EP2955251B1 - Procédé de formation d'un film d'isolation thermique et structure d'un tel film - Google Patents

Procédé de formation d'un film d'isolation thermique et structure d'un tel film Download PDF

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Publication number
EP2955251B1
EP2955251B1 EP15170930.0A EP15170930A EP2955251B1 EP 2955251 B1 EP2955251 B1 EP 2955251B1 EP 15170930 A EP15170930 A EP 15170930A EP 2955251 B1 EP2955251 B1 EP 2955251B1
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EP
European Patent Office
Prior art keywords
heat insulating
coating film
insulating film
anodic oxidation
sealing
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Not-in-force
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EP15170930.0A
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German (de)
English (en)
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EP2955251A1 (fr
Inventor
Hiroki IGUMA
Akio Kawaguchi
Manabu Tateno
Hideo Yamashita
Yoshifumi Wakisaka
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Toyota Motor Corp
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Toyota Motor Corp
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    • 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
    • C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
    • 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
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Definitions

  • This invention relates to a method for forming a heat insulating film, and a structure of a heat insulating film.
  • the aforementioned conventional method includes a first step of forming an aluminum plating film over the entire circumference of an engine valve, a second step of, after formation of the aluminum plating film, subjecting the entire circumference of the engine valve to an anodic oxidation treatment to form an anodic oxidation coating film, and a third step of, after formation of the anodic oxidation coating film, subjecting an umbrella portion of the engine valve to a sealing treatment to form a sealing coating film.
  • a heat insulating film can be obtained that has a structure in which a sealing coating film is formed on an anodic oxidation coating film. Further, according to the engine valve on which the above described heat insulating film is formed, in addition to improving the heat resistance and a heat insulating property of a combustion chamber of the engine, a heat radiation property can also be improved.
  • WO2014/030297 discloses a heat insulating structure for an engine combustion chamber and CA2847549 discloses an anti-virus aluminum member.
  • the surface of the heat insulating film having a structure in which the anodic oxidation coating film and the sealing coating film are formed can be made smooth to a certain extent. Ideally, it is desirable for the surface of the heat insulating film to be made as smooth as the surface of the aluminum alloy prior to the anodic oxidation treatment.
  • the sealing coating film is formed by subjecting a sealing material that is the raw material of the sealing coating film to a drying and baking process. Consequently, in order to make the surface of the heat insulating film smooth by means of the sealing coating film, it is necessary to provide a large amount of the sealing material in concave portions of the surface of the anodic oxidation coating film to thereby make the sealing material thick at such concave portions.
  • the sealing material contains a solvent, the thicker the sealing material, the more difficult it becomes for a gas of the solvent that is generated at the time of drying and baking to escape to the outside. Therefore, there is the problem that cracks are liable to arise in the sealing coating film.
  • an object of the present invention is, with respect to a heat insulating film having a structure in which a sealing coating film is formed on the surface of an anodic oxidation coating film, to smooth the surface of the heat insulating film and also reduce the occurrence of cracks in the sealing coating film in a compatible manner.
  • a first aspect of the present invention is a method for forming a heat insulating film, according to claim 1, including:
  • the particles have a hollow structure.
  • an average primary particle diameter of the particles is greater than 30 nm.
  • a second aspect of the present invention is a structure of a heat insulating film, according to claim 2, that is formed by a formation method according to the first invention, and includes:
  • the particles are particles that have a hollow structure.
  • a porosity of the sealing coating film may be from 27.3 to 57.7%.
  • a sealing treatment can be performed using a sealing material that includes a silicon-based polymer solution and particles of a heat insulating material that are dispersed in the silicon-based polymer solution and are particles having an average particle diameter that is larger than an average pore diameter of pores of an anodic oxidation coating film.
  • a sealing material including particles of a heat insulating material of the aforementioned size the occurrence of cracks in a drying and baking process can be suppressed in comparison to when using a sealing material that does not include the particles.
  • the occurrence of cracks can be suppressed even when a sealing material is made thicker by providing a large amount thereof on concave portions of the surface of an anodic oxidation coating film. Further, the surface of the heat insulating film can be made smooth by means of a thick sealing coating film that is formed by drying and baking of the sealing material.
  • a heat insulating film can be formed that has a high heat insulating property in comparison to a heat insulating film that does not include particles that have a hollow structure.
