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WO2018051527A1 - Composant de moteur à combustion interne et procédé de fabrication dudit composant de moteur à combustion interne - Google Patents

Composant de moteur à combustion interne et procédé de fabrication dudit composant de moteur à combustion interne Download PDF

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Publication number
WO2018051527A1
WO2018051527A1 PCT/JP2016/085044 JP2016085044W WO2018051527A1 WO 2018051527 A1 WO2018051527 A1 WO 2018051527A1 JP 2016085044 W JP2016085044 W JP 2016085044W WO 2018051527 A1 WO2018051527 A1 WO 2018051527A1
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WO
WIPO (PCT)
Prior art keywords
layer
heat insulating
base material
iron
insulating layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/085044
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English (en)
Japanese (ja)
Inventor
鳥井　秀雄
鈴木　孝芳
雅章 井上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KOBE CERAMICS Corp
Nittan Corp
Original Assignee
KOBE CERAMICS Corp
Nittan Valve Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KOBE CERAMICS Corp, Nittan Valve Co Ltd filed Critical KOBE CERAMICS Corp
Publication of WO2018051527A1 publication Critical patent/WO2018051527A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B23/00—Other engines characterised by special shape or construction of combustion chambers to improve operation
    • F02B23/02—Other engines characterised by special shape or construction of combustion chambers to improve operation with compression ignition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B23/00—Other engines characterised by special shape or construction of combustion chambers to improve operation
    • F02B23/02—Other engines characterised by special shape or construction of combustion chambers to improve operation with compression ignition
    • F02B23/06—Other engines characterised by special shape or construction of combustion chambers to improve operation with compression ignition the combustion space being arranged in working piston
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B23/00—Other engines characterised by special shape or construction of combustion chambers to improve operation
    • F02B23/08—Other engines characterised by special shape or construction of combustion chambers to improve operation with positive ignition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F1/00—Cylinders; Cylinder heads 
    • F02F1/24—Cylinder heads
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/26—Pistons  having combustion chamber in piston head
    • 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
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J1/00—Pistons; Trunk pistons; Plungers
    • F16J1/01—Pistons; Trunk pistons; Plungers characterised by the use of particular materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a novel internal combustion engine component and a manufacturing method thereof.
  • FIG. 22 shows a schematic cross-sectional view of an automotive gasoline direct injection engine centered on a combustion chamber.
  • the main components constituting the combustion chamber 202 of the gasoline direct injection engine 201 include, for example, a cylinder head 203, a cylinder liner 204, an intake side engine valve 205, an exhaust side engine valve 206, a piston 207, a spark plug 208, fuel injection, and the like. Nozzle 209 etc. are mentioned.
  • the porous heat insulation layer As a member constituting the inner wall surface of the combustion chamber of the internal combustion engine in which the porous heat insulation layer is to be formed, for example, in the combustion chamber 202 shown in FIG. 22, the bottom surface of the umbrella portion of each of the engine valves 205 and 206 described above, Examples include the top surface of the piston 207 and the bottom surface of the cylinder head 203. It is conceivable to form a heat insulating layer on these surfaces.
  • the cylinder liner 204 it is not usually considered to arrange a porous heat insulating layer on the surface thereof. The reason is that the property that the piston 207 slides on the inner wall surface of the cylinder liner without causing atmospheric pressure leakage is the most important role. Therefore, the formation of the porous heat insulating layer increases the sliding frictional resistance. This is because there is a gap between the piston 207 due to wear due to mechanical sliding movement.
  • Examples of the internal combustion engine having the heat insulating layer as described above include a porous heat insulating material having a porosity of 80% or more formed of, for example, a mixed fired body of silicon nitride and hollow carbon spheres such as a piston top surface and a cylinder head lower surface of the internal combustion engine.
  • a porous heat insulating material having a porosity of 80% or more formed of, for example, a mixed fired body of silicon nitride and hollow carbon spheres such as a piston top surface and a cylinder head lower surface of the internal combustion engine.
  • Patent Document 1 An internal combustion engine coated with
  • the valve for an engine includes a valve body including a shaft portion and an umbrella portion, and opens and closes a port opened in the combustion chamber of the engine, and the valve head surface facing the combustion chamber in the umbrella portion includes A concave portion that is recessed from the valve head surface is formed in a portion excluding the central portion of the surface, the outer peripheral edge portion, and an intermediate portion therebetween, and the concave portion is filled so that the concave portion contains air.
  • the porous material is bonded to at least the central portion, outer peripheral edge portion and intermediate portion of the valve head surface to cover the valve head surface including the concave portion, and has a thermal conductivity higher than that of the valve body.
  • an engine valve using an anodized aluminum film as a heat insulating layer comprising an umbrella portion facing a combustion chamber of an internal combustion engine and a shaft portion that is integral with the umbrella portion and extends into an intake valve or an exhaust valve, and is formed of an iron-based material.
  • the film thickness of the aluminum plating film is set to 1 ⁇ 2 or less of the film thickness of the anodized film to be formed.
  • Patent Document 4 A method of manufacturing an engine valve to be adjusted has been proposed (Patent Document 4).
  • each member including a piston and the like.
  • a method for manufacturing a heat insulating structure for an engine combustion chamber in which a heat insulating layer is provided on the surface of a ferrous alloy member facing the engine combustion chamber comprising forming a silicone resin film on the surface of the member; A step of performing a first baking at 170 ° C. to 200 ° C. for 5 hours to 20 hours with respect to the silicone resin film, and a temperature of 250 ° C. to 350 ° C. with respect to the silicone resin film after the first baking. And a process of performing the second firing for 30 minutes to 3 hours has been proposed (Patent Document 5).
  • the heat insulating structure of the engine combustion chamber is provided with a heat insulating layer on the combustion chamber wall surface of the member facing the combustion chamber of the engine, the heat insulating layer includes a resin layer containing a silicone resin and hollow particles,
  • a heat insulating structure for an engine combustion chamber is disclosed that includes a metal foil layer provided on the surface of the resin layer (Patent Document 6).
  • An engine combustion chamber structure is disclosed (Patent Document 7).
  • Patent Document 8 a technique that employs a porous layer as a heat insulating film has been proposed (Patent Document 8), but it is not used under extremely severe conditions such as an engine valve. Has not been studied or developed under the most favorable conditions.
  • JP-A-60-182340 JP-A-4-311611 Japanese Patent No. 5625690 Japanese Patent No. 5607582 JP 2014-173396 A JP 2014-152735 A Patent No. 5696351 Patent No. 4966437
  • the parts constituting the inner wall surface of the combustion chamber of the internal combustion engine in which these heat insulating layers (porous membranes) are arranged can provide predetermined heat insulating properties, but there is room for further improvement.
  • a member such as an engine valve must have not only heat insulation (low thermal conductivity) but also oxidation resistance, deflection resistance, thermal shock resistance, and the like.
  • the bending resistance for example, as represented by an engine valve, for a member that operates on its own, continuous and continuous contact with other members, friction, etc. (in the case of an engine valve, contact with the valve seat and friction)
  • the part itself will bend instantaneously.
  • the heat insulating layer on the component does not peel off or drop off.
  • thermal shock resistance it is necessary for the parts to withstand a rapid temperature difference during heating and cooling because the combustion explosion and intake cycles are repeated in the combustion chamber of the engine.
  • the heat-insulating layer using the zirconia sprayed film shown in Patent Documents 1 to 2 is manufactured by a film-forming method in which zirconia particles whose surface is melted with high energy are sprayed onto the surface of the substrate and rapidly cooled, and further, the top surface of the piston Is a portion having a relatively large area, so that cracks due to repeated stresses of thermal expansion and contraction and cracks are likely to occur.
  • a porous material (metal non-woven fabric) prepared separately from the engine valve body is filled in the concave portion of the engine valve umbrella, and is sealed with a coating by plasma spraying.
  • the durability becomes a problem.
  • the engine valve body and the coating are in contact with each other in the region not filled with the porous material, heat conduction occurs from that region, and it is difficult to say that a sufficient heat insulating effect is obtained.
  • Patent Document 4 Anodizes an aluminum plating film, but when the aluminum plating film remains, the risk of peeling, dropping off, etc. cannot be completely avoided because of its low melting point. Problems remain in reliability and durability.
  • Patent Document 5 and Patent Document 6 are composed of a resin layer and a metal layer, since the base material and the metal layer are joined via the resin layer, intake air that occurs in the combustion chamber of the engine, There is a problem in reliability and durability with respect to repeated temperature changes accompanying continuous cycles of compression, explosion, and exhaust, and pressure changes such as explosion pressure, thermal expansion, and thermal contraction.
  • the heat insulating layer shown in Patent Document 7 is a porous anodic oxide film having a porosity of 30 to 60% formed on the top surface of an aluminum alloy base material (piston body).
  • the anodic oxide film directly formed on the base material is not sufficient in terms of adhesion and the like when it is applied to an engine valve or the like to which a stronger deflection is loaded, and there is a possibility that peeling or dropping off may occur.
  • the size and shape of the fine holes formed in this anodized film strongly depend on the type of solution used in the preparation of the anodized film and the formation conditions (voltage, current, time), so the pore diameter is uniform and It is difficult to make holes with a long depth stably.
  • the heat insulating film disclosed in Patent Document 8 is proposed as a heat insulating film in a resin molding die. That is, the heat insulating film is disposed between a transfer surface layer composed of a Ni-plated thick film precision-machined with a fine pattern directly touched by a high-temperature molten resin, and the metal base material. It aims at securing the fluidity of the molten resin by blocking the heat escaping to the heat and keeping the molten resin warm. For this reason, the operating temperature range is at most from room temperature to about 400 ° C., and stress deformation is not applied to the base metal. In contrast, engine parts (for example, engine valves) that form the inner wall of an internal combustion engine must withstand a high-temperature environment around 800 ° C.
  • the main object of the present invention is to provide an internal combustion engine component having both good heat insulation and higher durability than the prior art.
  • the present invention also provides an internal combustion engine component such as an engine valve that has high heat insulation (low thermal conductivity) and excellent durability such as oxidation resistance, deflection resistance, and thermal shock resistance. Objective.
  • the present invention relates to the following internal combustion engine component and a manufacturing method thereof.
  • a component constituting the inner wall surface of a combustion chamber of an internal combustion engine (1) The component includes (a) a base material containing an iron component, and (b) a heat insulating layer formed on the surface of the base material.
  • the heat insulating layer includes (b1) an intermediate layer formed on the base material, and (b2) an outer layer formed on the intermediate layer and exposed to the combustion chamber, (3)
  • the intermediate layer is a ferrite-containing layer substantially free of voids, (4)
  • the outer layer is a ferrite-containing layer in which substantially octahedral particles are fixed in a three-dimensional manner while forming voids.
  • An internal combustion engine component characterized by the above. 2.
  • Item 2 The internal combustion engine component according to Item 1, wherein the surface of the outer layer is formed with irregularities by substantially octahedral particles. 3. The internal combustion according to Item 1, wherein the base material containing an iron component is a) a material made of an iron-based metal, or b) a material in which part or all of the surface of the iron-based metal is covered with an iron nitride layer.
  • Item 5 The internal heat engine component according to Item 4, wherein a heat insulating layer is formed in a concentric region including a center of the top surface of the piston. 6).
