WO2022014614A1 - 排気管 - Google Patents

排気管 Download PDF

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Publication number
WO2022014614A1
WO2022014614A1 PCT/JP2021/026361 JP2021026361W WO2022014614A1 WO 2022014614 A1 WO2022014614 A1 WO 2022014614A1 JP 2021026361 W JP2021026361 W JP 2021026361W WO 2022014614 A1 WO2022014614 A1 WO 2022014614A1
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Prior art keywords
inorganic porous
porous layer
mass
less
exhaust pipe
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PCT/JP2021/026361
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English (en)
French (fr)
Japanese (ja)
Inventor
裕亮 尾下
崇弘 冨田
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to JP2022536404A priority Critical patent/JPWO2022014614A1/ja
Publication of WO2022014614A1 publication Critical patent/WO2022014614A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features
    • F01N13/08—Other arrangements or adaptations of exhaust conduits
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features
    • F01N13/14—Exhaust or silencing apparatus characterised by constructional features having thermal insulation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features
    • F01N13/16—Selection of particular materials
    • 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
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/14—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups

Definitions

  • Patent Document 1 Japanese Patent Application Laid-Open No. 2018-031346 (hereinafter referred to as Patent Document 1) describes an exhaust pipe of an internal combustion engine in which an inorganic porous layer (heat insulating material) is arranged between a metal inner pipe and a metal outer pipe. It has been disclosed.
  • an inorganic porous layer is provided between the inner pipe and the outer pipe to insulate the space between the inner pipe and the outer pipe, and the temperature of the exhaust gas flowing into the catalyst provided downstream of the exhaust pipe. The decline is suppressed. By suppressing the temperature drop of the exhaust gas flowing into the catalyst, the warm-up of the catalyst is completed at an early stage.
  • the inorganic porous layer When the inorganic porous layer is arranged between the double pipes as in Patent Document 1, the exhaust gas does not come into direct contact with the inorganic porous layer. Therefore, the inorganic porous layer only needs to have heat insulating performance.
  • the inorganic porous layer is provided inside the inner tube of the double tube or inside the single tube, the exhaust gas comes into direct contact with the inorganic porous layer, and the inorganic porous layer is exposed to a high temperature. Therefore, when the inorganic porous layer is provided at the portion through which the exhaust gas passes, it is effective to provide a coating layer on the surface of the inorganic porous layer in order to protect the inorganic porous layer. For that purpose, it is necessary to study a coating layer that can satisfactorily protect the inorganic porous layer. It is an object of the present specification to provide an exhaust pipe in which a coating layer is provided on the surface of an inorganic porous layer.
  • the exhaust pipe disclosed in the present specification includes a metal pipe, an inorganic porous layer provided at a portion of the inner surface of the metal pipe through which exhaust gas passes, and a coating layer provided on the surface of the inorganic porous layer. You may be prepared.
  • the inorganic porous layer has a porosity of 45% by mass or more, contains ceramic fibers, and may be composed of an alumina component of 15% by mass or more and a titania component of 45% by mass or more. Further, the coating layer may have a porosity of less than 45% by volume.
  • the perspective view of the exhaust pipe is shown.
  • a partially enlarged view of the exhaust pipe is shown.
  • the sectional view of the exhaust pipe is shown.
  • the results of the experimental example are shown.
  • the results of the experimental example are shown.
  • the exhaust pipe disclosed in the present specification includes a metal pipe, an inorganic porous layer provided at a portion of the inner surface of the metal pipe through which exhaust gas passes, and a coating layer provided on the surface of the inorganic porous layer.
  • the inorganic porous layer may contain ceramic fibers.
  • the ceramic fiber can absorb the influence of the difference in the coefficient of thermal expansion between the metal tube and the inorganic porous layer.
  • the inorganic porous layer can be deformed following the deformation (heat expansion, heat contraction) of the metal tube, it is possible to prevent the inorganic porous layer from peeling off from the metal tube. That is, the adhesion between the metal tube and the inorganic porous layer is improved.
  • the inorganic porous layer can suppress the exhaust gas from coming into contact with the metal pipe and prevent the metal pipe from deteriorating. Further, since the inorganic porous layer is composed of 15% by mass or more of an alumina component and 45% by mass or more of a titania component, the melting point of the inorganic porous layer itself is high, and the shape changes due to the heat of the exhaust gas. Can also be suppressed.
  • a coating layer may be provided on the surface of the inorganic porous layer (the surface opposite to the metal pipe side). That is, the inorganic porous layer may be sandwiched between the metal tube and the coating layer.
  • the coating layer may be provided on the entire surface of the surface of the inorganic porous layer, or may be provided on a part of the surface of the inorganic porous layer.
  • the inorganic porous layer may contain flat plate-shaped plate-shaped ceramic particles.
  • the plate-shaped ceramic particles may have an aspect ratio of 10 or more and 60 or less when the cross section is observed by SEM.
  • the aspect ratio of the cross section of the plate-shaped ceramic particles contained in the inorganic porous layer can be confirmed by observing the cross section of the inorganic porous layer by SEM.
  • the plate-shaped ceramic particles appear in a rod shape in the SEM.
  • the plate-shaped ceramic particles can suppress a decrease in the strength (mechanical strength) of the inorganic porous layer itself.