  • a heat insulating film that has a high heat insulating property can be formed by using particles which have an average primary particle diameter that is greater than 30 nm.
  • a sealing coating film is provided that is formed so as to cover an opening portion of pores of an anodic oxidation coating film
  • a structure of a heat insulating film having a high heat insulating property can be provided that utilizes a heat insulating function of air inside the pores that is located at a deeper place than the opening portion.
  • a structure of a heat insulating film having a high heat insulating property that is obtained by means of a sealing coating film in which the porosity is between 27.3 and 57.7% can be provided.
  • Fig. 1 is a flowchart for describing the embodiment of the method for forming a heat insulating film.
  • an anodic oxidation coating film is formed on the surface of an aluminum alloy by subjecting a base material to an anodic oxidation treatment (step S1).
  • a treatment apparatus (not illustrated) that includes a flow channel through which an electrolytic solution is circulated and a pair of electrodes is used.
  • a base material is used that is made of aluminum alloy.
  • a base material may be used in which an aluminum alloy plating film is formed on a surface such as heat-resisting steel, carbon steel, or a titanium material.
  • step S1 specifically, the aforementioned base material is placed in the aforementioned treatment apparatus, and a voltage is applied between the aforementioned pair of electrodes while circulating an electrolytic solution through the aforementioned flow channel.
  • an anodic oxidation coating film is formed on the surface of the base material.
  • the anodic oxidation coating film is a coating film of porous alumina that has a large number of pores that open at the surface thereof (described in detail later).
  • the anodic oxidation coating film realizes a low thermal conductivity and a low heat capacity per unit volume (described in detail later).
  • Fig. 2 is a vertical cross-sectional view of the anodic oxidation coating film.
  • concavities and convexities have arisen on the surface of an anodic oxidation coating film 10
  • a surface roughness (arithmetic mean roughness) Ra thereof is an average of 4 to 5 ⁇ m.
  • the reason concavities and convexities arise on the surface of the anodic oxidation coating film 10 is that inclusions that are contained in the aluminum alloy affect the formation of the anodic oxidation coating film 10.
  • One object of steps S2 and S3 that are described hereunder is to smooth the surface of a heat insulating film in which the anodic oxidation coating film 10 is a constituent element.
  • a sealing material is coated onto the surface of the anodic oxidation coating film (step S2).
  • a sealing material is used that includes a silicon-based polymer solution that includes silicon in a main chain backbone (more specifically, a polymer solution including polysilazane or polysiloxane and an ether-based solvent), and silica particles that are dispersed in the silicon-based polymer solution.
  • the polymer solution may include an additive as necessary.
  • a dispersant that enhances the dispersibility of the particles, a leveling agent, a surfactant, a viscosity modifier and the like may be mentioned as examples of the additive.
  • the silica particles used in the present step have an average primary particle diameter (average particle diameter before the particles agglomerate and become secondary particles) that is larger than an average pore diameter of pores of the anodic oxidation coating film, and the silica particles also have a hollow structure.
  • silica particles with a solid structure may be used instead of the silica particles with a hollow structure (hereunder, referred to as "hollow silica particles"), and particles of a heat insulating material other than silica (for example, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), or titania (TiO 2 ) particles) may also be used.
  • alumina (Al 2 O 3 ), zirconia (ZrO 2 ), or titania (TiO 2 ) particles may also be used.
  • two or more kinds among the aforementioned three kinds of particles may be used at the same time.
  • the average pore diameter of the pores of the anodic oxidation coating film is approximately 30 nm. Therefore, in the present step, hollow silica particles for which the average primary particle diameter is greater than 30 nm (preferably, 50 nm) are used. However, a target value of the surface roughness Ra of the heat insulating film that is formed by the present embodiment is approximately 1 ⁇ m, and therefore in the present step hollow silica particles are used with respect to which an average secondary particle diameter is less than 1 ⁇ m (preferably 500 nm, more preferably 150 nm).
  • the term “average pore diameter” refers to an arithmetic mean diameter that is determined by photographing sectional images at a plurality of magnifications using a scanning electron microscope and digitalizing the obtained images by a scanner input method, and thereafter calculating a distribution of diameters of circles having an area that is equal to the area of respective pores extracted by computer image analysis.
  • the term “average primary particle diameter” refers to an arithmetic mean diameter that is determined by photographing transparent particle images at a plurality of magnifications using a transmission electron microscope and digitalizing the obtained images by a scanner input method, and thereafter calculating a distribution of diameters of circles having an area that is equal to a projected area of respective pores extracted by computer image analysis.