  • Item 7 The method according to Item 6, wherein at least one of the first Fe-containing liquid and the second Fe-containing liquid contains a chelating agent.
  • the present invention it is possible to provide an internal combustion engine component having both good thermal insulation properties and physical properties superior to those of the prior art.
  • the internal combustion engine component of the present invention exhibits excellent performance in physical and mechanical properties such as oxidation resistance, deflection resistance, and thermal shock resistance as well as good heat insulation (low thermal conductivity). Can do.
  • the internal combustion engine component of the present invention effectively suppresses or prevents the heat insulation layer from being peeled off or dropped off even after repeated use over a long period of time, and can also achieve excellent durability. More specifically, the following effects can be obtained.
  • the heat insulation layer has a two-layer structure of an intermediate layer (dense ferrite-containing layer) and an outer layer (porous ferrite-containing layer), and these are integrally formed on the surface of the base material. Therefore, excellent physical properties such as oxidation resistance, deflection resistance, and thermal shock resistance can be exhibited. That is, the heat insulating layer is formed by integrating a base material, an intermediate layer (or adhesion reinforcing layer), and an outer layer, so that it is formed by a conventional oxide film (for example, an anodic oxide film) and a general coating technique. Since higher adhesion, flexibility, impact resistance, and the like can be exhibited than the applied layer (for example, a sprayed film), the heat insulation layer is more effectively prevented from being peeled off or dropped off.
  • a conventional oxide film for example, an anodic oxide film
  • the heat insulating layer has low thermal conductivity (excellent heat insulating property) and low specific heat (heat capacity per unit volume), high combustion efficiency can be obtained in the combustion chamber of the engine. That is, the heat insulating layer is a porous ferrite-containing layer composed of particles having a specific shape, and the outer layer is formed on the base material via the intermediate layer. Specific heat (heat capacity per unit volume) can be exhibited. Therefore, during explosion combustion, the generated thermal energy can be effectively maintained, while during intake, expansion of air flowing into the combustion chamber can be suppressed and air with a higher oxygen concentration can be introduced into the combustion chamber. As a result, combustion efficiency can be increased.
  • the components of the internal combustion engine of the present invention having such characteristics are preferably used as components (valves, pistons, etc.) constituting various engines such as automobile engines, motorcycle engines, marine engines, etc. be able to. Further, the present invention can be applied to any gasoline engine, diesel engine, or the like.
  • the internal combustion engine component of the present invention is suitable as an engine valve.
  • the valve base material when used as an exhaust valve for an engine, by providing the same heat insulation layer not only on the bottom surface of the umbrella portion on the wall surface side of the combustion chamber but also on the top surface of the umbrella portion, the valve base material is directly applied to the high-temperature exhaust gas after combustion. Therefore, it is possible to prevent the valve base material from being thermally deteriorated by high-temperature exhaust gas.
  • FIG. 1 is a schematic diagram of an engine valve in Embodiment 1.
  • FIG. 3 is a schematic cross-sectional view of a heat insulating layer provided on the engine valve of Example 1.
  • FIG. 3 is a process diagram showing a manufacturing process of the engine valve of Example 1.
  • 2 is an X-ray diffraction pattern diagram of a heat insulating layer and an intermediate layer of Example 1.
  • FIG. The pattern of the heat insulation layer is shown by (a), and the pattern of the intermediate layer is shown by (b). It is a figure which shows the scanning electron microscope image of the surface of the heat insulation layer of Example 1, and an intermediate
  • FIG. 5A shows the surface of the outer layer, and FIG. 5B shows the surface of the intermediate layer.
  • FIG. 2 is a cross-sectional view of a sample for evaluation of radiant heat absorbability of a heat insulating layer in Example 1.
  • FIG. It is the schematic which shows the radiant heat absorptivity evaluation apparatus of the heat insulation layer in Example 1.
  • FIG. It is a figure which shows the radiant heat absorbability evaluation result of the heat insulation layer in Example 1.
  • FIG. 1 is a schematic view showing a heat insulation layer durability test evaluation apparatus in Example 1.
  • FIG. It is a figure which shows the durability test evaluation result of the heat insulation layer in Example 1.
  • FIG. It is a figure which shows the time-dependent change of the durability test of the heat insulation layer in Example 1, and a comparative sample.
  • FIG. It is a figure which shows the rapid-heat rapid-cooling response evaluation result of the heat insulation layer in Example 1.
  • FIG. It is the schematic which shows the radiant heat absorptivity evaluation apparatus of the heat insulation layer in Example 1.
  • FIG. It is a figure which shows the radiant heat absorbability evaluation result of the heat insulation layer in Example 1.
  • FIG. 1 is
  • FIG. 13 It is a schematic sectional drawing of the vertical direction of the piston in Example 13.
  • FIG. It is process drawing which shows the manufacturing process of the piston of Example 13.
  • It is a schematic sectional drawing of the vertical direction of the piston in Example 14.
  • FIG. It is a schematic sectional drawing of the combustion chamber of a common motor vehicle engine.
  • the internal combustion engine component of the present invention is a component constituting the inner wall surface of the combustion chamber of the internal combustion engine, (1)
  • the component includes (a) a base material containing an iron component, and (b) a heat insulating layer formed on the surface of the base material.
  • the heat insulating layer includes (b1) an intermediate layer formed on the base material, and (b2) an outer layer formed on the intermediate layer and exposed to the combustion chamber, (3)
  • the intermediate layer is a ferrite-containing layer substantially free of voids,
  • the outer layer is a ferrite-containing layer in which substantially octahedral particles are fixed in a three-dimensional manner while forming voids. It is characterized by that.
  • FIG. 1 shows a component in which a heat insulating layer 3 is formed on the surface of the bottom surface 6 of the umbrella portion of the engine valve 1.
  • the umbrella bottom surface 6 is made of a base material containing an iron component.
  • a base material containing an iron component an iron-based metal is usually used, but an iron-containing film (not shown) such as iron oxide or iron nitride is formed on at least a part of the surface of the base material. It may be a material (base material).
  • the engine valve 1 has an umbrella bottom surface 6 constituting at least a part of an inner wall surface of an engine combustion chamber. Therefore, when the heat insulating layer is not formed, the engine valve 1 is exposed to the combustion flame generated in the combustion chamber because the bottom surface 6 of the umbrella portion itself is exposed to the combustion chamber of the automobile engine. On the other hand, in the present invention component, since the heat insulating layer 3 is formed on the surface of the umbrella bottom surface 6, the heat insulating layer 3 is exposed to the combustion chamber and exposed to the combustion flame.
  • the heat insulating layer 3 is composed of an intermediate layer 4 and an outer layer 5, and the outer layer 5 is arranged with the combustion chamber exposed.
  • the intermediate layer 4 is formed in contact with the surface of the base material 2 constituting the component of the present invention.
  • the intermediate layer 4 is preferably formed by causing a liquid phase reaction on the surface of the base material.
  • the intermediate layer 4 is a ferrite-containing layer that is substantially free of voids. That is, it is a region where no void is observed when the cross section is observed with a scanning electron microscope (100 times) (see, for example, FIG. 6 “Example”, FIG. 7, etc.).
  • the outer layer 5 is formed in contact with the surface of the intermediate layer 4.
  • the outer layer 5 is a ferrite-containing layer in which substantially octahedral-shaped particles are fixed in a three-dimensional manner while forming voids. That is, when the cross section is observed with a scanning electron microscope (100 times), in a region where a large number of substantially octahedron-shaped particles are gathered at random, a large number of spaces are observed between the particles. (For example, refer to FIG. 6 “this embodiment”, FIG. 7, etc.).
  • the intermediate layer 4 and the outer layer 5 may be composed of a single layer or may be composed of a plurality of layers. Also in this case, it is desirable that all the layers are formed by a liquid phase reaction of the underlying layer.
  • the base material of the component of the present invention may be made of a material containing an iron component, but the same iron-based metal that is usually used in known or commercially available internal combustion engines can also be suitably used.
  • iron-based metals include iron and iron alloys.
  • the iron alloy is not particularly limited as long as it contains iron (Fe), and various alloys such as carbon steel, stainless steel (SUS), and heat resistant steel (SUH) can be suitably used.
  • an iron-based alloy containing iron (particularly carbon steel) as a main component and containing at least one of chromium, nickel, cobalt, tungsten, manganese and the like can be used.
  • the alloy structure is not limited, and any of martensite, ferrite, austenite, precipitation hardening, and the like can be employed.
  • a material in which part or all of the surface of the iron-based metal is coated with a film of an iron compound (excluding ferrite) can also be used as the base material.
  • a film for example, a layer made of iron nitride may be included.
  • the iron nitride is not particularly limited, and includes any composition / crystal form such as Fe 3 N, Fe 4 N, and Fe 2 N.
  • the intermediate layer is one of the layers constituting the heat insulating layer and functions as a seed layer for forming the outer layer, and also has a function of firmly joining the base material and the outer layer.
  • the intermediate layer is a ferrite-containing layer substantially free of voids.
  • the intermediate layer is made of a spinel ferrite polycrystal.
  • ferrite crystals are easily generated and grown from the surface of the polycrystal (the outer layer is laminated) as a growth starting point. It is possible to effectively form the outer layer.
  • the following general formula A x Fe 3-x O 4 (However, A represents at least one metal element that can be substituted for the Fe site constituting the spinel-type iron oxide crystal, and x satisfies 0 ⁇ x ⁇ 1.) It is preferable that it is a compound which has a spinel type crystal structure shown by these.
  • the A is not limited as long as it is at least one metal element that can be substituted for the Fe site constituting the spinel-type iron oxide crystal, but in the present invention, it is at least one of Al, Mg, Mn, and Zn. Is desirable. Therefore, in the present invention, the A may be a composition in which at least one of Al, Mg, Mn, and Zn. Such a composition itself may be any known one, for example, AlFe 2 O 4 (that is, Fe 2+ (Al 3 + ⁇ Fe 3+ ) O 4 ), MgFe 2 O 4, MnFe 2 O 4 , ZnFe 2 O 4 or the like.
  • Such an intermediate layer is a layer of an intermediate layer (a base material containing an iron component, that is, a material made of an iron-based metal or an iron compound formed on the surface of an iron-based metal (excluding ferrite)). ) Is preferably a layer produced by a liquid phase reaction. More specifically, the intermediate layer is preferably an intermediate layer formed by a hydrothermal synthesis reaction in the Fe-containing liquid.
  • the thickness of the intermediate layer is not particularly limited, but it is usually preferable to set the thickness within a range of about 2 to 15 ⁇ m from the viewpoint of effectively exhibiting the above functions.
  • the outer outer layer is formed on the intermediate layer and exposed to the combustion chamber. As shown in FIG. 1, when the component of the present invention is an engine valve, the heat insulating layer 3 is exposed to the combustion chamber. In particular, the outer layer 5 shown in FIG. Will be exposed to.
  • the outer layer is a ferrite-containing layer in which substantially octahedral-shaped particles are three-dimensionally connected and fixed while forming voids.
  • the substantially octahedral particles are three-dimensionally deposited while forming voids.
  • the outer layer becomes porous.
  • a high heat insulation effect can be expressed.
  • a large number of substantially octahedral (substantially octahedral) particles are fixed in a random manner, and voids are formed between the particles. It is desirable to constitute a porous layer.