  • the plate-shaped ceramic particles having a cross-sectional aspect ratio of 10 or more and 60 or less can have an aspect ratio in the manufacturing process of the inorganic porous layer by using, for example, plate-shaped ceramic particles having a cross-sectional aspect ratio of 60 or more and 100 or less as a raw material. Becomes smaller and remains in the inorganic porous as a result.
  • the plate-shaped ceramic particles By using the plate-shaped ceramic particles, a part of the ceramic fiber can be replaced with the plate-shaped ceramic particles.
  • the length of the plate-like ceramic particles (longitudinal size) is shorter than the length of the ceramic fibers.
  • the heat transfer path in the inorganic porous layer is divided, and heat transfer in the inorganic porous layer is less likely to occur.
  • the heat insulating performance of the inorganic porous layer is further improved.
  • the inorganic porous layer may contain granular particles of 0.1 ⁇ m or more and 10 ⁇ m or less. When the inorganic porous layer is formed (baked), the ceramic fibers are bonded to each other via granular particles to obtain a high-strength inorganic porous layer. Further, the thickness of the inorganic porous layer may be 1 mm or more. As a result, the heat insulating property of the exhaust pipe can be sufficiently exhibited. In the exhaust pipe, since the inorganic porous layer contains ceramic fibers, it is possible to realize an inorganic porous layer of 1 mm or more.
  • the inorganic porous layer can be formed to 1 mm or more.
  • the inorganic porous layer does not contain ceramic fibers, the inorganic porous layer shrinks during the molding process and cracks or the like occur. Therefore, when the inorganic porous layer does not contain ceramic fibers, the inorganic porous layer is inorganic porous. It is difficult to form the quality layer into a thick film of 1 mm or more.
  • the inorganic porous layer is composed of an alumina (Al 2 O 3 ) component of 15% by mass or more and 55% by mass or less and a titania (TiO 2 ) component of 45% by mass or more and 85% by mass or less. ..
  • the alumina component contained in the inorganic porous layer may be 25% by mass or more, 30% by mass or more, or 40% by mass or more.
  • the porosity of the inorganic porous layer may be 45% by volume or more and 90% by volume or less. When the porosity is 45% by volume or more, the heat insulating property can be sufficiently exhibited. Further, when the porosity is 90% by volume or less, sufficient strength can be secured.
  • the porosity of the inorganic porous layer may be 55% by volume or more, 60% by volume or more, or 65% by volume or more. Further, the porosity of the inorganic porous layer may be 85% by volume or less, 80% by volume or less, 70% by volume or less, 65% by volume or less, and 60% by volume. It may be as follows.
  • the porosity of the inorganic porous layer may be 45% by volume or more and 90% by volume or less as a whole, and the porosity may differ in the thickness direction. .. In this case, there may be a portion having a porosity of less than 45% by volume or a portion having a porosity of more than 90% by volume.
  • the thickness of the inorganic porous layer may be 1 mm or more, although it depends on the required performance. When the thickness of the inorganic porous layer is 1 mm or more, the heat insulating property can be sufficiently exhibited. In the case of the inorganic porous layer in which the ceramic fiber is not used, it is difficult to maintain the thickness at 1 mm or more because it shrinks in the manufacturing process (for example, the firing step). Since the inorganic porous layer disclosed in the present specification contains ceramic fibers, shrinkage in the manufacturing process is suppressed, and a thickness of 1 mm or more can be maintained.
  • the thickness of the inorganic porous layer may be 30 mm or less, 20 mm or less, 15 mm or less, 10 mm or less, and 5 mm or less.
  • the material of the coating layer may be a porous or dense ceramic.
  • the porous ceramic used in the coating layer include zirconia (ZrO 2 ), partially stabilized zirconia, stabilized zirconia and the like.
  • yttria-stabilized zirconia ZrO 2- Y 2 O 3 : YSZ
  • a metal oxide obtained by adding Gd 2 O 3 , Yb 2 O 3 , Er 2 O 3, etc.
  • the coating layer may be one in which ceramic fibers and plate-shaped ceramic particles are removed from the constituent materials of the inorganic porous layer to have a lower porosity (denseness) than that of the inorganic porous layer. That is, the coating layer may be composed of a material of the same quality as the inorganic porous layer (alumina component of 15% by mass or more and 55% by mass or less and a titania component of 45% by mass or more and 85% by mass or less).
  • alumina component of 15% by mass or more and 55% by mass or less
  • a titania component of 45% by mass or more and 85% by mass or less
  • the inorganic porous layer can be reinforced and the inorganic porous layer can be prevented from peeling off from the surface of the metal tube.
  • a dense ceramic is used as the coating layer, for example, it is possible to suppress the permeation of high-temperature gas through the inorganic porous layer and the retention of exhaust gas in the inorganic porous layer. As a result, the effect of suppressing the heat transfer of the exhaust gas to the metal pipe can be expected.
  • the porosity of the coating layer is lower than the porosity of the inorganic porous layer, and specifically, it may be less than 45% by volume.
  • the porosity is less than 45% by volume, it is possible to prevent the exhaust gas from passing through the coating layer and coming into contact with the inorganic porous layer. Further, when the porosity is less than 45% by volume, the strength of the coating layer is sufficiently secured, and the coating layer is suppressed from being damaged due to the vibration of the exhaust pipe and the force applied from the exhaust gas.