  • the term “average secondary particle diameter” refers to an average particle diameter (D50 value) that is obtained by a dynamic scattering method, and is a diameter that can be simply measured by a commercially available particle size analysis and measurement apparatus.
  • the mixing ratio of the hollow silica particles in the sealing material is appropriately adjusted in accordance with the target value (for example, a value in a range from 27.3% to 57.7%) of the porosity of the sealing coating film to be formed after drying and baking of the sealing material (after step S3).
  • the target value for example, a value in a range from 27.3% to 57.7%
  • FIG. 3 is a partially enlarged schematic view of the anodic oxidation coating film 10 shown in Fig. 2 .
  • the anodic oxidation coating film 10 is constituted by alumina 10a having a nonuniform length in a perpendicular direction relative to the surface of the aluminum alloy, and pores 10b.
  • a sealing material 12 constituted by a silicon-based polymer solution 14 and hollow silica particles 16 is provided so as to cover an opening portion 10c of the pores lOb.
  • a large amount of the sealing material 12 is provided at concave portions of the surface of the anodic oxidation coating film 10, and a small amount of the sealing material 12 is provided at protruding portions of the anodic oxidation coating film 10.
  • a method for coating the sealing material in step S2 is not particularly limited, and examples thereof include a spray method, a blade coating method, a spin coating method, and a brush application method.
  • step S3 the sealing material is dried and baked to form a sealing coating film (step S3).
  • the conditions (temperature, time period and the like) at the time of drying and baking are appropriately adjusted in accordance with the thickness of the sealing material that was coated onto the surface of the anodic oxidation coating film.
  • a heat insulating film is formed by performing the present step.
  • Fig. 4 is a vertical cross-sectional view of a heat insulating film that is formed by the formation method of the present embodiment. As shown in Fig. 4 , a sealing coating film 20 constituted by hollow silica particles 16 and silica 18 derived from a silicon-based polymer is formed on the surface of the anodic oxidation coating film 10.
  • a heat insulating film 22 is constituted by the anodic oxidation coating film 10 and the sealing coating film 20.
  • a surface roughness Ra of the heat insulating film 22 is equal to or less than 1 ⁇ m. The details of the structure of the heat insulating film 22 as well as the effects obtained by the structure of the heat insulating film 22 will be described later.
  • Heat insulating films 30a and 30b shown in Figs. 5A and 5B are heat insulating films that were formed for the purpose of comparison with the heat insulating film 22.
  • the heat insulating film 30a is constituted by a sealing coating film 32a that does not include hollow silica particles, and the anodic oxidation coating film 10.
  • the heat insulating film 30b shown in Fig. 5B is constituted by a sealing coating film 32b that does not include hollow silica particles, and the anodic oxidation coating film 10.
  • the thickness of the sealing coating film 32b is greater than the thickness of the sealing coating film 32a, and is approximately equal to the thickness of the sealing coating film 20 in Fig. 4 . However, cracks 34 have arisen in the sealing coating film 32b.
  • Fig. 6A is a view illustrating a process for forming the sealing coating film 32a.
  • Fig. 6B and Fig. 6C are views illustrating a process for forming the sealing coating film 32b.
  • a drying rate of an upper part (surface part) of the sealing material 36a at the time of drying and baking is approximately equal to a drying rate of an inner part of the sealing material 36a. Consequently, gas of a solvent that is generated during drying and baking is released from the inner part of the sealing material 36a to the outside thereof.
  • a sealing material 36b that does not include hollow silica particles is thickly coated ( Fig.
  • the upper part of the sealing material 36b hardens before the inner part of the sealing material hardens. Consequently, gas of a solvent that is generated during drying and baking cannot escape from the inner part of the sealing material 36b, and cracks 34 arise in the sealing coating film 32b ( Fig. 6C ).
  • Fig. 7 is a view for describing the periphery of a combustion chamber to which the structure of a heat insulating film of the present invention is applied. Note that although Fig. 7 is described on the premise that the engine is a spark-ignition type engine, the structure of a heat insulating film of the present invention can also be applied to a compression-ignition type engine.
  • a cylinder 42 of an engine 40 is formed inside a cylinder block 44.
  • a cylinder liner 46 is provided at an inner circumferential face of the cylinder 42. Further, inside the cylinder 42, a piston 48 is slidably disposed with respect to the cylinder liner 46.
