WO2020008561A1 - Matériau poreux et matériau d'isolation thermique - Google Patents

Matériau poreux et matériau d'isolation thermique Download PDF

Info

Publication number
WO2020008561A1
WO2020008561A1 PCT/JP2018/025358 JP2018025358W WO2020008561A1 WO 2020008561 A1 WO2020008561 A1 WO 2020008561A1 JP 2018025358 W JP2018025358 W JP 2018025358W WO 2020008561 A1 WO2020008561 A1 WO 2020008561A1
Authority
WO
WIPO (PCT)
Prior art keywords
porous material
particles
zirconia
heat insulating
pore diameter
Prior art date
Application number
PCT/JP2018/025358
Other languages
English (en)
Japanese (ja)
Inventor
晃暢 織部
崇弘 冨田
Original Assignee
日本碍子株式会社
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 日本碍子株式会社 filed Critical 日本碍子株式会社
Priority to PCT/JP2018/025358 priority Critical patent/WO2020008561A1/fr
Publication of WO2020008561A1 publication Critical patent/WO2020008561A1/fr

Links

Images

Classifications

    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • 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

Definitions

  • the present invention relates to a porous material and a heat insulating material.
  • Insulation materials are required to have low thermal conductivity. Also, depending on the use of the heat insulating material, the heat insulating material may be required to have a low heat capacity.
  • the heat insulating film described in Patent Document 1 includes a porous material (paragraph 0064).
  • the porous material has a skeleton (paragraph 0024). A plurality of pores are formed in the porous material (paragraph 0024).
  • the skeleton is composed of ZrO 2 particles (paragraph 0022).
  • the porous material preferably has an average pore size of 0.5-500 nm (paragraph 0026). Further, the porous material preferably has a thermal conductivity of 1.5 W / mK or less, and preferably has a heat capacity of 1500 kJ / m 3 K or less (paragraphs 0069-0070).
  • the present invention has been made in view of this problem.
  • the problem to be solved by the present invention is to provide a porous material having low thermal conductivity and low heat capacity.
  • the porous material has a skeleton including a plurality of zirconia particles made of zirconia. A plurality of pores are formed in the porous material.
  • the plurality of pores are such that when the pore diameter becomes the first pore diameter, the log differential pore volume reaches the first peak value, and the pore diameter becomes the second pore diameter larger than the first pore diameter.
  • the plurality of pores formed in the porous material include many small pores having a pore diameter close to the first pore diameter of 0.05 ⁇ m or more and 2 ⁇ m or less, and are larger than the first pore diameter. Many pores having a pore diameter close to the second pore diameter of 0.2 ⁇ m or more and 50 ⁇ m or less are included. Small pores contribute to lowering the thermal conductivity of the porous material. In addition, the pores contribute to lowering the heat capacity of the porous material. Thereby, a porous material having low heat conductivity and low heat capacity can be provided.
  • FIG. 1 It is a perspective view which illustrates typically the heat insulating material with a sheet
  • FIG. 4 is a graph showing a pore size distribution of a plurality of pores formed in the porous material according to the first embodiment. It is a figure which shows the TEM image obtained by observing the 1st trial product of the porous material of 1st Embodiment with a transmission electron microscope (TEM).
  • FIG. 8 is a diagram showing a binarized image obtained by binarizing the TEM image shown in FIG. 7.
  • FIG. 4 is a graph showing a pore size distribution of a plurality of pores formed in a second prototype of the porous material of the first embodiment. It is a figure showing the SEM picture obtained by observing the 2nd trial product of the porous material of a 1st embodiment with a scanning electron microscope (SEM). It is a figure showing the graph showing the pore diameter distribution of a plurality of pores formed in the 3rd prototype of the porous material of a 1st embodiment.
  • SEM scanning electron microscope
  • the porous material of the first embodiment can constitute a heat insulating material, can constitute a material other than the heat insulating material, and can also constitute a material that also functions as a heat insulating material and a material other than the heat insulating material. .
  • a case where the porous material of the first embodiment forms a heat insulating material will be exemplified.