  • the thickness of the coating layer may be determined according to the thickness of the inorganic porous layer. Specifically, the thickness of the coating layer may be 0.05 times or more and 0.5 times or less the thickness of the inorganic porous layer. When the thickness of the coating layer is 0.05 times or more the thickness of the inorganic porous layer, it is possible to prevent the inorganic porous layer from being damaged by a physical impact (for example, vibration of the exhaust pipe). Further, if the thickness of the coating layer is 0.5 times or less the thickness of the inorganic porous layer, the heat impact resistance of the coating layer is ensured. It is possible to prevent the coating layer from being damaged even when the gas passes through the exhaust pipe.
  • Equation 1 0.5 ⁇ 1 / ⁇ 2 ⁇ 1.2
  • the difference in thermal conductivity between the metal tube and the inorganic porous layer is large.
  • the thermal conductivity of the metal tube may be 100 times or more the thermal conductivity of the inorganic porous layer.
  • the thermal conductivity of the metal tube may be 150 times or more the thermal conductivity of the inorganic porous layer, 200 times or more the thermal conductivity of the inorganic porous layer, and the heat of the inorganic porous layer.
  • the conductivity may be 250 times or more, and the thermal conductivity of the inorganic porous layer may be 300 times or more.
  • the thermal conductivity of the metal tube may be 10 W / mK or more and 400 W / mK or less.
  • the thermal conductivity of the metal tube may be 25 W / mK or more, 50 W / mK or more, 100 W / mK or more, 150 W / mK or more, and 200 W / mK or more. It may be 250 W / mK or more, 300 W / mK or more, or 380 W / mK or more.
  • the thermal conductivity of the metal tube may be 350 W / mK or less, 300 W / mK or less, 250 W / mK or less, 200 W / mK or less, 150 W / mK or less. May be.
  • the thermal conductivity of the inorganic porous layer may be 0.05 W / mK or more and 3 W / mK or less.
  • the thermal conductivity of the inorganic porous layer may be 0.1 W / mK or more, 0.2 W / mK or more, 0.3 W / mK or more, and 0.5 W / mK or more. It may be 0.7 W / mK or more, 1 W / mK or more, 1.5 W / mK or more, or 2 W / mK or more.
  • the thermal conductivity of the inorganic porous layer may be 2.5 W / mK or less, 2.0 W / mK or less, 1.5 W / mK or less, and 1 W / mK or less. It may be 0.5 W / mK or less, 0.3 W / mK or less, and 0.25 W / mK or less.
  • the metal pipe may be a single pipe or a multiple pipe (for example, a double pipe).
  • the metal tube may be linear, the whole (or a part) may be curved, the intermediate portion may be tapered, or the metal tube may be a branch tube.
  • the inorganic porous layer may be provided on the inner surface of the metal tube in the case of a single tube, or on the inner surface of the metal tube arranged on the innermost side in the case of a multiple tube.
  • the inorganic porous layer may cover the entire inner surface of the metal tube or a part of the inner surface of the metal tube.
  • the inorganic porous layer may cover a portion other than the end portion (one end or both ends) of the metal tube.
  • the inorganic porous layer may be made of a uniform material in the thickness direction. That is, the inorganic porous layer may be a single layer. Further, the inorganic porous layer may be composed of a plurality of layers having different compositions in the thickness direction. That is, the inorganic porous layer may have a multi-layer structure in which a plurality of layers are laminated. Alternatively, the inorganic porous layer may have an inclined structure in which the composition gradually changes in the thickness direction.
  • the exhaust pipe can be easily manufactured (the step of forming the inorganic porous layer on the inner surface of the metal pipe).
  • the characteristics of the inorganic porous layer can be changed in the thickness direction.
  • the ratio of the rutile-type crystal phase to the titania component can be made larger than that of other portions.
  • the structure of the inorganic porous layer (single layer, multi-layer, inclined structure) can be appropriately selected according to the purpose of use of the exhaust pipe.
  • the inorganic porous layer is composed of one or more materials of ceramic particles (granular particles), plate-shaped ceramic particles, and ceramic fibers.
  • the ceramic particles, the plate-shaped ceramic particles, and the ceramic fibers may contain alumina and / or titania as constituent components.
  • the ceramic particles, the plate-shaped ceramic particles, and the ceramic fibers may be formed by alumina and / or titania. That is, the inorganic porous layer may contain 15% by mass or more of an alumina component and 45% by mass or more of a titania component in the entire constituent material (constituting substance).
  • the inorganic porous layer contains at least ceramic fibers, although the constituent components are arbitrary (alumina component and titania component may or may not be contained).
  • the ceramic particles may be used as a bonding material for joining aggregates forming the skeleton of an inorganic porous layer such as plate-shaped ceramic particles and ceramic fibers.
  • the ceramic particles may be granular particles of 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the ceramic particles may have a larger particle size due to sintering or the like in the manufacturing process (for example, firing process). That is, as a raw material for producing the inorganic porous layer, the ceramic particles may be granular particles having a size of 0.1 ⁇ m or more and 10 ⁇ m or less (average particle size before firing).
  • the ceramic particles may be 0.5 ⁇ m or more, and may be 5 ⁇ m or less.
  • a metal oxide may be used as the material of the ceramic particles.