  • a cylinder head 50 is installed at an upper portion of the cylinder block 44.
  • An intake port 52 and an exhaust port 54 are formed in the cylinder head 50.
  • An intake valve 56 is provided in the intake port 52, and an exhaust valve 58 is provided in the exhaust port 54.
  • a space that is surrounded by an inner circumferential face of the cylinder liner 46, a top face of the piston 48, a bottom face of the cylinder head 50, a bottom face of an umbrella portion of the intake valve 56 and a bottom face of an umbrella portion of the exhaust valve 58 corresponds to a combustion chamber 60. That is, an inner wall of the combustion chamber 60 is constituted by the inner circumferential face of the cylinder liner 46, the top face of the piston 48, the bottom face of the cylinder head 50, the bottom face of the umbrella portion of the intake valve 56 and the bottom face of the umbrella portion of the exhaust valve 58.
  • the heat insulating film 22 formed by the above described method is provided on the inner wall of the combustion chamber 60.
  • Fig. 8 is a partially enlarged schematic view of the heat insulating film 22 shown in Fig. 7 .
  • the heat insulating film 22 has a structure that includes the anodic oxidation coating film 10 and the sealing coating film 20.
  • the anodic oxidation coating film 10 is constituted by the alumina 10a and the pores 10b.
  • the sealing coating film 20 is constituted by the hollow silica particles 16 and the silica 18, and is formed so as to cover the opening portions 10c.
  • the silica 18 has a lower thermal conductivity than the aluminum alloy, and has a lower heat capacity per unit volume (volumetric heat capacity) than the aluminum alloy. Further, the alumina 10a has a lower thermal conductivity and a lower volumetric heat capacity than not only the aluminum alloy, but also than a conventional ceramic-based heat insulation material. Therefore, by applying the structure of the heat insulating film 22, in addition to improving the heat resistance and the heat insulating property of the combustion chamber 60, a heat radiation property thereof can also be improved.
  • Fig. 9 is a view showing results of measuring a thermal conductivity ⁇ of two kinds of heat insulating films.
  • Fig. 10 is a view showing results of measuring a volumetric heat capacity C of the two kinds of heat insulating films.
  • the thermal conductivity ⁇ and the volumetric heat capacity C were calculated based on the following equations after measuring a specific heat capacity Cp and a thermal diffusivity ⁇ with respect to two kinds of samples (a sample containing hollow silica particles and a sample that did not contain hollow silica particles).
  • Cp represents specific heat capacity
  • p represents density
  • ⁇ thermal diffusivity
  • sample A The sample containing hollow silica particles (hereunder, referred to as "sample A”) was prepared as follows. First, a base material (test piece of aluminum alloy) was subjected to an anodic oxidation treatment to form an anodic oxidation coating film. Next, hollow silica particles (hollow silica particles manufactured by GRANDEX Co., Ltd (primary particle diameter 90 to 110 nm)) were mixed in a polysilazane solution (ingredients and percentages: diethyl ether 72%, poly(perhydrosilazane) 20%, and anisole 8%) and stirred adequately using a stirrer to thereby prepare a sealing material.
  • sample B The sample that did not contain the hollow silica particles (hereunder, referred to as "sample B") was prepared in the same manner as the sample A except that the polysilazane solution was used as the sealing material.
  • Measurement method DSC method Measurement apparatus: DSC Q1000 manufactured by TA Instruments Reference sample: Sapphire Measurement atmosphere: N 2 atmosphere
  • Measurement method Laser flash method Measurement apparatus: LFA 457 manufactured by NETZSCH Temperature measurement method: Noncontact temperature measurement using InSb sensor Surface treatment: Graphite spray Measurement atmosphere: N 2 atmosphere
  • the measurement results in Fig. 9 and Fig. 10 are shown as percentages based on the sample B as 100%. As shown in Fig. 9 and Fig. 10 , the thermal conductivity ⁇ of the sample A (with particles) is low in comparison to the sample B (without particles), and the volumetric heat capacity C of the sample A is also lower than the sample B. These results indicate that the heat insulating property of the sample A is superior to that of the sample B.
  • the fact that the sample A includes hollow silica particles and the air in the internal space of the hollow silica particles functions similarly to the air inside the pores 10b may be mentioned as one of the reasons why the heat insulating property of the sample A is superior to that of the sample B.