  • the substantially octahedral-shaped particles are usually ferrite crystal particles, and in particular, spinel-type ferrite (for example, iron ferrite) crystal particles.
  • spinel-type ferrite for example, iron ferrite
  • the heat insulating layer is made of a porous film in which iron ferrite crystal particles are accumulated, high heat insulating properties are obtained and a low specific heat is exhibited at the time of use of the component of the present invention. As a result, higher combustion efficiency can be obtained.
  • the bonding state of the ferrite crystal particles may be due to twin crystal growth, or may be a structure in which a plurality of crystals are connected and solidified. It should be noted that the size and the like of the crystal particles constituting the porous layer can be appropriately controlled depending on, for example, the synthesis conditions.
  • the following general formula A x Fe 3-x O 4 (However, A represents at least one metal element that can be substituted for the Fe site constituting the spinel-type iron oxide crystal, and x satisfies 0 ⁇ x ⁇ 1.) It is preferable that it is a compound which has a spinel type crystal structure shown by these.
  • the thermal conductivity of iron ferrite having a spinel crystal structure is 6.2 W / m ⁇ K at room temperature and 3.5 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 at 400 ° C.
  • the outer layer of the component of the present invention is porous, it exhibits lower thermal conductivity.
  • the volume specific heat of iron ferrite having a spinel crystal structure is 5.6 J ⁇ cm ⁇ 3 ⁇ K ⁇ 1 at 530 ° C.
  • the outer layer is porous, the volume specific heat is lower. Become. Therefore, the porosity of the porous layer of the component of the present invention is not particularly limited as long as it can be set to be lower than the thermal conductivity of the material having the same composition and the theoretical density.
  • the A is not limited as long as it is at least one metal element that can be substituted for the Fe site constituting the spinel-type iron oxide crystal, but in the present invention, it is at least one of Al, Mg, Mn, and Zn. Is desirable. Therefore, in the present invention, a composition in which the A component is at least one of Al, Mg, Mn, and Zn may be used.
  • a composition itself may be any known one, for example, AlFe 2 O 4 (that is, Fe 2+ (Al 3 + ⁇ Fe 3+ ) O 4 ), MgFe 2 O 4, MnFe 2 O 4 , ZnFe 2 O 4 or the like.
  • the particle size of the substantially octahedral particles is not limited, for example, as shown in FIG. 5, the particle size is usually 200 ⁇ m or less, and preferably 150 ⁇ m or less.
  • the lower limit of the particle size is not limited, but it is usually about 20 ⁇ m. Further, it is preferable that there are no coarse particles having a particle size exceeding 250 ⁇ m. Furthermore, it is preferable that fine particles having a particle size of less than 10 ⁇ m do not exist.
  • the particle size in the present invention refers to an average value of the longest diameters of 20 arbitrarily selected particles in observation with a scanning electron microscope (SEM).
  • the porosity of the outer layer is not particularly limited as long as voids are secured by the deposition of substantially octahedral particles.
  • the outer layer preferably has an inclined structure in which the porosity increases as it goes to the surface.
  • the porosity becomes the maximum value on the surface, and becomes a value lower than the maximum value in a region deeper than the surface. Therefore, the overall porosity can be adjusted by controlling the porosity of the surface.
  • the porosity of the outer layer surface immediately after being formed by the hydrothermal synthesis reaction described later is usually 100%, but the porosity of the outer layer surface is adjusted to a value lower than 100% by a method of polishing the surface. be able to.
  • the porosity of the outer layer surface when the porosity of the outer layer surface is adjusted to 90%, the entire outer layer has a porosity in the range of 0 to 90%.
  • the porosity of the surface of the outer layer can be set according to, for example, desired heat insulation properties, use conditions / environment of parts, etc., but is usually within a range of about 5 to 100%, and particularly 5 to 95. %, And more preferably 10 to 90%.
  • the porosity of the surface region of the thickness portion of 50% of the total thickness of the outer layer may be 10 to 90%, 30 to 60%, and further 40 to 60%.
  • the porosity in this invention can be measured and calculated by the method shown in the below-mentioned Example.
  • the pores existing at least on the surface where the outer layer is exposed are open pores.
  • the lower part of the outer layer has a relatively dense structure and maintains high adhesion with the intermediate layer, while the upper part of the outer layer has relatively large particles.
  • the stress is absorbed, so that fatal defects such as peeling that may occur between the outer layer and the intermediate layer can be effectively avoided.
  • the outer layer preferably has a structure in which the porosity increases from the bottom to the top. That is, it is desirable that the porosity of the outer layer increases as it goes to the exposed surface. Thereby, the performance (flexibility resistance) which can track the bending of a base material etc. can be effectively exhibited with high heat insulation.
  • the thickness of the outer layer can be appropriately set within the range of usually about 40 to 500 ⁇ m depending on the desired heat insulating property, etc., but from the viewpoint of more reliably obtaining excellent heat resistance and excellent durability, Usually, it is about 50 to 350 ⁇ m, and preferably 50 to 200 ⁇ m.
  • Step for forming an intermediate layer (intermediate layer formation step) (2) A step of forming an outer layer by causing a hydrothermal synthesis reaction on the surface of the intermediate layer in a second Fe-containing liquid having an Fe concentration exceeding 0.10 mol / L (outer layer forming step) can be suitably manufactured by a method for manufacturing an internal combustion engine component.
  • a base material surface containing an iron component is subjected to a hydrothermal synthesis reaction in a first Fe-containing liquid having an Fe concentration of 0.10 mol / L or less.
  • Step for forming an intermediate layer (intermediate layer formation step)
  • middle layer formation process it can also pre-process on the preform
  • Pre-treatment step In the present invention, a pre-treatment can be carried out prior to the intermediate layer forming step, if necessary.
  • the pretreatment step can be suitably performed when an iron-based metal (more specifically, an iron-based metal that has not been surface-coated) is used as the base material. Therefore, as the pretreatment, a step of cleaning the iron-based metal surface shown below can be performed.
  • a light sandblasting process (a method of polishing the surface by causing fine ceramic particles, glass beads or the like to collide with the iron-based metal surface) or the like can be employed.
  • step b for example, a method of cleaning the surface of the iron-based metal with an alkaline solution can be employed.
  • a method of washing the iron-based metal surface with weak hydrochloric acid or the like can be employed.
  • the intermediate layer is formed by subjecting the surface of the base material containing the iron component to a hydrothermal synthesis reaction in a first Fe-containing liquid having an Fe concentration of 0.10 mol / L or less.
  • an iron-based metal is usually used as a base material, and the surface can be treated in an intermediate layer forming step.
  • the first Fe-containing liquid an aqueous solution or an aqueous dispersion containing an iron component can be used.
  • the first Fe-containing liquid can be prepared, for example, by dissolving or dispersing a compound serving as a supply source of the iron component in a solvent.
  • a metal salt, a metal oxide, a metal hydroxide etc. can be used, for example.
  • the metal salt at least one of an inorganic acid salt and an organic acid salt can be used.
  • the inorganic acid salt for example, sulfate, carbonate, chloride and the like can be used.
  • an organic acid salt acetate, an oxalate, etc. can be used, for example.
  • any of water-soluble (water-soluble) or poorly water-soluble metal compounds can be used, but in the present invention, a water-soluble metal compound (iron compound) can be used more suitably.
  • water-soluble iron compounds include ferrous chloride, iron citrate, ammonium iron citrate, iron lactate, ferrous sulfate, and ferrous gluconate.
  • iron salts of divalent iron ions such as ferrous sulfate and ferrous chloride can be more preferably used.
  • the solvent to be used is not limited, and water and a mixed solution (mixed solution) of water and a water-soluble organic solvent can be used.
  • water-soluble organic solvent for example, alcohols such as methanol, ethanol and isopropyl alcohol can be suitably used.
  • the Fe concentration of the first Fe-containing liquid is 0.10 mol / L or less, preferably 0.065 to 0.10 mol / L. Therefore, for example, the Fe concentration can be 0.08 mol / L or less.
  • the lower limit value of the Fe concentration of the first Fe-containing liquid is not limited, but is usually about 0.01 mol / L.
  • the first Fe-containing liquid preferably contains an alkali.
  • the intermediate layer can be more reliably formed.
  • the alkali is not particularly limited, and for example, at least one kind such as sodium hydroxide and potassium hydroxide can be used.
  • the molar ratio of alkali to the total amount of iron ions in the first Fe-containing liquid is usually preferably 4.00 to 25.00 mol, particularly 6.00 to 20. More preferably 00 mol
  • each component such as an iron compound and an alkali, may melt
  • the first Fe-containing liquid may contain a chelating agent as necessary.
  • a chelating agent By containing a chelating agent, Fe ions bind to the chelating agent, increasing the solubility, and generating colloidal precipitates such as iron hydroxide generated by the reaction of Fe ions and hydroxide ions in a strong alkaline aqueous solution As a result, it is possible to obtain the effect of preventing the uneven concentration of Fe ions in the reaction solution during the hydrothermal reaction.
  • a known or commercially available chelating agent can be used.
  • Any chelating agent capable of forming a stable chelate compound with iron ions such as ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexane-N, N, N, N-tetraacetic acid monohydrate ( CyDTA), diethylenetriaminepentaacetic acid (DTPA), glycol ether diamine tetraacetic acid (GEDTA), and aminocarboxylic acid chelating agents.
  • EDTA ethylenediaminetetraacetic acid
  • CyDTA trans-1,2-diaminocyclohexane-N, N, N, N-tetraacetic acid monohydrate
  • DTPA diethylenetriaminepentaacetic acid
  • GEDTA glycol ether diamine tetraacetic acid
  • aminocarboxylic acid chelating agents aminocarboxylic acid chelating agents.
  • the amount added in the case of using a chelating agent can be appropriately set according to the type of chel
  • the ferrite-containing layer is formed by hydrothermal synthesis reaction of the base material surface in the first Fe-containing liquid as described above.
  • the conditions for the hydrothermal synthesis reaction are preferably heat treatment in an environment of 105 to 150 ° C. or higher saturated water vapor pressure.
  • a predetermined intermediate layer can be suitably formed by heat treatment under such temperature and pressure.
  • Such temperature and pressure conditions can be set using a known device such as an autoclave device (sealed system).
  • the hydrothermal synthesis reaction can be performed in the presence of a reducing agent.
  • a reducing agent By using a reducing agent, an excellent intermediate layer made of ferrite can be formed more reliably by suppressing or preventing the production of trivalent iron ions in the reaction system. Therefore, the reducing agent is not limited as long as it can suppress or prevent the production of trivalent iron ions, and can be appropriately selected from known reducing agents. For example, compounds known as antioxidants such as ascorbic acid and hydroquinones can be suitably used.
  • the reducing agent is preliminarily contained in the first Fe-containing liquid (particularly, the reducing agent is dissolved in the first Fe-containing liquid).
  • middle layer in a 1st Fe containing liquid can be employ
  • reaction time for hydrothermal synthesis reaction can be appropriately adjusted according to the desired thickness of the intermediate layer. That is, the reaction may be continued until the intermediate layer having the preferred thickness is formed. In order to obtain an intermediate layer having a uniform thickness with a desired thickness, the reaction is usually performed for 10 to 48 hours in the case of hydrothermal synthesis reaction. The reaction may be performed within the range.