  • FIG. 1 is a perspective view schematically showing a heat insulation material with a sheet including the heat insulation material of the first embodiment.
  • the heat insulating material with a sheet 100 shown in FIG. 1 includes a plurality of heat insulating materials 110 and sheets 112.
  • the plurality of heat insulating materials 110 are made of ceramics and have heat insulating properties.
  • Each heat insulating material 110 included in the plurality of heat insulating materials 110 has a plate-like shape.
  • Each heat insulating material 110 has an irregular planar shape.
  • the heat insulator 110 having the irregular planar shape may be replaced with a heat insulator having a planar shape different from the irregular planar shape.
  • the heat insulating material 110 having an irregular planar shape may be replaced with a heat insulating material having a square planar shape.
  • the plane size of each heat insulating material 110 is not limited, but is desirably 500 ⁇ m square or less.
  • each heat insulating material 110 is not limited, but is preferably 100 ⁇ m or less, and more preferably 80 ⁇ m or less.
  • the plurality of heat insulating materials 110 are arranged on a plane. Each heat insulator 110 has a gap 120 between itself and the heat insulator 110 adjacent to each heat insulator 110.
  • the sheet 112 is made of resin and has flexibility.
  • the sheet 112 made of resin may be replaced with a sheet made of a different material from resin.
  • the sheet 112 made of resin may be replaced with a sheet made of paper, metal foil, or the like.
  • One main surface of the sheet 112 has adhesiveness.
  • a plurality of heat insulating materials 110 are fixed to one main surface of the sheet 112.
  • FIG. 2 is a perspective view schematically illustrating a procedure of forming a heat insulating film provided with the heat insulating material of the first embodiment on the surface of the substrate.
  • the above-described heat insulating material with sheet 100 is prepared, and the base material 202 is prepared.
  • the substrate 202 is an object to be thermally insulated. Further, an adhesive is applied to the surface of the base material 202. As a result, the adhesive layer 204 before curing is formed on the surface of the substrate 202.
  • the base 202 is an engine or the like.
  • the surface of the base member 202 is an inner surface or the like surrounding the combustion chamber of the engine.
  • the plurality of heat insulating materials 110 are pressed against the adhesive layer 204 before curing, and the adhesive layer 204 before curing is cured and changed to the adhesive layer 206 as shown in FIG. Then, the sheet 112 is peeled from the plurality of heat insulating materials 110. As a result, the plurality of heat insulating materials 110 are transferred from one main surface of the sheet 112 to the surface of the substrate 202, and the heat insulating film 200 including the plurality of heat insulating materials 110 is formed.
  • a heat insulating structure 210 including the material 202 is manufactured. In the heat insulating structure 210, the heat insulating film 200 is bonded to the surface of the base 202 via the adhesive layer 206.
  • Each heat insulator 110 has a gap 120 between the heat insulator 110 and the heat insulator 110 adjacent to each heat insulator 110. Further, the sheet 112 has flexibility. For this reason, the heat insulating film 200 can be formed on a curved surface. Further, the plurality of heat insulating materials 110 have a certain thickness. Therefore, the surface of the heat insulating film 200 has only small irregularities.
  • the heat insulating film described in Patent Literature 1 has a problem that it is difficult to uniformly disperse a porous material in a matrix, so that there is a limit in reducing thermal conductivity. 200 can solve this problem.
  • the plurality of heat insulating materials 110 may be directly bonded to the surface of the base 202 without passing through one main surface of the sheet 112. Further, only one heat insulating material 110 may be bonded to the surface of the base 202. Further, a heat insulating material having a shape different from the plate shape may be bonded to the surface of the base 202. For example, a heat insulating material having a block shape may be adhered to the surface of the base 202. A heat insulating film including a plurality of heat insulating materials 110 and a matrix and in which the plurality of heat insulating materials 110 are dispersed in the matrix may be bonded to the surface of the base 202.
  • FIG. 3 is a cross-sectional view schematically illustrating a thermal insulation structure including the thermal insulation according to the first embodiment.
  • the heat insulating structure 210 includes the above-described heat insulating film 200, the adhesive layer 206, and the base material 202.
  • the heat insulating film 200 includes the plurality of heat insulating materials 110 described above.