  • metal oxide alumina (Al 2 O 3), spinel (MgAl 2 O 4), titania (TiO 2), zirconia (ZrO 2), magnesia (MgO), mullite (Al 6 O 13 Si 2) , cordierite (MgO ⁇ Al 2 O 3 ⁇ SiO 2), yttria (Y 2 O 3), steatite (MgO ⁇ SiO 2), forsterite (2MgO ⁇ SiO 2), lanthanum aluminate (LaAlO 3), strontium titanate (SrTiO 3 ) and the like can be mentioned.
  • These metal oxides have high corrosion resistance and can be suitably applied as a protective layer for an exhaust pipe.
  • the ceramic particles contain titania particles, the inclusion of the rutile-type crystal phase in the ceramic particles improves the thermal impact resistance of the bonding material that joins the aggregates, and suppresses the deterioration of the inorganic porous layer.
  • the plate-shaped ceramic can function as an aggregate or a reinforcing material in the inorganic porous layer. That is, the plate-shaped ceramic, like the ceramic fiber, improves the strength of the inorganic porous layer and further suppresses the shrinkage of the inorganic porous layer in the manufacturing process. By using the plate-shaped ceramic particles, the heat transfer path in the inorganic porous layer can be divided. Therefore, the heat insulating property can be improved as compared with the form in which only the ceramic fiber is used as the aggregate.
  • the surface shape (shape observed from the thickness direction) of the flat plate-shaped ceramic particles is not particularly limited, and is, for example, a polygon such as a rectangle, a substantially circular shape, a curved line, and / or an indefinite shape surrounded by a straight line. If the size in the longitudinal direction when observing the cross section is 5 ⁇ m or more, excessive sintering of the ceramic particles can be suppressed. When the size in the longitudinal direction is 100 ⁇ m or less, the effect of dividing the heat transfer path in the inorganic porous layer can be obtained as described above, and it can be suitably applied to an exhaust pipe used in a high temperature environment. Further, the plate-shaped ceramic particles may have an aspect ratio of 10 or more and 60 or less in cross section.
  • the aspect ratio of the cross section is 10 or more, sintering of the ceramic particles can be satisfactorily suppressed, and the inorganic porous layer becomes too hard (Young's modulus becomes too high) after production (after firing). Can be suppressed. As a result, it is possible to prevent the inorganic porous layer from being damaged (cracking or the like) due to thermal shock immediately after the start of the internal combustion engine (contact of high-temperature exhaust gas with the inorganic porous in a low temperature state).
  • the aspect ratio of the cross section is 60 or less, the decrease in the strength of the plate-shaped ceramic particles themselves is suppressed, and the damage of the inorganic porous layer due to the vibration of the exhaust pipe or the gas flow of the exhaust gas can be suppressed.
  • the material of the plate-shaped ceramic particles in addition to the metal oxide used as the material of the ceramic particles described above, talc (Mg 3 Si 4 O 10 (OH) 2 ), minerals such as mica and kaolin, clay, glass and the like. Can also be used.
  • the ceramic fiber can function as an aggregate or a reinforcing material in the inorganic porous layer. That is, the ceramic fiber improves the strength of the inorganic porous layer and further suppresses the shrinkage of the inorganic porous layer in the manufacturing process.
  • the length of the ceramic fiber may be 50 ⁇ m or more and 200 ⁇ m or less.
  • the diameter (average diameter) of the ceramic fiber may be 1 to 20 ⁇ m.
  • the volume fraction of the ceramic fiber in the raw material for forming the inorganic porous layer may be 5% by volume or more and 25% by volume or less.
  • the shrinkage of the ceramic particles in the inorganic porous layer can be sufficiently suppressed in the manufacturing process (firing step) of the inorganic porous layer. Further, by setting the volume ratio of the ceramic fibers in the raw material to 25% by volume or less (that is, the volume ratio of the ceramic fibers in the inorganic porous layer is 25% by volume or less), the heat transfer path in the inorganic porous layer is set. It can be divided and heat transfer to the metal tube can be suitably suppressed.
  • the ratio (volume ratio) of the ceramic fiber in the inorganic porous layer should be measured by image processing the result of EDS analysis. Can be done.
  • alumina Al 2 O 3
  • spinel MgAl 2 O 4
  • titania TiO 2
  • zirconia ZrO 2
  • magnesia MgO
  • mullite Al 6 O 13 Si 2
  • cordierite MgO ⁇ Al 2 O 3 ⁇ SiO 2
  • yttria Y 2 O 3
  • steatite MgO ⁇ SiO 2
  • forsterite 2MgO ⁇ SiO 2
  • LaAlO 3 lanthanum aluminate
  • strontium The same material as the above-mentioned ceramic particles such as titanate (SrTiO 3) can be used.
  • the inorganic porous layer may contain one or more kinds of ceramic fibers formed of the above materials.
  • the content of aggregates and reinforcing materials (ceramic fibers, plate-shaped ceramic particles, etc., hereinafter simply referred to as aggregates) in the raw materials for forming the inorganic porous layer is 15% by mass or more and 55% by mass or less. May be.
  • the content of the aggregate in the raw material is 15% by mass or more, the shrinkage of the inorganic porous layer in the firing step can be sufficiently suppressed.
  • the content of the aggregate in the raw material is 55% by mass or less, the aggregates are satisfactorily bonded to each other by the ceramic particles.
  • the content of the aggregate in the raw material may be 20% by mass or more, 30% by mass or more, 50% by mass or more, or 53% by mass or more.