  • Fig. 11 is a view illustrating results of measuring the surface roughness Ra.
  • the surface roughness Ra was measured with respect to both the sample A and the sample B that were prepared in the same manner as described above.
  • three different kinds of samples were prepared using three kinds of sealing materials that were prepared by changing the mixing ratio of the hollow silica particles.
  • the porosity ( volume of internal space of hollow silica particles/volume of sample ⁇ 100) after drying and baking the three kinds of sealing materials was as follows.
  • Sample A1 27.3% (porosity: low)
  • Sample A2 46.3% (porosity: medium)
  • Sample A3 57.7% (porosity: high)
  • the surface roughness Ra was measured in accordance with JIS B601 (2001).
  • the measurement results in Fig. 11 are shown as percentages based on the sample B as 100%.
  • the surface roughness Ra of the samples A1 to A3 (with particles) was less than that of the sample B (without particles).
  • the surface roughness Ra of the sample A3 was less than that of the sample A1 and the sample A2.
  • the fact that the surface roughness Ra is small means that the surface of the relevant sample is smooth and a heat transfer area is small. Accordingly, it was found that the heat insulating property of the sample A is superior to that of the sample B. Further, it was found that the heat insulating property of the sample A3 is superior to that of the sample A1 and the sample A2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Thermal Insulation (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)

Claims (3)

  1. Procédé de formation d'un film d'isolation thermique (22), caractérisé en ce qu'il comporte :
    une étape destinée à soumettre un alliage d'aluminium constituant une surface d'une matière de base à un traitement d'oxydation anodique pour former un film de revêtement d'oxydation anodique (10), le film de revêtement d'oxydation anodique (10) ayant une surface dans laquelle des pores sont formés et ayant également une rugosité de surface moyenne Ra de 4 à 5 µm ;
    une étape de dépôt sur la surface du film de revêtement d'oxydation anodique (10) d'une matière d'étanchéité (12) qui comprend une solution de polymère à base de silicium (14) et de particules (16) d'une matière d'isolation thermique qui sont dispersées dans la solution de polymère à base de silicium (14) et dans laquelle les particules (16) sont des particules de silice creuses ayant un diamètre de particule primaire moyen qui est plus grand qu'un diamètre extérieur des pores et plus grand que 30 nm et un diamètre de particule secondaire moyen de moins de 1 µm ; et
    une étape de séchage et de cuisson de la matière d'étanchéité (12) destinée à former un film de revêtement d'étanchéité (20),
    pour obtenir un film d'isolation thermique (22) ayant une rugosité de surface Ra qui est égale ou inférieure à 1 µm.
  2. Structure d'un film d'isolation thermique (22) qui est formée par un procédé de formation selon la revendication 1, caractérisée en ce qu'elle comporte :
    un alliage d'aluminium constituant une surface d'une matière de base ;
    un film de revêtement d'oxydation anodique (10) qui est formé sur une surface de l'alliage d'aluminium ayant une rugosité de surface moyenne Ra de 4 à 5 µm, et qui a une surface dans laquelle des pores sont formés ; et
    un film de revêtement d'étanchéité (20) qui est formé de façon à recouvrir la surface du film de revêtement d'oxydation anodique (10), et qui comprend des particules (16) d'une matière d'isolation thermique, les particules (16) étant des particules de silice creuses ayant un diamètre de particule primaire moyen qui est plus grand qu'un diamètre extérieur des pores et plus grand que 30 nm et un diamètre de particule secondaire moyen de moins de 1 µm ;
    dans laquelle la rugosité de surface Ra du film d'isolation thermique (22) est égale ou inférieure à 1 µm.
  3. Structure d'un film d'isolation thermique (22) selon la revendication 2, dans laquelle une porosité du film de revêtement d'étanchéité (20) est de 27,3 à 57,7%.
EP15170930.0A 2014-06-10 2015-06-08 Procédé de formation d'un film d'isolation thermique et structure d'un tel film Not-in-force EP2955251B1 (fr)

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FR3116823A1 (fr) 2020-11-30 2022-06-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Revêtement d’isolation thermique à base d’un Polymere PREcéramique pour améliorer les performances des moteurs thermiques

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CN105274599B (zh) 2018-11-23
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JP2015232163A (ja) 2015-12-24
EP2955251A1 (fr) 2015-12-16
US20150354083A1 (en) 2015-12-10

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