  • Outer layer forming step In the outer layer forming step, the outer layer is formed by subjecting the surface of the intermediate layer to a hydrothermal synthesis reaction in a second Fe-containing liquid in which the Fe concentration exceeds 0.10 mol / L.
  • an aqueous solution or an aqueous dispersion containing an iron component can be used.
  • the preparation of the second Fe-containing liquid can be performed by, for example, dissolving or dispersing a compound serving as a supply source of the iron component in a solvent.
  • a metal salt, a metal oxide, a metal hydroxide etc. can be used, for example.
  • the metal salt at least one of an inorganic acid salt and an organic acid salt can be used.
  • the inorganic acid salt for example, sulfate, carbonate, chloride and the like can be used.
  • an organic acid salt acetate, an oxalate, etc. can be used, for example.
  • any of water-soluble (water-soluble) or poorly water-soluble metal compounds can be used, but in the present invention, a water-soluble metal compound (iron compound) can be used more suitably.
  • water-soluble iron compounds include ferrous chloride, iron citrate, ammonium iron citrate, iron lactate, ferrous sulfate, and ferrous gluconate.
  • iron salts of divalent iron ions such as ferrous sulfate and ferrous chloride can be more preferably used.
  • the solvent to be used is not limited, and water and a mixed solution of water and a water-soluble organic solvent can be used.
  • water-soluble organic solvent alcohols such as methanol, ethanol and isopropyl alcohol alcohol can be preferably used.
  • the Fe concentration of the second Fe-containing liquid is a concentration exceeding 0.10 mol / L, preferably 0.11 to 0.50 mol / L, more preferably 0.11 to 0.25 mol / L. Therefore, for example, the Fe concentration can be 0.5 mol / L or more.
  • the upper limit value of the Fe concentration of the second Fe-containing liquid is not limited, but is usually about 1.00 mol / L.
  • the second Fe-containing liquid preferably contains an alkali.
  • the outer layer can be more reliably formed.
  • the alkali is not particularly limited, and for example, at least one kind such as sodium hydroxide and potassium hydroxide can be used.
  • the molar ratio of alkali to the total amount of iron ions in the second Fe-containing liquid is usually preferably from 3.00 to 30.00 mol, particularly from 7.50 to 27. More preferably, it is 50 mol.
  • each component such as an iron compound and an alkali
  • the second Fe-containing liquid may contain a chelating agent as necessary.
  • a chelating agent By including a chelating agent, the solubility of Fe can be improved, and as a result, crystals can be grown greatly.
  • a known or commercially available chelating agent can be used. Any chelating agent capable of forming a stable chelate compound with iron ions, such as ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexane-N, N, N, N-tetraacetic acid monohydrate ( CyDTA), diethylenetriaminepentaacetic acid (DTPA), glycol ether diamine tetraacetic acid (GEDTA), and aminocarboxylic acid chelating agents.
  • EDTA ethylenediaminetetraacetic acid
  • CyDTA trans-1,2-diaminocyclohexane-N, N, N, N-tetraacetic acid monohydrate
  • DTPA diethylenetriamine
  • the amount added in the case of using a chelating agent can be appropriately set according to the type of chelating agent used, etc., but it is usually preferably 0.50 to 3.00 mol with respect to 1 mol of the total amount of iron ions. More preferably, it is 1.00 to 1.50 mol.
  • the ferrite-containing layer is formed by hydrothermal synthesis reaction of the base material surface in the second Fe-containing liquid as described above.
  • the conditions for the hydrothermal synthesis reaction are preferably heat treatment in an environment of 105 to 150 ° C. or higher saturated water vapor pressure.
  • a predetermined outer layer can be suitably formed by heat treatment under such temperature and pressure.
  • Such temperature and pressure conditions can be set using a known device such as an autoclave device (sealed system).
  • the hydrothermal synthesis reaction can be performed in the presence of a reducing agent.
  • a reducing agent By using a reducing agent, an excellent outer layer made of ferrite can be formed more reliably by suppressing or preventing the production of trivalent iron ions in the reaction system. Therefore, the reducing agent is not limited as long as it can suppress or prevent the production of trivalent iron ions, and can be appropriately selected from known reducing agents. For example, compounds known as antioxidants such as ascorbic acid and hydroquinones can be suitably used.
  • the reducing agent is preliminarily contained in the second Fe-containing liquid (particularly, the reducing agent is dissolved in the second Fe-containing liquid).
  • part which should form an outer layer in a 2nd Fe containing liquid can be employ
  • reaction time for hydrothermal synthesis reaction can be appropriately adjusted according to the desired thickness of the outer layer and the like. That is, the reaction may be continued until the outer layer having the preferred thickness is formed.
  • the reaction is usually within a range of 10 to 48 hours in the case of hydrothermal synthesis reaction. It can be formed by reaction. If the thickness of the outer layer is not sufficient for one reaction, the reaction can be repeated multiple times.
  • Example 1 Engine valve and production thereof (1-1) Structure of engine valve
  • An internal combustion engine component having a porous layer of the present embodiment is an engine valve 1 for exhaust gas having the configuration shown in FIG.
  • the engine valve 1 is mainly composed of an umbrella bottom surface 6, an umbrella top surface 8, a face surface 7, and a shaft portion 9.
  • the size of the engine valve 1 is that the diameter of the bottom surface 6 of the umbrella is 27.5 mm, the diameter of the shaft 9 is 5.5 mm, the length is 80.0 mm, The length to the apex is 108.0 mm.
  • the base material 2 constituting the engine valve 1 is made of heat resistant steel (austenitic heat resistant steel SUH35: carbon steel containing chromium, nickel, manganese) as a base material, and the entire surface thereof is nitrided by a nitriding treatment. The material formed was used.
  • heat resistant steel austenitic heat resistant steel SUH35: carbon steel containing chromium, nickel, manganese
  • a porous heat insulating layer 3 made of iron ferrite and having a thickness of 150 ⁇ m is formed on the surface of the region excluding the umbrella bottom surface 6, the face surface 7 and the shaft portion 9 (that is, the umbrella top surface 8).
  • a schematic diagram of a cross-sectional configuration including the heat insulating layer 3 is shown in FIG.
  • the heat insulating layer 3 is composed of a laminate of the intermediate layer 4 and the outer layer 5.
  • the heat insulation layer 3 is black and is made of iron oxide (that is, iron ferrite) having a crystalline spinel crystal structure.
  • the intermediate layer 4 is a layer directly formed on the surface of the base material 2 and has a thickness of about 6 ⁇ m.
  • the intermediate layer 4 is substantially free of voids and is composed of a dense polycrystalline film.
  • the outer layer 5 is formed such that new crystal particles generated from the surface of the intermediate layer 4 are randomly grown upward with each crystal particle on the surface of the intermediate layer 4 as a nucleus. It is a porous film containing voids. Its thickness is about 144 ⁇ m.
  • the outer layer 5 made of this porous film is a layer formed by growing and growing on the intermediate layer 4 by a liquid phase reaction, and has a structure in which the porosity increases toward the upper side. Further, since crystal growth mainly proceeds upward, the voids are not closed, and are open pores that open toward the surface. More specifically, the upper crystal particles are three-dimensionally stacked and connected while sharing a part of the iron ferrite crystal particles present below. For this reason, the crystal grains are denser as they go down, and there are a lot of voids as they go up, and crystal grains that have roughly octahedral shapes with horns are three-dimensionally connected. The shape is such that more voids exist as it goes upward.
  • the iron ferrite crystal particles are not particularly limited as long as they exhibit a crystalline diffraction peak in X-ray diffraction.
  • the size of the crystal particles constituting the outer layer depends greatly on the synthesis conditions and is not particularly limited.
  • the engine valve 1 was manufactured according to the manufacturing process shown in FIG. Hereinafter, each process will be described with reference to the schematic diagram shown in FIG. First, the base material 2 of the engine valve 1 described above was prepared by machining a heat-resistant steel material and forming a nitride film on the entire surface (FIG. 3 (1)). As shown in FIG. 2, the portion where the heat insulating layer is to be formed is the umbrella bottom surface 6 and the umbrella top surface 8. Therefore, the face surface 7 and the shaft portion 9 shown in FIG. 2 were masked with the resin coating film 10 as shown in FIG. 3B, and the coating was dried.
  • the intermediate layer and the outer layer were formed according to the conditions shown in Tables 1 and 2.
  • Tables 1 and 2 also show the thickness of the obtained intermediate layer, the thickness of the heat insulating layer, the peel rate after the durability test, and the like.
  • Tables 1 and 2 also describe conditions and the like in Example 2 and later.
  • Pretreatment Prior to the formation of the intermediate layer, first, as a pretreatment, sandblast treatment, alkali degreasing washing treatment and hydrochloric acid treatment were performed.
  • the sand blasting was performed under the condition that an abrasive consisting of alumina particles having an average particle diameter of 57 ⁇ m was ejected at a pressure of 0.3 MPa, the distance between the nozzle and the workpiece was 8 cm, and the blasting time was 20 seconds.
  • an alkaline degreasing cleaning treatment was performed.
  • the alkaline degreasing treatment is an operation for removing oil adhering to the surface.
  • the base material 2 is immersed in an aqueous solution of sodium hydroxide prepared by dissolving 400 g of sodium hydroxide (NaOH) in 2000 mL of purified water, and is heated to about 60 ° C. Treated at temperature for 30 minutes. Subsequently, hydrochloric acid treatment was performed. Hydrochloric acid treatment is an operation to remove the oxide film on the surface generated by air oxidation of chromium or the like, which is a component contained in a base material made of heat-resistant steel, and the base material 2 that has been subjected to alkaline degreasing cleaning treatment is made into a 30% hydrochloric acid aqueous solution. It was performed by dipping for 15 seconds at room temperature.
  • a first Fe-containing liquid used for forming the intermediate layer 4 was prepared.
  • 278 g of ferrous sulfate (FeSO 4 ⁇ 7H 2 O) and 0.8 g of ascorbic acid were mixed and dissolved to prepare an iron ion-containing aqueous solution (iron ion concentration: 1 mol / L) (A solution).
  • 200 g of sodium hydroxide was dissolved in 1000 mL of purified water to prepare an aqueous sodium hydroxide solution (concentration 5 mol / L) (solution B).
  • the container containing the suspension treatment liquid and the base material 2 was placed in the same autoclave apparatus as above and sealed, and a hydrothermal synthesis reaction was performed at 135 ° C. for 16 hours. Thereafter, the base material 2 was taken out together with the jig and sufficiently washed with water. In this way, a dense intermediate layer 4 (thickness 6 ⁇ m) serving as a seed crystal film for forming the heat insulating layer 3 was formed.
  • the reason why the shaft of the engine valve is horizontal and is positioned higher than the bottom surface of the cylindrical container is that the colloidal suspension layer and the mother layer located in the lower part of the suspension treatment liquid when placed at rest. This is to reduce the probability that the surface of the material contacts and to form a film in the supernatant liquid layer above the material surface.
  • an outer layer 5 made of a porous ferrite film was formed on the intermediate layer 4.
  • a chelate solution (C solution) was used in addition to the A solution and the B solution.
  • EDTA ⁇ 4Na ⁇ 4H 2 O ethylenediamine-N, N, N ′, N′-tetraacetic acid, tetrasodium salt / tetrahydrate
  • L Liquid C
  • C liquid 750 mL and B liquid 750 mL were mixed with the A liquid 500 mL, and a transparent second Fe-containing liquid (Fe concentration: 0.25 mol / L, NaOH concentration: 1.875 mol / L, [chelating agent] concentration: 0.375 mol) / L, NaOH molar ratio to Fe: 7.5, and chelating agent molar ratio to Fe: 1.5).