  • the content of the aggregate in the raw material may be 53% by mass or less, 50% by mass or less, 30% by mass or less, or 20% by mass or less.
  • both the ceramic fiber and the plate-shaped ceramic particle can function as an aggregate and a reinforcing material in the inorganic porous layer.
  • the inorganic porous layer is used.
  • the content of the ceramic fiber in the raw material when forming the layer may be at least 5% by mass or more.
  • the content of the ceramic fiber in the raw material may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more.
  • the content of the ceramic fiber in the raw material may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, and 10% by mass. It may be less than or equal to%.
  • the ratio of the plate-shaped ceramic particles to the entire aggregate may be 70% by mass or less. That is, in terms of mass ratio, at least 30% by mass or more of the aggregate may be ceramic fibers.
  • the ratio of the plate-shaped ceramic particles to the entire aggregate may be 67% by mass or less, 64% by mass or less, 63% by mass or less, 60% by mass or less, and 50. It may be mass% or less.
  • the plate-shaped ceramic particles are not always essential as an aggregate.
  • the ratio of the plate-shaped ceramic particles to the entire aggregate may be 40% by mass or more, 50% by mass or more, 60% by mass or more, and 62% by mass or more. , 63% by mass or more, and may be 65% by mass or more.
  • the content of the plate-shaped ceramic particles in the raw material for forming the inorganic porous layer may be 5% by mass or more and 35% by mass or less.
  • 5% by mass or more of plate-shaped ceramic particles as the raw material of the inorganic porous layer it is possible to sufficiently suppress the shrinkage of the ceramic particles in the inorganic porous layer in the manufacturing process (firing step) of the inorganic porous layer. can.
  • the content of the plate-shaped ceramic particles in the raw material is 35% by mass or less (that is, the ratio of the plate-shaped ceramic particles in the inorganic porous layer to 35% by mass or less)
  • the content of the plate-shaped ceramic particles in the inorganic porous layer is 35% by mass or less.
  • the heat transfer path can be divided, and heat transfer to the metal tube can be suitably suppressed.
  • the content of the plate-shaped ceramic particles in the raw material may be 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, and 33% by mass. It may be% or more.
  • the content of the plate-shaped ceramic particles in the raw material may be 35% by mass or less, 33% by mass or less, 30% by mass or less, or 20% by mass or less. It may be 10% by mass or less.
  • the SiO 2 contained in the inorganic porous layer may be 25% by mass or less.
  • the formation of an amorphous layer in the inorganic porous layer is suppressed, and the heat resistance (durability) of the inorganic porous layer is improved.
  • a raw material in which a binder, a pore-forming material, and a solvent are mixed may be used in addition to ceramic particles, plate-shaped ceramic particles, and ceramic fibers.
  • a binder an inorganic binder may be used.
  • the inorganic binder include alumina sol, silica sol, titania sol, zirconia sol and the like. These inorganic binders can improve the strength of the inorganic porous layer after firing.
  • a polymer-based pore-forming material, carbon-based powder, or the like may be used as the pore-forming material.
  • the pore-forming material may have various shapes depending on the purpose, and may be, for example, spherical, plate-shaped, fibrous, or the like. By selecting the addition amount, size, shape, etc. of the pore-forming material, the porosity and pore size of the inorganic porous layer can be adjusted.
  • the solvent may be any solvent as long as the viscosity of the raw material can be adjusted without affecting other raw materials, and for example, water, ethanol, isopropyl alcohol (IPA) or the like can be used.
  • the above-mentioned inorganic binder is also a constituent material of the inorganic porous layer. Therefore, when alumina sol, titania sol, etc. are used to form the inorganic porous layer, the inorganic porous layer contains 15% by mass or more of the alumina component and 45% by mass or more of the titania component in the entire constituent material including the inorganic binder. It may be included.
  • the composition and raw material of the inorganic porous layer are adjusted according to the type of the metal tube.
  • the exhaust pipe disclosed in the present specification is not particularly limited, but as the metal pipe, stainless steel such as SUS430, SUS429, SUS444, iron, cast iron, copper, Hastelloy, Inconel, Kovar, nickel alloy and the like can be used.
  • the composition and raw material of the inorganic porous layer may be adjusted according to the coefficient of thermal expansion of the metal tube used. Specifically, when the coefficient of thermal expansion of the inorganic porous layer is ⁇ 1 and the coefficient of thermal expansion of the metal tube is ⁇ 2, the following equation 1 may be adjusted to be satisfied.
  • the coefficient of thermal expansion ⁇ 1 is 6 ⁇ 10 -6 / K ⁇ 1 ⁇ 14 ⁇ 10 -6 / K, and more preferably the coefficient of thermal expansion ⁇ 1 is 6 ⁇ 10 -6.
  • the composition and raw materials of the inorganic porous layer may be adjusted so that / K ⁇ 1 ⁇ 11 ⁇ 10-6 / K.
  • the coefficient of thermal expansion ⁇ 1 is 8.5 ⁇ 10 -6 / K ⁇ 1 ⁇ 20 ⁇ 10 -6 / K, and more preferably, the coefficient of thermal expansion ⁇ 1 is 8.5.
  • composition and raw materials of the inorganic porous layer may be adjusted so that ⁇ 10-6 / K ⁇ 1 ⁇ 18 ⁇ 10-6 / K.