  • Each heat insulator 110 includes a porous material 300 and a dense layer 302.
  • the dense layer 302 can prevent gas, liquid, or solid from entering the porous material 300.
  • the dense layer 302 prevents the combustion gas, fuel droplets, fuel cinders, and the like from entering the porous material 300. can do. If there is no possibility that a gas, liquid or solid enters the porous material 300, the dense layer 302 may be omitted.
  • FIG. 4 is a diagram schematically illustrating a first microstructure example of the porous material according to the first embodiment.
  • FIG. 5 is a diagram schematically illustrating a second microstructure example of the porous material according to the first embodiment.
  • the porous material 300 includes the skeleton 400.
  • the skeleton 400 includes a plurality of particles and has a three-dimensional network structure. In the porous material 300, spaces other than the space occupied by the skeleton 400 are voids. For this reason, a plurality of pores 402 that form voids are formed in the porous material 300.
  • the skeleton 400 includes a plurality of zirconia particles 410.
  • the skeleton 400 further includes a plurality of dissimilar material particles 412.
  • the plurality of zirconia particles 410 are made of zirconia.
  • the plurality of different material particles 412 are made of a different material different from zirconia.
  • Each zirconia particle 410 included in the plurality of zirconia particles 410 may be a single crystal particle composed of one crystal grain, or may be a polycrystalline particle composed of two or more crystal grains.
  • Each of the different material particles 412 included in the plurality of different material particles 412 may be a single crystal particle composed of one crystal grain, or may be a polycrystalline particle composed of two or more crystal grains.
  • the skeleton 400 may include particles different from the plurality of zirconia particles 410 and the plurality of dissimilar material particles 412.
  • the content ratio of the zirconia particles 410 and the foreign material particles 412 indicating the ratio of the volume occupied by the plurality of zirconia particles 410 and the plurality of different material particles 412 to the volume occupied by the plurality of particles provided in the skeleton 400 is desirably 90. % Or more. Thereby, high heat resistance and high strength inherent to zirconia can be exhibited.
  • each dissimilar material particle 412 included in the plurality of dissimilar material particles 412 is at least included in the plurality of zirconia particles 410. It contacts the surface of one zirconia particle 410. Therefore, phonons are scattered at a grain boundary between each of the different material particles 412 and at least one zirconia particle 410 in contact with each of the different material particles 412. Thereby, the thermal conductivity of the porous material 300 can be reduced.
  • the contact between the foreign material particles 412 and the surface of the at least one zirconia particle 410 may be caused by the contact between the foreign material particles 412 and the surface of the two zirconia particles 410 sandwiching the foreign material particle 412 as shown in FIG. Including doing.
  • phonon scattering increases, and the thermal conductivity of the porous material 300 can be further reduced.
  • the fact that the foreign material particles 412 contact the surface of at least one zirconia particle 410 means that the foreign material particles 412 contact the surface of only one zirconia particle 410, Contacting the surface of the neck with which it contacts.
  • the zirconia constituting the plurality of zirconia particles 410 is selected from the group consisting of oxides of Zr (ZrO 2 ) and composite oxides of two or more elements including Zr. At least one oxide. Among two or more elements including Zr, Zr is a main component.
  • the at least one element other than Zr included in the two or more elements including Zr may be Mg, Ca, Y or the like that forms stabilized zirconia or partially stabilized zirconia, or a different material described below. Or at least one element similar to at least one element selected from the group consisting of Si, Ti, La, Al, Sr, Gd, Nb and Y. .
  • At least one element other than Zr enters the Zr site of zirconia. Whether at least one element other than Zr is present in the Zr site of zirconia can be confirmed by performing elemental analysis by TEM and crystal structure analysis by X-ray diffraction.
  • the heterogeneous material constituting the plurality of heterogeneous material particles 412 is an oxide of an element other than Zr, a composite oxide of two or more elements other than Zr, and At least one oxide selected from the group consisting of composite oxides of two or more elements containing Zr.
  • the heterogeneous material constituting the plurality of heterogeneous material particles 412 is an oxide of an element other than Zr, a composite oxide of two or more elements other than Zr, and At least one oxide selected from the group consisting of composite oxides of two or more elements containing Zr.