  • the base material shaft held by the fluororesin jig is placed in the liquid at a height of 4 cm from the bottom surface. I sunk.
  • the container containing the treatment liquid and the base material was placed in an autoclave and sealed.
  • an outer layer 5 made of a porous ferrite crystal was formed on the surface of the intermediate layer 4, and a heat insulating layer 3 having a total thickness of about 150 ⁇ m was obtained.
  • the base material was taken out together with the jig, sufficiently washed with water and dried. In this way, an engine valve having the heat insulating layer 3 formed at a desired portion was obtained.
  • a plate-shaped sample having the same structure as the layer structure shown in FIG.
  • the sample 11 has a heat insulating layer 13 disposed on one surface of a base material 12 made of a rectangular pure iron substrate having a length of 50 mm, a width of 20 mm, and a thickness of 0.3 mm, and is used for different evaluations. Three pieces of the same were prepared.
  • Sample 21 was produced by machining a lump of heat-resistant steel (SUH35), which is the same as the engine valve base material, for the purpose of evaluating the cross-sectional structure and void ratio (void ratio) of the heat insulating layer.
  • a heat insulating layer 23 which is a laminated structure of an intermediate layer 24 and an outer layer 25 is disposed on one surface of a base material 22 having a thickness of 10 mm.
  • Sample 11 was prepared as follows. In the same manner as the manufacturing process of the engine valve 1 shown in FIG. 3, one side of these base materials 12 was coated with a resin paint and masked, and then a heat insulating layer 13 was formed. The intermediate layer 14 and the outer layer 15 are formed together with the base material 1 of the engine valve in the processing liquid of the same reaction vessel at the time of forming each layer of the engine valve. It used for the thermosynthesis reaction. The three plate samples 11 thus produced were used for measuring the thickness of the layer formed on the surface and observing the film shape. Furthermore, these samples were also used for composition analysis and crystal structure analysis.
  • One of the three substrates on which the heat insulating layer 13 was formed was taken out after the formation of the intermediate layer 14 and used as a plate sample 11A.
  • the remaining two sheets were taken out after completion of the heat insulation layer 13 in which the outer layer 15 was formed on the intermediate layer 14, and were used as Sample 11B and Sample 11C, respectively.
  • sample 11A and sample 11B were used for material analysis.
  • Sample 11C was used for the evaluation of heat resistance described below, and further used for evaluation of adhesion after the evaluation.
  • Both of the above-mentioned two layers constituting the heat insulating layer 13 were black films.
  • FIG. 4A shows a diffraction pattern of the surface (sample 11B) after the outer layer 15 is formed
  • FIG. 4B shows a diffraction pattern of the surface (sample 11A) after the formation of the intermediate layer 14.
  • the intermediate layer 14 has a high intensity of the (400) peak and the (220) and (440) peaks, the iron ferrite having a surface in which the (100) and (110) crystal faces are slightly preferentially oriented crystallographically. It was confirmed that it was a crystalline film.
  • the intermediate layer 14 is thin, an iron peak (indicated by ⁇ ) of the base material existing therebelow is observed.
  • the outer layer 15 constituting the upper layer of the heat insulating layer 13 is grown from the surface of the intermediate layer 4 made of a crystal layer in which the (100) and (110) crystal faces are slightly preferentially oriented. It is also understood that the crystal planes are not oriented in these crystal planes and show a diffraction pattern similar to a general powder X-ray diffraction pattern of Fe 3 O 4 , and the crystal planes are disordered (random).
  • the octahedral crystal grains grow on the crystal grains forming the surface of the dense intermediate layer 14 with a certain interval in plan, and each of these octahedral crystal grains is formed.
  • the crystal grains are repeatedly grown in various directions while sharing one crystal face, and the outer layer 15 is formed while the crystal grains are connected and a space is formed between the crystal grains. It is thought that it is formed. Therefore, even though the specific crystal plane is slightly preferentially oriented in the intermediate layer, the outer layer 15 has a disordered orientation that does not show a specific crystal plane as if the crystal powder of Fe 3 O 4 is hardened. Conceivable.
  • FIG. 5A shows an SEM image of the outermost surface of the heat insulating layer 13 of the sample 11B (that is, the outermost surface of the outer layer 15).
  • substrate sample 11A is shown in FIG.5 (b). It can be seen that the intermediate layer 14 has a dense film quality without voids.
  • two base materials 22 and 122 having the same shape prepared by machining a lump of the same heat-resistant steel (SUH35) as the engine valve base material into a size of 30 mm long ⁇ 30 mm wide ⁇ 10 mm thick were prepared.
  • One side of 30 mm in length ⁇ 30 mm in width was left, and the other side was masked by the same method as in FIG.
  • one of the base materials 22 was formed with the heat insulating layer 23 of the present invention having a thickness of about 250 ⁇ m (Sample 21).
  • the heat insulating layer 23 includes an intermediate layer 24 (thickness of about 10 ⁇ m) and an outer layer 25 (thickness of about 240 ⁇ m) formed thereon.
  • the heat insulating layer 23 was formed on the base material 22 of the sample 21 in the same manner as the method for forming the heat insulating layer 3 shown in FIG.
  • the conditions for forming the intermediate layer 24 were changed to a temperature of 135 ° C. for 26 hours, and then the intermediate layer 24 having a thickness of about 10 ⁇ m was formed on the base material 22.
  • a sample 21 was prepared by removing the resin film used for the mask.
  • an iron plating film 124 having a thickness of 3 ⁇ m is formed as a base layer on the surface of the base material, and a heat insulating layer 125 of about 250 ⁇ m is formed thereon.
  • This heat insulation layer 125 was produced as follows, following the heat insulation film described in Japanese Patent No. 4966437. An iron plating film 124 having a thickness of about 3 ⁇ m was first formed on the masked base material 122 using an iron sulfate plating bath on the surface thereof. Subsequently, a heat insulating layer 125 having a thickness of about 250 ⁇ m was formed on the surface.
  • the heat insulation layer 125 was formed as follows. That is, an aqueous iron solution in which 41.7 g of ferrous sulfate (FeSO 4 .7H 2 O) was dissolved in 60 mL of water prepared by distillation in nitrogen gas, and 60 mL of an aqueous solution in which 21.6 g of sodium hydroxide were dissolved were added. A suspension treatment liquid (second Fe-containing liquid) was prepared by mixing. The suspension treatment liquid was placed in an autoclave reaction vessel made of stainless steel having an internal volume of 200 mL, and the base material 122 on which the iron plating film 124 was formed was immersed therein and held using a jig. The above operation was performed in a nitrogen gas atmosphere.
  • ferrous sulfate FeSO 4 .7H 2 O
  • the autoclave reaction vessel was heated from the outside at 150 ° C. for 10 hours by heating from outside, and then the mold base material was taken out together with the jig, and washed sufficiently with water in order to separate from the generated reaction residue powder compound. .
  • the autoclave reaction vessel was also washed with water in order to remove the reaction residue produced in the same manner, and again the same amount of suspension treatment solution as above was prepared, and the base material was attached together with the jig. Reacted for hours. Further, the same hydrothermal synthesis reaction was repeated 8 times to form a heat insulating layer 125 having a film thickness of about 250 ⁇ m.
  • Example (1-1) and “Comparative example 1 (1-1)” in FIG. 6 show the results of observing the surface of each sample with an SEM.
  • Example (1-2) and “Comparative Example 1 (1-2)” in FIG. 6 show the results of observing the cross sections of the respective samples with an SEM.
  • the sample 23 of this example is made of porous and rugged crystalline ferrite on a dense intermediate layer 24.
  • the porous outer layer 25 formed grows while being connected while sharing a part among the crystal grains to form a laminated film.
  • the outer layer 25 is dense with few pores on the side close to the intermediate layer 24, while the volume of pores formed by a large number of gaps formed between crystal grains increases as it approaches the surface (exposed surface). Recognize.
  • the heat insulating film 125 of the comparative sample 121 is formed on the iron plating film 124 formed on the surface of the base material as compared with the present example. It can be seen that it is an aggregate of very small crystal particles and consists of a porous film that grows upward while being three-dimensionally connected. Moreover, it can be seen that, unlike the heat insulating layer 23 of this example, the heat insulating layer 125 has many pores immediately above the iron plating film 124.
  • the relationship between the thickness of the heat insulating layer and the porosity was examined in more detail.
  • the substrate sample was gradually mechanically polished from the outermost surface of the substrate sample, and in the process, the substrate sample was taken out and the surface was observed with an SEM to examine the relationship between the porosity and the thickness. The result is shown in FIG.
  • the porosity in the present invention is a value obtained from an SEM image. That is, the outermost surface of the sample is a plane cut by a plane parallel to the base material surface where the apex portion of the porous film is in point contact, and at this time, the porosity is defined as 100%.
  • the above ratio was calculated using the cut-out weight method.
  • the calculation method will be described in detail. SEM images at a magnification of 100 times were taken using a scanning electron microscope at a total of five locations, one near the four corners and one at the center of the film formation surface that was partially polished to the desired thickness in sample 21. did. Each SEM image was enlarged and printed out on paper having a uniform thickness, and a single image having a size of 246 mm ⁇ 309 mm was created. First, the weight A of this entire image was measured. Next, an image portion of the polished film surface that was scattered was cut out using a scissors. All the cut out pieces were collected and the weight B was measured. The ratio of (AB) / A is calculated for each SEM image, and the above-mentioned ratios at five locations are simply averaged for the polished surface of each thickness obtained by polishing, and the porosity is displayed as a percentage. It was.
  • FIG. 7A shows the results of observing each surface with an SEM when the heat-insulating layer was gradually polished from the surface, and the film thickness.
  • FIG. 7B shows the result of observing the outermost surface (that is, the surface of the heat insulating layer before polishing) with an SEM.
  • FIG. 7C shows a graph showing the relationship between the film thickness and the porosity. As is apparent from these results, it can be seen that the porosity of the heat insulating layer 23 gradually increases from the surface of the base material toward the upper side. Further, as apparent from the result of FIG. 7C, the porosity of the surface region having a thickness of 50% of the total thickness 250 ⁇ m of the outer layer 25 (that is, a thickness of 125 ⁇ m) was about 40%.
  • the heat insulating layer 23 of the present invention is a film structure made of a black iron ferrite polycrystal.
  • the lower layer is a dense film, but the porosity increases toward the surface. Therefore, it is possible to obtain a surface with a desired porosity by scraping the film from the surface.
  • the ferrite ceramic sintered body (the thermal conductivity is about 3.5 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 at 400 ° C. due to the porous film structure as described above. It can also be seen that the volume specific heat is a film having properties of a density lower than 5.6 J ⁇ cm ⁇ 3 ⁇ K ⁇ 1 ) at 530 ° C. and a small heat capacity.
  • FIG. 8 shows an observation result before the bending test (FIG. 8A) and an observation result after the 30 ° bending test (FIG. 8B), respectively.
  • a1 shows the cross section (side surface) of the sample
  • a2 shows the result of SEM observation of the sample surface at 100 times
  • a3 shows the result of SEM observation of the sample surface at 300 times.