  • the value of " ⁇ 1 / ⁇ 2" may be 0.55 or more, 0.6 or more, 0.65 or more, 0.75 or more, and 0.8. It may be the above. Further, the value of " ⁇ 1 / ⁇ 2" may be 1.15 or less, 1.1 or less, 1.05 or less, or 1.0 or less. Equation 1: 0.5 ⁇ 1 / ⁇ 2 ⁇ 1.2
  • the above raw material may be applied to the inner surface of the metal pipe, dried and fired to form an inorganic porous layer on the inner surface of the metal pipe.
  • a method for applying the raw material dip coating, spin coating, aerosol deposition (AD) method, brush coating, trowel coating, mold cast molding and the like can be used. If the target inorganic porous layer is thick, or if the inorganic porous layer has a multi-layer structure, the application of the raw material and the drying of the raw material are repeated multiple times to adjust the thickness to the target or the multi-layer structure. You may.
  • the above coating method can also be applied as a coating method for forming a coating layer, which will be described later.
  • the exhaust pipe 10 will be described with reference to FIGS. 1 to 3.
  • the exhaust pipe 10 is provided with an inorganic porous layer 4 on the inner surface of a metal pipe 2 made of SUS430. Further, a coating layer 6 is provided on the surface of the inorganic porous layer 4.
  • the inorganic porous layer 4 is bonded to the inner surface of the metal tube 2, and the coating layer 6 is bonded to the inner surface of the inorganic porous layer 4.
  • the exhaust pipe 10 was manufactured by immersing the metal pipe 2 in the raw material slurry, drying and firing the metal pipe 2 with the outer surface of the metal pipe 2 masked.
  • the raw material slurry of the inorganic porous layer 4 includes alumina fibers (average fiber length 140 ⁇ m), plate-like alumina particles (average particle diameter 6 ⁇ m), titania particles (average particle diameter 0.25 ⁇ m), and alumina sol. (Alumina amount 1.1% by mass), acrylic resin (average particle size 8 ⁇ m), and ethanol were mixed to prepare the mixture.
  • the raw material slurry was adjusted so that the viscosity was 2000 mPa ⁇ s.
  • the raw material slurry of the coating layer 6 is plate-shaped alumina particles (average particle diameter 6 ⁇ m), titania particles (average particle diameter 0.25 ⁇ m), alumina sol (alumina amount 1.1% by mass), and acrylic resin (average). Particle size 8 ⁇ m) and ethanol were mixed to prepare. That is, the raw material slurry used for molding the coating layer 6 is obtained by removing the alumina fibers from the raw material slurry used for forming the inorganic porous layer 4. The raw material slurry for molding the coating layer 6 was also adjusted so that the viscosity was 2000 mPa ⁇ s.
  • the metal tube 2 After immersing the metal tube 2 in the raw material slurry for the inorganic porous layer and applying the raw material to the inner surface of the metal tube 2, the metal tube 2 was put into a dryer and dried at 200 ° C. (atmospheric atmosphere) for 1 hour. As a result, an inorganic porous layer 4 having a thickness of about 300 ⁇ m was formed on the inner surface of the metal tube 2. Then, the step of immersing the metal tube 2 in the raw material slurry for the inorganic porous layer and drying it was repeated three times to form the 1.2 mm inorganic porous layer 4 on the inner surface of the metal tube 2. Next, the steps of immersing and drying the metal tube 2 on which the inorganic porous layer 4 was formed in the coating layer raw material slurry were performed twice to form a 0.6 mm coating layer 6 on the inner surface of the inorganic porous layer 4.
  • the metal pipe 2 was placed in an electric furnace and fired at 800 ° C. in an atmospheric atmosphere to prepare an exhaust pipe 10.
  • the inorganic porous layer 4 was formed on the entire inner surface of the metal tube 2, and the coating layer 6 was formed on the entire inner surface of the inorganic porous layer 4 (see FIG. 3).
  • the porosity of the inorganic porous layer 4 was 70% by volume, and the porosity of the covering layer 8 was 30% by volume.
  • Example 1 As described above, for the inorganic porous layer, a raw material slurry in which alumina fibers, plate-like alumina particles, titania particles, alumina sol, acrylic resin and ethanol are mixed is prepared, a metal tube is immersed in the raw material slurry, and then dried and It was created by firing.
  • the proportions of the alumina fiber, the plate-like alumina particle and the titania particle were changed, and the alumina fiber was changed to the mullite fiber.
  • the plate-like alumina particles were replaced with plate-like mica, and the state of the inorganic porous layer after firing was confirmed.
  • the blending amounts of ceramic fibers (alumina fibers,glasse fibers), plate-shaped ceramic particles (plate-shaped alumina particles, plate-shaped mica), titania particles, and zirconia particles are changed as shown in FIG. , Plate-shaped ceramic particles, titania particles and zirconia particles are blended so that the total is 100% by mass, and further, 10% by mass of alumina sol (1.1% by mass of alumina contained in the alumina sol), acrylic resin 40 A raw material slurry was prepared by adding mass% and adjusting the slurry viscosity with ethanol. Note that sample 5 does not use plate-shaped ceramic particles, and samples 1 to 7, 10, 12 and 13 do not use zirconia particles.