  • at least one element other than Zr is a main component.
  • Elements other than Zr are Si, Ti, La, Al, Sr, Gd, Nb or Y.
  • the two or more elements other than Zr are two or more elements selected from the group consisting of Si, Ti, La, Al, Sr, Gd, Nb, and Y.
  • At least one element other than Zr included in the two or more elements including Zr is at least
  • the dissimilar material desirably includes two or more oxides. Accordingly, phonon scattering increases, and the thermal conductivity of the porous material 300 can be further reduced.
  • the volume ratio indicating the ratio of the volume occupied by the second oxide to the volume occupied by the first oxide is: , Preferably 1/9 or more and 9 or less.
  • the thermal conductivity of the porous material 300 can be further reduced.
  • the volume ratio is out of this range, it tends to be difficult to further reduce the thermal conductivity of the porous material 300.
  • the content ratio of the different material particles 412 indicating the ratio of the volume occupied by the plurality of different material particles 412 to the volume occupied by the plurality of zirconia particles 410 and the plurality of different material particles 412 is preferably 0.1% by volume or more and 30% by volume or less. And more preferably 0.5% by volume or more and 20% by volume or less, particularly preferably 1% by volume or more and 18% by volume or less.
  • the thermal conductivity of the porous material 300 can be further reduced. Further, high heat resistance and high strength inherently possessed by zirconia can be exhibited.
  • the content ratio of the heterogeneous material particles 412 is smaller than these ranges, it tends to be difficult to further reduce the thermal conductivity of the porous material 300.
  • the content ratio of the different kind of material particles 412 is larger than these ranges, it tends to be difficult to develop the inherently high heat resistance and high strength of zirconia.
  • the presence or absence of the zirconia particles 410 and the foreign material particles 412, the elements contained in the zirconia particles 410 and the foreign material particles 412, and the content ratio of the foreign material particles 412 are determined by a transmission electron microscope (TEM), a scanning electron microscope (SEM), or The porous material 300 is observed using a field emission scanning electron microscope (FE-SEM), and a field emission electron beam microanalyzer (FE-EPMA), energy dispersive X-ray spectroscopy (TEM-EDX), or the like is used. It is confirmed by performing elemental analysis using the same.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • FE-EPMA field emission electron beam microanalyzer
  • TEM-EDX energy dispersive X-ray spectroscopy
  • FIG. 6 is a graph showing a pore size distribution of a plurality of pores formed in the porous material of the first embodiment.
  • the pore size distribution of the plurality of pores 402 shown in FIG. 6 indicates a change in log differential pore volume depending on the pore size.
  • the horizontal axis represents the pore diameter
  • the vertical axis represents the log differential pore volume.
  • the horizontal axis is a logarithmic axis
  • the vertical axis is a linear axis.
  • the plurality of pores 402 have a bimodal pore diameter distribution. Therefore, when the pore diameter becomes the first pore diameter P1, the log differential pore volume of the plurality of pores 402 reaches the first peak value V1, and the pore diameter of the second pores 402 is larger than the first pore diameter P1. Has a pore diameter distribution in which the log differential pore volume reaches the second peak value V2 when the pore diameter becomes P2.
  • the first pore diameter P1 is 0.05 ⁇ m or more and 2 ⁇ m or less.
  • the second pore diameter P2 is 0.2 ⁇ m or more and 50 ⁇ m or less.
  • the plurality of pores 402 include many small pores having a pore diameter close to the first pore diameter P1 of 0.05 ⁇ m or more and 2 ⁇ m or less, and 0.2 ⁇ m or more and 50 ⁇ m or less. Many pores having pore diameters close to the following second pore diameter P2 are included.
  • the small pores contribute to lowering the thermal conductivity of the porous material 300.
  • the air holes contribute to lowering the heat capacity of the porous material 300. Thereby, the porous material 300 having low heat conductivity and low heat capacity can be provided.
  • the pore size distribution of the plurality of pores 402 is measured by a mercury porosimetry using a mercury porosimeter.