  • b1 shows the cross section (side surface) of the sample
  • b2 shows the result of SEM observation of the sample surface at 100 times
  • b3 shows the result of SEM observation of the sample surface at 300 times.
  • Samples 31 and 131 were produced as follows. First, prepare two blocks made of carbon steel (S45C) having a rectangular shape with a side of 30.0 mm on the bottom and a height of 100.0 mm, and the side of the side with a height of 90.0 mm from the bottom of each carbon steel block. A temperature sensor mounting hole having a diameter of 3.5 mm and a depth of 15.0 mm was formed in the central portion, and base materials 32 and 132 were produced. On one base material 32, a heat insulating layer 33 was formed above the bottom surface by the same method as the formation of the heat insulating layer 23 of the sample 21 described above.
  • the heat insulating layer 33 was prepared by first forming an intermediate layer 34 having a thickness of about 10 ⁇ m and laminating an outer layer 35 having a thickness of about 240 ⁇ m on the surface thereof. Subsequently, the obtained heat insulating layer 33 was polished from the surface to a thickness of about 150 ⁇ m. When the porosity of this surface was measured in the same manner as described above, it was about 53%. This was designated as Sample 31. Further, a base material 132 having the same shape as the base material 32 of the sample 31 was used as it was as a sample, and a comparative sample 131 without a heat insulating layer was obtained.
  • the heat insulation evaluation device 41 has a structure in which a soaking plate 43 made of a copper plate having a size of 200 mm ⁇ 150 mm and a thickness of 10 mm is disposed on the electric heater 42. Due to this configuration, the entire surface of the heat equalizing plate 43 is structured to have a uniform temperature when the heater is heated.
  • the sample 31 and the comparative sample 131 were placed on the surface of the heat equalizing plate 43 with the heat conduction grease 44 uniformly applied to the bottom surfaces thereof.
  • Temperature sensors 45 and 46 are attached to the temperature sensor attachment holes of the sample 31 and the comparative sample 131, respectively, so that the temperatures of the sample 31 and the comparative sample 131 can be recorded simultaneously on the temperature recorder 47.
  • the thermal insulation evaluation procedure was performed by heating the above two samples simultaneously and uniformly and comparatively measuring the temperatures of the blocks of the respective base materials. That is, the heating was started from room temperature in the air atmosphere using the electric heater 42, and the temperature rise of each sample for 40 minutes when the heater surface was heated to 230 ° C. was compared. The result is shown in FIG. It can be seen that the temperature of the sample 31 is slower in the sample 31 than in the comparative sample 131. It can also be seen that the higher the heating temperature, the greater the difference between the temperatures indicated by them, and the equilibrium state with the temperature difference.
  • the thermal energy supplied from the electric heater 42 is transmitted to the inside of the base material block and released to the atmosphere from the surface of the base material, but passes through the heat insulating layer 33 because there is a heat insulating layer 33 having high heat insulating properties. It is considered that the thermal energy is limited, the thermal energy escaping from the surface of the base material is increased, and equilibrium is reached at a temperature lower than that of the comparative sample 131. From these, it can be seen that the heat insulating layer has low thermal conductivity and has an effect of making it difficult to transfer heat.
  • the above-described heat insulating film has both heat insulating properties (that is, low thermal conductivity) and heat resistance, so that the engine valve of the present invention exhibits excellent performance that cannot be found anywhere else.
  • the heat insulating layer 53 was formed on the bottom surface of the base material 52 by the same method as that for forming the heat insulating layer.
  • the heat insulating layer 53 was prepared by first forming the intermediate layer 54 having a thickness of about 10 ⁇ m and laminating the outer layer 55 having a thickness of about 240 ⁇ m on the surface thereof. Subsequently, the obtained heat insulating layer 53 was polished from the surface to a thickness of about 100 ⁇ m. Next, as a result of measuring the porosity of this surface in the same manner as described above, it was 32%. This was designated as Sample 51.
  • a base material 152 having exactly the same shape as the base material 52 of the sample 51 was used as a sample as it was, and a comparative sample 151 without a heat insulating layer was used.
  • FIG. 12 shows the radiant heat absorption evaluation apparatus 61 used in this example.
  • This apparatus has a structure in which a soaking plate 63 made of an aluminum plate having a size of 200 mm ⁇ 150 mm and a thickness of 10 mm is anodized on an electric heater 62. Further, a black paint layer 67 is formed on the anodized upper side surface. Because of this configuration, the surface of the heat equalizing plate 63 is configured to emit heat uniformly when the heater is heated.
  • the sample 51 is placed at a height of 50 mm from the surface of the heat equalizing plate 63 by a resin holder attached to the column 68 so that the heat insulating layer 52 faces and is parallel to the heat equalizing plate 63. Arranged and suspended. Similarly, the comparative sample 151 was also arranged at the same height as the sample 51.
  • temperature sensors 64 and 65 are attached to the upper surfaces of the sample 51 and the comparative sample 151, respectively, so that their temperatures can be recorded in the temperature recorder 66 at the same time.
  • the heat insulation is evaluated by operating the electric heater 62 to uniformly heat the surface of the soaking plate 63 at the same time, and by measuring the temperature of the back surface of the metal flat plate of each sample, the state of temperature rise is compared. Went by.
  • the state in which the temperature of the back surface of the sample 51 placed on the support column and the comparative sample 151 rises is measured for 20 minutes while being heated and maintained at 230 ° C. in the air atmosphere using the electric heater 62. Was done.
  • the result is shown in FIG. It can be seen that the sample 51 is in an equilibrium state with the base material temperature rising faster than the comparative sample 151 and with a large temperature difference.
  • a part of the thermal energy supplied from the electric heater 62 heats the surface of the black paint layer 67, warms the contacted atmosphere, and warms the samples 51 and 151 arranged directly above by air convection.
  • the surface of the black paint layer 67 is also radiated as radiant heat, and is absorbed by the samples 51 and 151 arranged right above through the space. These heat energies are transmitted to the inside of the flat plate-shaped base material.
  • the temperature sensor installed on the back surface allows the temperature rise of the base material to be observed. Since the sample 51 has a high effect of absorbing a large amount of radiant heat, it is considered that the temperature of the sample 51 is increased by absorbing more heat energy. Part of the thermal energy absorbed by the base material escapes from the surface of the base material to the atmosphere, and it is considered that the sample 51 is in equilibrium at a higher temperature than the comparative sample 151 that absorbs less radiant heat energy. It can be seen that the heat insulating layer 53 has an effect of easily absorbing radiant heat. Thus, in the component of the present invention, the heat insulating layer can quickly absorb the heat rays generated by the flame caused by the explosion in the engine.
  • the used durability test evaluation device 71 includes a valve driving device 73 for installing an engine valve 72 to be tested and a combustion burner heating mechanism 74.
  • the valve drive device 73 is provided with a water cooling mechanism 78 for cooling the drive portion of the device.
  • the face surface of the engine valve 72 is disposed in a positional relationship in direct contact with the surface of the valve seat 75 when stationary.
  • the engine valve 72 has a structure in which a valve opening / closing mechanism 76 and a valve rotating mechanism 77 perform an operation similar to a valve opening / closing operation in the engine. For this reason, when the valve is driven, particularly around the umbrella portion of the valve 72 violently collides with the valve seat 75, an environment in which mechanical distortion is applied is created. At the same time, the bottom surface of the umbrella portion of the engine valve 72 is heated to a high temperature by the flame 79 ejected from the combustion burner heating mechanism 74.
  • the heat insulating layer is disposed on the entire bottom surface of the umbrella portion. Therefore, in this test, the heat insulating layer on the bottom surface of the umbrella portion is subjected to intermittent mechanical strain in a high temperature atmosphere. Thus, an accelerated evaluation of durability against the delamination phenomenon of the heat insulating layer that may occur in the engine can be tested.
  • the engine valve 1 of the above-described embodiment of the present invention was used.
  • a durability test was conducted for a total of 50 hours under the test conditions of a valve vertical speed of 3000 rpm and a valve rotation speed of 20 rpm while keeping the bottom surface of the umbrella part constant at 400 ° C. using a flame caused by the combustion of liquefied natural gas. .
  • the operation of the durability test apparatus 71 is temporarily stopped at the elapse of 1 hour, 3 hours, 5 hours, 10 hours, 20 hours, 30 hours, and 40 hours from the start of the operation of the durability test. After taking out and cooling to room temperature, it observed by observing the peeling state of the heat insulation layer 3 from the bottom face of the umbrella part. Thereafter, the engine valve 1 was again installed in the durability test apparatus 71, and the operation was continued until the next observation time. The durability test was repeated until the total operation time reached 50 hours. In that case, the percentage of the area of the peeled portion relative to the total area of the surface of the porous heat insulating layer was taken as the peel rate, and the peel rate was calculated for each take-out and observation during the durability test.
  • Engine Valve of Comparative Example 1 As an engine valve of Comparative Example 1, a base material for an engine valve having the same material, shape, and dimensions as those used in this example was prepared, and the same resin molding as that of Comparative Sample 121 was used. An engine valve having a heat insulating layer for mold (thickness 150 ⁇ m) was produced, and the same durability test was performed. The manufacturing method of the heat insulating layer was performed in accordance with the manufacturing method of the heat insulating film described in Japanese Patent No. 4966437. That is, in this engine valve, an iron plating film having a thickness of 3 ⁇ m is first formed on the surface of the base material in the formation portion of the heat insulation layer shown in FIG. By repeating the hydrothermal synthesis similar to the formation of 6 times, a heat insulating layer having a thickness of about 150 ⁇ m was formed.
  • an engine valve having a zirconia sprayed film which is a conventional porous heat insulating layer material, was prepared and subjected to the same durability test.
  • the engine valve of Comparative Example 2 was produced as follows. A base material similar to that used in this example is prepared, and a bonding base layer made of a nickel / chromium / aluminum / yttrium alloy sprayed film is formed on the bottom of the umbrella using an atmospheric plasma spraying method to a thickness of about 30 ⁇ m. Then, a zirconia film having a thickness of 100 ⁇ m on average was laminated and coated thereon by the same atmospheric plasma spraying method to obtain an engine valve of Comparative Example 2.
  • the heat insulating layer of this example and the heat insulating layer of Comparative Example 1 were black ceramic films, whereas the zirconia sprayed film that was the heat insulating layer of Comparative Example 2 was white.
  • the engine valve of the present example did not peel off the heat insulating layer even after 50 hours of the durability test.
  • the engine valve of Comparative Example 1 is slightly small in the peripheral portion of the bottom surface of the valve umbrella where the mechanical strain is most likely to be applied to the engine valve in the durability test, as shown in FIG. Generation of a plurality of peeled portions is observed. It was found that peeling occurred at the interface between the base material and the heat insulating film. It can be seen that after 20 hours, the areas of the peeled portions increased, and after 50 hours, the areas of the peeled portions further increased, and the number of peeled portions increased. The peeling rate after 50 hours was 6%.
  • the heat insulating film for molds of Comparative Example 1 made of iron ferrite having the same composition as in Example 1 has the adhesiveness at the interface between the base material and the heat insulating film against mechanical strain applied continuously and intermittently at high temperatures. It can be seen that the durability is relatively low.