  • the raw material slurry was applied to the SUS430 plate for the samples 1 to 8, 11 to 13, and the raw material slurry was applied to the copper plate for the samples 9 and 10, and dried at an air atmosphere of 200 ° C. for 1 hour, and then the air atmosphere 800. It was baked at ° C for 3 hours.
  • the number of times the raw material slurry was applied (the number of times the metal plate was immersed) in each sample was adjusted so that an inorganic porous layer of about 1.2 mm was formed on the metal plate (SUS430 plate and copper plate).
  • the purpose of this experimental example was to confirm the effect of the amounts of the alumina component (ceramic fiber, plate-shaped ceramic particles) and the titania component on the appearance of the inorganic porous layer (presence or absence of cracks, peeling, etc.). Therefore, the coating layer is not formed on the surface of the inorganic porous layer.
  • the prepared samples 1 to 13 measurement of the ratio (mass%) of the alumina component and the titania component in the inorganic porous layer, measurement of the porosity (volume%) of the inorganic porous layer, the inorganic porous layer and the metal.
  • the thermal expansion coefficient of the plate was also measured.
  • the sample for measuring the component ratio and the porosity and the sample for measuring the thermal expansion coefficient of the inorganic porous layer are formed into a bulk body of the inorganic porous layer using the above-mentioned raw material slurry, and then the bulk body is formed at 800 ° C. It was produced by firing in.
  • Alumina and titania component ICP emission spectrometer (Hitachi High-Tech Science Ltd., PS3520UV-DD) was used to measure the aluminum and titanium amounts, indicates terms of oxides (Al 2 O 3, TiO 2 ) as a result ing.
  • the coefficient of thermal expansion was obtained by molding the above-mentioned raw material slurry into a bulk body of 3 mm ⁇ 4 mm ⁇ 20 mm and then calcining the bulk body at 800 ° C. to prepare a sample for measurement. Then, the measurement sample was measured using a thermal expansion meter in accordance with JIS R1618 (a method for measuring thermal expansion by thermomechanical analysis of fine ceramics). The coefficient of thermal expansion was measured separately for the inorganic porous layer and the metal plate.
  • thermal conductivity of the inorganic porous layers of Samples 1 to 4 and the metal plates of Samples 1 to 13 was measured. Thermal conductivity was also measured using separate bulk bodies for the inorganic porous layer and the metal plate. The thermal conductivity was calculated by multiplying the thermal diffusivity, the specific heat capacity and the bulk density. For the heat diffusion rate, a laser flash method heat constant measuring device is used, and for the specific heat capacity, a DSC (differential scanning calorimetry) is used. Method) was measured at room temperature.
  • the bulk density (unit: g / cm 3 ) of the inorganic porous layer was calculated from the following formula (3).
  • the thermal diffusivity is obtained by molding the above-mentioned raw material slurry into a bulk body having a diameter of 10 mm ⁇ 1 mm
  • the specific heat capacity is obtained by molding the above-mentioned raw material slurry into a bulk body having a diameter of 5 mm ⁇ a thickness of 1 mm, and then each bulk body is 800.
  • the proportion of the alumina component in the sample 11 is less than 15% by mass, it is presumed that the bonding force between the ceramics (particles, fibers) is reduced and cracks are generated in the inorganic porous layer.
  • the proportion of the titania component in the sample 12 is less than 45% by mass, it is presumed that the bonding force between the ceramics is lowered and cracks are generated in the inorganic porous layer.
  • the content of the titania component (titania particles) having a high coefficient of thermal expansion is low, and the ratio of the coefficient of thermal expansion to the metal ( ⁇ 1 / ⁇ 2) is small (less than 0.5).
  • the inorganic porous layer was separated from the metal based on the difference in thermal expansion. From the above, regardless of the type of ceramic fiber (alumina fiber, mullite fiber) and the type of plate-shaped ceramic particles (plate-shaped alumina particle, plate-shaped mica), 15% by mass or more of alumina component and 45% by mass or more of titania component. It was confirmed that the inorganic porous layer containing the above was less likely to cause deterioration such as cracks and peeling after firing.
  • Example 2 In this experimental example, in order to confirm the influence of the morphology of the inorganic porous layer and the coating layer on the characteristics of the exhaust pipe, the porosity of the inorganic porous layer and the coating layer and the thickness of the coating layer with respect to the thickness of the inorganic porous layer The thermal shock resistance and vibration resistance of the exhaust pipe were evaluated by changing the proportions and the proportions of the alumina component and the titania component contained in the inorganic porous layer and the coating layer. The porosity measurement and the alumina / titania component measurement were carried out by the same method as in Experimental Example 1.
  • the mixing amounts of alumina fibers, plate-shaped alumina particles, titania particles, and acrylic resin, and the number of times the coating layer is immersed in the raw material slurry are adjusted, and the porosity of the inorganic porous layer and the coating layer and the inorganic porous layer are adjusted.
  • the ratio of the thickness of the coating layer to the thickness of the coating layer and the ratio of the alumina component and the titania component contained in the inorganic porous layer and the coating layer were changed as shown in FIG.
  • the thickness of the inorganic porous layer was 1.2 mm.
  • the sample 21 does not form a coating layer.
  • the alumina fiber was replaced with a mullite fiber, and the plate-shaped alumina particles were replaced with a plate-shaped mica.
  • Thermal impact resistance and vibration resistance were evaluated by conducting a heating vibration test.