  • a mercury porosimeter AutoPore IV 9520 manufactured by Micromeritics Instrument Corporation is preferably used. This is the same for the mercury porosimeter described below.
  • the porosity of the porous material 300 is desirably from 20% to 80%, more desirably from 20% to 70%, and desirably from 40% to 70%. It is particularly preferably 50% or more and 70% or less. When the porosity of the porous material 300 is within these ranges, the thermal conductivity of the porous material 300 can be further reduced. Further, the strength of the porous material 300 can be increased. However, when the porosity of the porous material 300 is smaller than these ranges, it tends to be difficult to further reduce the thermal conductivity of the porous material 300. If the porosity of the porous material 300 is larger than these ranges, it tends to be difficult to increase the strength of the porous material 300.
  • the porosity of the porous material 300 is measured by a mercury porosimetry using a mercury porosimeter.
  • the average particle size of the plurality of zirconia particles 410 is desirably 70 nm or less. When the average particle size of the plurality of zirconia particles 410 is within this range, the thermal conductivity of the porous material 300 can be further reduced.
  • the minimum particle size of the plurality of zirconia particles 410 is desirably about 10 nm.
  • the maximum particle size of the plurality of zirconia particles 410 is desirably about 100 nm.
  • the plurality of zirconia particles 410 may slightly include large particles having a particle size of several hundred nm or more. Large particles are scattered throughout the porous material 300.
  • a flaky sample is prepared from the porous material 300.
  • the prepared sample is observed with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a TEM image including images of the plurality of zirconia particles 410 is obtained.
  • the field of view and observation conditions are selected so that each zirconia particle 410 and each pore 402 can be clearly identified.
  • the obtained TEM image is subjected to image processing using a personal computer (PC). Thereby, the area occupied by the image of each zirconia particle 410 in the obtained TEM image is calculated. Further, the particle size of each zirconia particle 410 is calculated from the calculated area.
  • the calculated particle size is the diameter of a sphere that forms an image that occupies the same area as the image of each zirconia particle 410. This calculation is performed because each zirconia particle 410 has a spherical shape.
  • the average particle size of the plurality of zirconia particles 410 is an average value of the particle sizes of the plurality of zirconia particles 410.
  • the minimum particle size and the maximum particle size of the plurality of zirconia particles 410 are the minimum value and the maximum value of the particle size of the plurality of zirconia particles 410, respectively.
  • the average particle size of the plurality of different material particles 412 is preferably 0.1 nm or more and 300 nm or less, more preferably 0.1 nm or more and 100 nm or less, and particularly preferably 0.1 nm or more and 50 nm or less. It is as follows. When the average particle size of the plurality of different material particles 412 is within these ranges, the porous material 300 can be manufactured at low cost. Further, high heat resistance and high strength inherently possessed by zirconia can be exhibited. However, when the average particle size of the plurality of different material particles 412 is smaller than these ranges, it tends to be difficult to produce the porous material 300 at low cost. When the average particle size of the plurality of different material particles 412 is larger than these ranges, it tends to be difficult to develop the inherent high heat resistance and high strength of zirconia.
  • the average particle size of the plurality of different material particles 412 is smaller than the average particle size of the plurality of zirconia particles 410. Thereby, high heat resistance and high strength inherent to zirconia can be exhibited.
  • Measurement of the particle size of the plurality of different material particles 412 can be performed in the same manner as measurement of the particle size of the plurality of zirconia particles 410.
  • Thermal conductivity and heat capacity of porous material The thermal conductivity of the porous material 300 is desirably 1.5 W / mk or less, more desirably 1 W / mK or less, particularly desirably 0.3 W / mK. is there.
  • the heat capacity of the porous material 300 is preferably 2000 kJ / m 3 K, and more preferably 1500 kJ / m 3 K or less.
  • the thermal conductivity of the porous material 300 is a product of the density, specific heat and thermal diffusivity of the porous material 300. Density is measured using a mercury porosimeter. Specific heat is measured by differential scanning calorimetry (DSC). The thermal diffusivity is measured by an optical alternating current method.
  • the heat insulating material with a sheet 100 may be manufactured by a procedure different from the procedure described below.
