (ja) * 1990-10-09 1992-05-21 Usui Internatl Ind Co Ltd アルミニウム材の耐摩耗皮膜及びその製造方法
JPH0643257B2 (ja) * 1987-11-27 1994-06-08 日本碍子株式会社 板状ほうろう製品
JP2004332081A (ja) * 2003-05-12 2004-11-25 Shin Etsu Chem Co Ltd 耐プラズマ部材及びその製造方法
JP2014162972A (ja) * 2013-02-27 2014-09-08 Kurashiki Boring Kiko Co Ltd マグネシウム基材の表面処理方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0643257B2 (ja) * 1987-11-27 1994-06-08 日本碍子株式会社 板状ほうろう製品
JPH04147985A (ja) * 1990-10-09 1992-05-21 Usui Internatl Ind Co Ltd アルミニウム材の耐摩耗皮膜及びその製造方法
JP2004332081A (ja) * 2003-05-12 2004-11-25 Shin Etsu Chem Co Ltd 耐プラズマ部材及びその製造方法
JP2014162972A (ja) * 2013-02-27 2014-09-08 Kurashiki Boring Kiko Co Ltd マグネシウム基材の表面処理方法

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