  • an inorganic porous layer is obtained by circulating LP gas at 900 ° C. for 5 minutes and then air gas at room temperature for 5 minutes while applying vibration of 100 Hz and 30 G to the inside of the sample (inside the exhaust pipe).
  • the rate of change in weight was measured.
  • the sample with a weight change rate of 0.8% or less after the test is “ ⁇ ”
  • the sample with a weight change rate of more than 0.8% and 1% or less is “ ⁇ ”
  • the weight change rate is more than 1%.
  • the sample is indicated by an "x”.
  • the samples (samples 22, 23, 25, 27 to 32) in which the porosity of the inorganic porous layer is 45% by volume or more and the porosity of the coating layer is less than 45% by volume are the coating layer.
  • the sample 24 having a porosity of 45% by volume or more (60% by volume) and the sample 26 having a porosity of less than 45% by volume (40% by volume) (evaluation "x"). It was confirmed that the weight loss rate after the test was low (evaluation " ⁇ " or " ⁇ ").
  • the strength of the coating layer of the sample 24 was lower than that of the other samples, and the coating layer was damaged due to the vibration applied to the coating layer and the force applied from the high-temperature LP gas. Further, it is presumed that in the sample 26, the heat insulating performance of the inorganic porous layer deteriorated as the porosity decreased, and a part of the inorganic porous layer was damaged by the thermal shock applied from the high temperature LP gas. ..
  • the sample 21 having no coating layer had a high weight loss rate (evaluation "x").
  • the porosity of the inorganic porous layer was 45% by volume or more regardless of the type of ceramic fiber (alumina fiber,glasse fiber) and the type of plate-shaped ceramic particles (plate-shaped alumina particle, plate-shaped mica). It was confirmed that the heat impact resistance and vibration resistance of the exhaust pipe were improved by adjusting the porosity of the coating layer to less than 45% by volume.
  • the thickness of the coating layer with respect to the thickness of the inorganic porous layer is further compared.
  • the sample 28 (evaluation " ⁇ ") having a low ratio and the sample 29 (evaluation " ⁇ ") having a high ratio of the thickness of the coating layer to the thickness of the inorganic porous layer are compared with other samples (evaluation " ⁇ "). Therefore, the weight loss rate after the heating vibration test tended to increase. It is presumed that the sample 28 had a low thickness ratio of the coating layer (0.03 times), and the effect of reinforcing the inorganic porous layer was not sufficiently obtained.
  • the thickness ratio of the coating layer was high (1 times), and the high temperature LP gas came into contact with the low temperature coating layer immediately after the start of the heating vibration test, so that a part of the coating layer was damaged by thermal shock. It is inferred that. From the above results, by adjusting the ratio of the thickness of the coating layer to the thickness of the inorganic porous layer to 0.05 times or more and 0.5 times or less, an exhaust pipe having excellent heat impact resistance and vibration resistance can be obtained. It was confirmed that.
  • the coating layer is 15.
  • the samples (samples 22, 23, 25, 32) containing an alumina component of mass% or more and a titania component of 45% by mass or more include a sample 30 (evaluation “ ⁇ ”) having a titania component of less than 45% by mass and an alumina component of 15. Compared with the sample 31 of less than mass% (evaluation “ ⁇ ”), the weight loss rate after the heating vibration test tended to be lower.
  • the proportion of the titania component was low, the bonding force between the ceramics in the coating layer was lowered, and the effect of reinforcing the inorganic porous layer was lowered. Further, it is presumed that the sample 31 had a low proportion of alumina components (that is, the amount of plate-like alumina particles added), and the strength of the coating layer itself was lowered. From the above results, regardless of the type of ceramic fiber (alumina fiber, mullite fiber) and the type of plate-shaped ceramic particles (plate-shaped alumina particles, plate-shaped mica), the coating layer has an alumina component of 15% by mass or more and 45% by mass. It was confirmed that the thermal shock resistance and vibration resistance of the exhaust pipe were improved by containing% or more of the titania component.

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JP2023146509A (ja) * 2022-03-29 2023-10-12 日本碍子株式会社 排気管

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06239656A (ja) * 1993-02-12 1994-08-30 Ibiden Co Ltd 触媒用断熱材
JP2012167543A (ja) * 2011-02-09 2012-09-06 Ibiden Co Ltd 構造体、及び、構造体の製造方法
WO2014034395A1 (ja) * 2012-08-27 2014-03-06 イビデン株式会社 排気系部品用塗料及び排気系部品
JP2018031346A (ja) * 2016-08-26 2018-03-01 トヨタ自動車株式会社 排気管

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06239656A (ja) * 1993-02-12 1994-08-30 Ibiden Co Ltd 触媒用断熱材
JP2012167543A (ja) * 2011-02-09 2012-09-06 Ibiden Co Ltd 構造体、及び、構造体の製造方法
WO2014034395A1 (ja) * 2012-08-27 2014-03-06 イビデン株式会社 排気系部品用塗料及び排気系部品
JP2018031346A (ja) * 2016-08-26 2018-03-01 トヨタ自動車株式会社 排気管

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023146509A (ja) * 2022-03-29 2023-10-12 日本碍子株式会社 排気管
JP7743345B2 (ja) 2022-03-29 2025-09-24 日本碍子株式会社 排気管

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