  • the engine valve of Comparative Example 2 starts to peel slightly at the outer edge of the bottom surface of the valve umbrella after 5 hours from the endurance test, and after 20 hours, the peeled portion is connected to the outer edge and spreads. Further, after 50 hours had passed, the peeling spread from the end near the bottom of the umbrella toward the inside. After 50 hours, the peeling rate reached 20%.
  • the zirconia sprayed film of Comparative Example 2 also has relatively low adhesion at the interface between the base material and the heat insulating film.
  • the temperature evaluation device 81 includes a sample heating mechanism 85 for holding the engine valve 1 of this embodiment and heating it to a constant temperature, and an air flow rate controller 84 connected to a heater controller 82 and an air compressor 83. .
  • the sample heating mechanism 85 has a structure that can heat the bottom surface of the engine valve 1 with hot air.
  • a heating wire heater 66 is disposed immediately below the bottom of the umbrella portion of the engine valve 1 installed for measurement.
  • a temperature measuring portion of a temperature sensor 87 for controlling the heating wire heater is disposed between the bottom surface of the umbrella portion of the engine valve 1 and the electric heater 86, and the heater controller 82 is operated by the temperature signal of the temperature sensor 87. The power input to the heating wire heater 86 is controlled.
  • the structure is such that air whose flow rate is controlled flows from the lower part of the heating wire heater 86 and is changed to hot air having a set constant temperature to heat the bottom surface of the umbrella portion of the engine valve 1 to a fixed temperature.
  • the test was carried out by controlling the air flow rate to 25 liters per minute and setting the temperature of hot air that heats the bottom of the umbrella part of the engine valve 1 to 400 ° C.
  • FIG. 18 shows the results of the rapid heating / cooling evaluation.
  • the temperature at the bottom surface of the umbrella portion of the engine valve 1 of the present embodiment recorded by the temperature sensor 88 for temperature measurement is shown on the vertical axis, and the elapsed time from the beginning of heating the bottom surface of the umbrella portion with hot air is shown on the horizontal axis. .
  • the results of the engine valve 1 of this example (indicated by a solid line (a)) and the engine valve of a comparative sample without a heat insulating layer (indicated by a dotted line (b)) are shown.
  • the temperature of hot air measured by the heater control temperature sensor 87 arranged to control the heating wire heater 86 is indicated by a one-dot chain line in FIG.
  • the bottom surface of the umbrella part of the engine valve of the comparative sample without the heat insulating layer increased in temperature up to the temperature range of 250 ° C. following the temperature of the hot air.
  • thermal energy given to the bottom surface of the umbrella portion of the engine valve by hot air is conducted to the upper surface of the sample through the inside of the base material 2 of the engine valve 1. Since the top surface of the sample is fixed in close contact with a holder and is always cooled by the outside air, the temperature of the bottom surface of the sample is determined by the heat energy conducted from the bottom surface of the sample as the heat to the outside air and the surrounding holder. This is the equilibrium temperature of the bottom surface of the bottom of the engine valve when the heat is dissipated by conduction.
  • the heat insulation layer 3 suppresses the transmission of heat energy transmitted to the base material 2, so that the amount of heat energy transmitted to the inside of the base material to the upper surface of the sample is reduced, so that the heat energy is transferred to the outside air. Release is suppressed.
  • the heat insulation layer 3 is heated not only by hot air but also by absorption of heat rays radiated from the heating wire heater 86, but at the same time, the property of low thermal conductivity is also effective to transfer heat energy to the base material 2. Therefore, the temperature of the bottom surface of the umbrella portion of the engine valve is considered to be in an equilibrium state at a temperature higher than that of the engine valve of the comparative sample without the heat insulating layer.
  • the temperature of the temperature measuring portion of the temperature sensor 88 for temperature measurement arranged in contact with the surface receiving the hot air of the heat insulating layer 3 of the engine valve 1 of the present embodiment is that of the engine valve of the comparative sample without the heat insulating layer.
  • the temperature is higher than the bottom of the umbrella.
  • the temperature of the substantially equilibrium state 15 minutes after a heating start is compared with the temperature of the bottom part of the umbrella part of the engine valve of the comparative sample without a heat insulation layer. A temperature rise of about 8 ° C. can be observed, confirming that it has a heat insulating effect.
  • the power source of the electric heater 86 was stopped after 15 minutes of heating the heater.
  • the hot air instantly changed to cold air to quench the sample.
  • the temperature indicated by the heater control temperature sensor 87 instantaneously became room temperature.
  • the temperature of the bottom surface of the umbrella portion of the engine valve 1 of this embodiment rapidly decreases to 250 ° C. following the temperature of the cold air, and then continues to decrease while drawing a steep curve. It was.
  • the surface of the bottom part of the umbrella part of the engine valve of the comparative sample without the heat insulation layer also drops rapidly following the temperature of the cold air down to 250 ° C, and then the temperature drops while drawing a gentle curve compared to the engine valve 1 In 10 minutes, the temperature dropped to about room temperature.
  • the heat insulating layer 3 is porous and has a small specific heat with respect to the rapid cooling by cold air, so the temperature of the bottom surface of the umbrella portion of the engine valve 1 of this embodiment is steeper than the bottom surface of the umbrella portion of the engine valve without the heat insulating layer. It is thought that it descended with a gradient.
  • the surface temperature of the heat insulating layer 3 on the bottom surface of the umbrella portion of the engine valve 1 of the present embodiment can be remarkably improved in response to rapid heating and quenching by blowing air than an engine valve without a heat insulating layer. Recognize.
  • Example 2 (1) Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. In addition, as shown in Table 1, a predetermined amount of chelating agent (EDTA ⁇ 4Na ⁇ 4H 2 O) was blended in the first Fe-containing liquid.
  • EDTA ⁇ 4Na ⁇ 4H 2 O a predetermined amount of chelating agent
  • Example 2 Material analysis of heat insulation layer The material analysis of the obtained heat insulation layer was conducted in the same manner as in “(2) Material analysis of heat insulation layer” in Example 1. As a result, the heat insulation layer of the present example was the same heat insulation layer as Example 1. Moreover, the intermediate
  • Example 3 Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. As shown in Table 1, a predetermined amount of chelating agent (DTPA (diethylenetriaminepentaacetic acid)) was blended in the first Fe-containing liquid. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • DTPA diethylenetriaminepentaacetic acid
  • Example 4 Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. As shown in Table 1, a predetermined amount of chelating agent (DTPA (diethylenetriaminepentaacetic acid)) was blended in the first Fe-containing liquid. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • DTPA diethylenetriaminepentaacetic acid
  • Example 5 Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. As shown in Table 1, a predetermined amount of chelating agent (CyDTA (trans-1,2-diaminocyclohexane-N, N, N, N-tetraacetic acid monohydrate)) was added to the first Fe-containing liquid. Blended. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • CyDTA trans-1,2-diaminocyclohexane-N, N, N, N-tetraacetic acid monohydrate
  • Example 6 Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. As shown in Table 1, a predetermined amount of chelating agent (CyDTA (trans-1,2-diaminocyclohexane-N, N, N, N-tetraacetic acid monohydrate)) was added to the first Fe-containing liquid. Blended. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • CyDTA trans-1,2-diaminocyclohexane-N, N, N, N-tetraacetic acid monohydrate
  • Example 7 Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • Example 8 (1) Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • Example 9 Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • Example 10 (1) Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • Example 11 Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used. In this example, in the intermediate layer forming step, hydrothermal synthesis was performed at a low temperature of 110 ° C. for 1 hour, and then hydrothermal synthesis was performed at 135 ° C. for 20 hours while the reaction vessel was sealed. (2) Evaluation of durability In the same manner as in Example 1, a durability test was performed. As a result, even after the end of the durability test for 50 hours, the heat insulating layer was not peeled off as in Example 1.
  • Example 12 Engine valve having a porous layer and production thereof An engine valve was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used.
  • hydrothermal synthesis was performed at a low temperature of 110 ° C. for 1 hour, and then hydrothermal synthesis was performed at 135 ° C. for 20 hours while the reaction vessel was sealed.
  • a predetermined amount of chelating agent EDTA ⁇ 4Na ⁇ 4H 2 O
  • Example 13 Piston having a porous layer and production thereof As an internal combustion engine component, a piston constituting an in-cylinder injection engine of an automobile was produced. The cross-sectional structure of this piston is shown in FIG.
  • the piston has a diameter of 84 mm and a height of 53 mm.
  • the material of the piston base material 92 is cast iron.
  • the central portion of the top surface of the piston 91 main body is perpendicular to the piston axis, has a circular cross section (diameter 50 mm), and has a recess having a depth of 6 mm.
  • a porous heat insulating layer 93 is formed on the entire top surface of the base material 92 on the top surface of the piston 91.
  • the heat insulating layer 93 is a laminate composed of an intermediate layer 94 and an outer layer 95, and in particular, the central portion (concave portion) where the injected fuel directly collides and the portion constituting the outer peripheral portion of the piston top surface are the thickness of the heat insulating layer.
  • the porosity is different.
  • the thickness of the heat insulating layer is about 75 ⁇ m at the center and about 200 ⁇ m at the outer periphery.
  • the porosity of the heat insulation layer is about 10% in the central portion and about 90% in the outer peripheral portion.
  • the surface portion of the piston top surface recess where the injected fuel directly falls is formed of a slightly dense film having a small porosity of the ferrite film. This is to avoid the risk that the injected fuel enters deep inside the heat insulating film having a porous structure and the timing of combustion is shifted.
  • the surface of the peripheral portion where the fuel does not fall directly has a high porosity, a high heat insulating property is obtained and a low specific heat is exhibited at the time of use of the present invention.
  • the heat insulation layer 93 formed on the top surface of the base material 92 is composed of a laminate of a dense film quality intermediate layer 94 having a thickness of 10 ⁇ m and an outer layer 95 formed by crystal growth of the intermediate layer 94 as a seed crystal. ing.
  • the heat insulating layer 93 is an iron ferrite having a crystalline spinel crystal structure similar to that of the heat insulating layer 3 of the first embodiment.
  • the intermediate layer 94 is a dense polycrystalline ferrite film having no voids formed in contact with the surface of the underlying cast iron base material 92.
  • the outer layer 95 is a porous film formed by growing each crystal grain on the surface of the intermediate layer 94 as a nucleus while growing the crystal grain upward from the surface and forming a void while growing the grain. is there. That is, the outer layer 95, which is a porous film, is a film grown from the intermediate layer 94, and has a form in which the porosity increases toward the upper side (surface). In addition, since the progress of crystal growth occurs mainly upwards, the fine structure of the film is that the upper crystal grains are stacked three-dimensionally while sharing a part of the iron ferrite crystal grains existing below.
  • the crystal grains are denser in the form of rock, the more upward, the more voids there are in the film, and the crystal particles are three-dimensionally connected. It has a form in which many voids exist.
  • the ferrite crystal particles may be any particles that exhibit a crystalline diffraction peak in X-ray diffraction. Note that the size of the crystal particles constituting the porous film is not particularly limited and greatly depends on the synthesis conditions.
  • FIG. 20 shows a schematic diagram of the manufacturing process of the piston 91 of the present invention. Hereinafter, each step will be described with reference to the schematic diagram shown in FIG.
  • a cast iron base material 92 was prepared. Only the top surface on which the heat insulating layer was to be formed was left, and the other portions were coated with a resin coating material for masking, thereby masking with a resin coating film 99 and drying the coating. Next, the entire surface was sandblasted with masking, further subjected to alkaline degreasing cleaning treatment and weak hydrochloric acid treatment, and then dried to produce a clean base material 92 masked with the resin coating film 99 ( FIG. 20 (1)). Next, an intermediate layer 94 having a thickness of about 10 ⁇ m was formed on the surface of the top surface of the base material. (FIG. 20 (2)).
  • an outer layer 95 made of a porous ferrite film having a thickness of about 240 ⁇ m was formed thereon (FIG. 20 (3)).
  • a heat insulating layer 93 made of a ferrite film having a total thickness of about 250 ⁇ m was obtained.
  • the surface of the heat insulating film formed on the bottom of the concave portion of the piston top where the injected fuel falls is mechanically polished to a thickness of about 75 ⁇ m and the outer peripheral portion to about 200 ⁇ m (FIG. 20 (4)).
  • the resin coating film 99 was peeled off to complete the piston 91 of this example (FIG. 20 (5)).
  • Pretreatment As a pretreatment, the entire surface of the base material was subjected to a sandblast treatment while being masked, and further subjected to an alkaline degreasing washing treatment and a hydrochloric acid treatment.
  • the sand blasting treatment was performed under the condition that the abrasive consisting of alumina particles having an average particle diameter of 57 ⁇ m was ejected at a pressure of 0.3 MPa, the distance between the nozzle and the workpiece was 8 cm, and the blasting time was 20 seconds.
  • Example 1 Formation of Intermediate Layer Liquid A and liquid B shown in Example 1 were used for preparing the first Fe-containing liquid.
  • 180 mL of the liquid A is mixed with 1420 mL of purified water and 400 mL of the liquid B, and 2000 mL of suspension treatment liquid (Fe concentration: 0.09 mol / L, NaOH molar ratio to Fe: 11.1) was prepared.
  • the suspension treatment liquid is placed in a stainless steel cylindrical container (inner volume of about 3100 mL, diameter 10 cm, height 40 cm), and the top surface of the piston, which is a heat insulating film forming part, is 10 cm or more in height from the bottom of the cylindrical container.
  • the base material held by the stainless steel jig was submerged in the liquid so that the height was reached.
  • the container containing the suspension treatment solution and the base material was sealed in an autoclave apparatus, and a hydrothermal synthesis reaction was performed at 135 ° C. for 26 hours. Thereafter, the base material was taken out together with the jig and thoroughly washed with water. In this way, a dense intermediate layer 94 (thickness 10 ⁇ m), which is a seed crystal film for forming a ferrite heat insulating film, was formed.
  • the reason why the top surface of the piston is arranged at a position higher than the bottom surface is to reduce the probability that the suspended fine particle layer in the suspension treatment solution comes into contact with the surface of the base material, and This is because a film is formed in the layer.
  • an outer layer 95 made of a porous ferrite film was formed using the second Fe-containing liquid.
  • the liquid A, liquid B and liquid C described in Example 1 were used.
  • C liquid 750mL and B liquid 750mL were mixed with A liquid 500mL.
  • the second Fe-containing liquid Fe concentration: 0.25 mol / L, NaOH concentration: 1.875 mol / L, chelating agent concentration: 0.375 mol / L, molar ratio of NaOH to Fe: 7.5, to Fe
  • a molar component ratio of the chelating agent: 1.5 was prepared.
  • the second Fe-containing liquid was poured into a stainless steel cylindrical container (with an internal volume of 3500 mL), and the base material held by the stainless steel jig was submerged in a liquid having a height of 2 cm from the bottom.
  • the container containing the reaction solution and the base material 92 is sealed in an autoclave apparatus and subjected to a hydrothermal synthesis reaction at 135 ° C. for 10 hours, whereby a porous ferrite crystal is formed on the surface of the seed crystal film of the initial layer. An outer layer consisting of was formed.
  • the base material was taken out together with the jig and thoroughly washed with water. Further, by carrying out a hydrothermal synthesis reaction at 135 ° C.
  • a thick outer layer of the ferrite heat insulating film is further formed on the surface of the outer layer made of the porous ferrite crystal of the first layer.
  • a heat insulating layer having a total thickness of 250 ⁇ m with the layer was obtained.
  • a surface heat insulating layer 93 was formed on the top surface of the piston.
  • the heat insulating layer of this example is a heat insulating layer similar to that of Example 1, and the intermediate layer is a dense film having no pores, similar to that shown in FIG. It was.
  • membrane which is a laminated body with an outer layer was the same surface form as Fig.5 (a) of Example 1.
  • FIG. It was also confirmed that each layer was a film made of iron ferrite having a high crystallinity and a spinel crystal structure having a lattice constant a 0 8.40 ⁇ .
  • the thickness of the heat insulation layer was determined by measuring the difference in thickness of the substrate before and after the formation of the heat insulation layer. As a result, the thickness of the formed intermediate layer 94 was about 10 ⁇ m, and the thickness of the heat insulating layer was about 250 ⁇ m. Therefore, the outer layer 95 was about 240 ⁇ m.
  • the porosity was measured when the thickness of the heat insulating layer after polishing was about 200 ⁇ m. Further, the polishing was advanced, and the porosity when the thickness of the heat insulating layer after polishing was about 75 ⁇ m was measured. The porosity of each was 90% and 10%.
  • the heat insulating layer 93 on the top surface of the piston subjected to mechanical polishing in this example has a porosity of 10% on the surface (film thickness 75 ⁇ m) of the heat insulating layer formed at the bottom of the concave portion of the top, It is considered that the porosity of the portion (thickness: 200 ⁇ m) is 90%.
  • the heat insulating layer 93 Since the heat insulating layer 93 has such a porous film structure, the heat insulating layer 93 has a property that the density is lower and the heat capacity is smaller than that of the ferrite ceramic sintered body having a lower thermal conductivity than the cast iron of the piston base material. You can see that it is layered.
  • Example 14 Piston having a porous layer and production thereof A piston used for an automobile engine was produced as an internal combustion engine component.
  • the cross-sectional structure of this piston is shown in FIG.
  • the piston 106 has a structure in which a heat insulating plate 101 is disposed in a concave portion at the center of the top surface of a base material 107 made of an aluminum-silicon alloy casting.
  • the piston has a diameter of 76 mm and a height of 58 mm.
  • a central portion of the top surface of the piston body has a circular cross section perpendicular to the piston axis, a diameter of 56 mm, and a depth of 3 mm.
  • a heat insulating plate 101 is disposed so as to be in close contact with the concave portion of the top surface.
  • a heat insulating layer 103 having a thickness of 75 ⁇ m made of a laminate of an intermediate layer 104 and an outer layer 105 is formed on the surface of a base material 102 made of an iron alloy thin plate (thickness 1.8 mm).
  • the intermediate layer 104 and the outer layer 105 disposed on the upper surface thereof were produced in the same manner as in Example 13.
  • the intermediate layer 104 is a dense polycrystalline film having no voids formed so that the underlying iron is in contact with the surface of the main component iron alloy 102.
  • the outer layer 105 is a porous film formed by growing each crystal particle forming the surface of the intermediate layer 104 as a nucleus while leaving a void upward from the surface. This is a porous film similar to the outer layer 93 of Example 13.
  • the heat insulating layer 103 is composed of a laminated body of a dense intermediate layer 104 and an outer layer 105 that is crystal-grown with each crystal particle of a polycrystalline body constituting the intermediate layer as a nucleus, and is a laminated body having a thickness of about 250 ⁇ m (that is, The surface of the upper layer (that is, the outer layer 105) of the heat insulating layer 103) was mechanically ground to a thickness of 75 ⁇ m to obtain a flat shape with a surface porosity of 10%.
  • the heat insulation layer 103 of the present embodiment is black, similar to the heat insulation layer 93 of the embodiment 13, and is made of iron ferrite having a crystalline spinel crystal structure.
  • the heat insulating plate 101 manufactured in this manner was simultaneously cast and integrated when a piston was manufactured using a molten aluminum alloy, thereby obtaining the piston 106 of the present invention.
  • the piston of the present embodiment having such a configuration can exhibit the same effect as the piston 91 of the third embodiment.
  • the internal combustion engine component according to the present invention can be suitably used as, for example, an engine valve, a piston, a cylinder head, or the like as a component that constitutes a combustion chamber of an engine that is an internal combustion engine such as an automobile, a motorcycle, or a ship.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un composant de moteur à combustion interne qui présente aussi bien de bonnes propriétés d'isolation qu'une durabilité supérieure à celle de l'état de la technique. La solution selon la présente invention concerne un composant qui forme une surface de paroi interne d'une chambre de combustion d'un moteur à combustion interne, le composant étant caractérisé en ce que : (1) le composant comprend (a) une matrice qui comprend un constituant de fer et (b) une couche isolante formée sur la surface de la matrice ; (2) la couche isolante comprend (b1) une couche intermédiaire formée sur la matrice et (b2) une couche externe formée sur la couche intermédiaire et exposée à la chambre de combustion ; (3) la couche intermédiaire est une couche comportant de la ferrite sensiblement dépourvue d'espaces d'air ; et (4) la couche externe est une couche comportant de la ferrite dans laquelle des particules grossièrement octaédriques sont fixées de façon à être continues en trois dimensions tout en formant des espaces d'air.
PCT/JP2016/085044 2016-09-13 2016-11-25 Composant de moteur à combustion interne et procédé de fabrication dudit composant de moteur à combustion interne Ceased WO2018051527A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
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JP2023048734A (ja) * 2021-09-28 2023-04-07 マツダ株式会社 ピストンの遮熱材塗布方法

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JP2023129167A (ja) * 2022-03-03 2023-09-14 洋 角田 太陽光と水で稼動するエンジン及び船舶

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WO2001033065A1 (fr) * 1999-10-29 2001-05-10 Nippon Piston Ring Co., Ltd. Combinaison chemise de cylindre et bague de piston pour moteur a combustion interne
JP2011032551A (ja) * 2009-08-04 2011-02-17 Hitachi-Ge Nuclear Energy Ltd 炭素鋼部材の防食方法
JP2013129899A (ja) * 2011-12-22 2013-07-04 Toyota Motor Corp 断熱部材の製造方法およびこれにより製造された内燃機関

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JP2011225407A (ja) * 2010-04-22 2011-11-10 Toyota Motor Corp 多孔質断熱部材およびこれを備えた内燃機関
WO2012008372A1 (fr) * 2010-07-12 2012-01-19 神戸セラミックス株式会社 Matrice à isolation thermique et son procédé de production

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Publication number Priority date Publication date Assignee Title
WO2001033065A1 (fr) * 1999-10-29 2001-05-10 Nippon Piston Ring Co., Ltd. Combinaison chemise de cylindre et bague de piston pour moteur a combustion interne
JP2011032551A (ja) * 2009-08-04 2011-02-17 Hitachi-Ge Nuclear Energy Ltd 炭素鋼部材の防食方法
JP2013129899A (ja) * 2011-12-22 2013-07-04 Toyota Motor Corp 断熱部材の製造方法およびこれにより製造された内燃機関

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023048734A (ja) * 2021-09-28 2023-04-07 マツダ株式会社 ピストンの遮熱材塗布方法
JP7694308B2 (ja) 2021-09-28 2025-06-18 マツダ株式会社 ピストンの遮熱材塗布方法

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