  • the zirconia powder, at least one kind of dissimilar material powder, the pore former, the binder, the plasticizer are used when the molding slurry is prepared. And the dispersion medium are mixed with each other. Thereby, the zirconia powder, at least one kind of different material powder, a pore former, a binder, a plasticizer and a dispersion medium are included, and the zirconia powder, at least one kind of different material powder, the pore former, the binder and the plasticizer are dispersed medium.
  • a slurry for molding is prepared.
  • the molding slurry may contain components other than zirconia powder, at least one kind of different material powder, a pore former, a binder, a plasticizer, and a dispersion medium.
  • the molding slurry may include a dispersant or the like.
  • the zirconia powder, the pore former, the binder, the plasticizer, and the dispersion medium are mixed with each other when the molding slurry is prepared.
  • a molding slurry containing the zirconia powder, the pore former, the binder, the plasticizer, and the dispersion medium, and the zirconia powder, the pore former, the binder, and the plasticizer dispersed in the dispersion medium is prepared.
  • the molding slurry may contain components other than the zirconia powder, the pore former, the binder, the plasticizer, and the dispersion medium.
  • the molding slurry may include a dispersant or the like.
  • At least one heterologous material powder is at least selected from the group consisting of SiO 2, TiO 2, La 2 O 3, Al 2 O 3, SrO, Gd 2 O 3, Nb 2 O 5 and Y 2 O 3 1 Seed oxide powder.
  • the powder of each oxide included in the powder of at least one oxide may be replaced with a powder of a precursor that changes to a powder of each oxide when the molded body is fired.
  • the powder of each oxide may be replaced with a powder of carbonate, hydroxide, oxalate, or the like.
  • the pore former is made of a material that disappears when the molded body is fired.
  • the pore-forming material is made of carbon black, latex particles, melamine resin particles, polymethyl methacrylate (PMMA) particles, polyethylene particles, polystyrene particles, a foamed resin, a water-absorbing resin, and preferably carbon black. It is desirable that the pore former is made of carbon black because the carbon black has a small particle diameter, so that when the pore former is made of carbon black, a plurality of pores 402 having a small pore diameter are formed in the porous material 300. This is because you can do it.
  • the binder is made of polyvinyl butyral resin (PVB), polyvinyl alcohol resin, polyvinyl acetate resin, polyacryl resin, or the like.
  • PVB polyvinyl butyral resin
  • polyvinyl alcohol resin polyvinyl alcohol resin
  • polyvinyl acetate resin polyvinyl acetate resin
  • polyacryl resin or the like.
  • Plasticizer is composed of dibutyl phthalate (DBP), dioctyl phthalate (DOP) and the like.
  • the dispersion medium is made of xylene, 1-butanol, or the like.
  • the content ratio of the zirconia powder in the molding slurry is desirably 5% by volume or more and 20% by volume or less.
  • the content ratio of at least one kind of different material powder in the molding slurry is 0.1% by volume or more and 5% by volume or less.
  • the content ratio of the pore-forming material in the molding slurry is desirably from 0% by volume to 20% by volume.
  • the content ratio of the remaining components for the molding slurry is desirably 70% by volume to 90% by volume.
  • the particle size distribution and other properties of the pore former affect the pore size distribution of the plurality of pores 402 formed in the porous material 300. For this reason, the particle size distribution and other properties of the pore former are selected so that the plurality of pores 402 having the pore size distribution described above are formed in the porous material 300.
  • the viscosity of the molding slurry whose viscosity has been adjusted is desirably from 0.1 Pa ⁇ s to 10 Pa ⁇ s.
  • the molded body is produced by tape molding.
  • the obtained viscosity-adjusted molding slurry is applied to the main surface of the polyester film.
  • a coating film made of the viscosity-adjusted molding slurry is formed on the main surface of the polyester film.
  • the thickness of the coating film is adjusted by a doctor blade or the like. The thickness of the coating film is adjusted so that a sintered body having a thickness corresponding to the thickness of the porous material 300 described above is manufactured. Volatile components, such as a dispersion medium, volatilize from the formed coating film.
  • a molded body made of a solid content composed of zirconia powder, at least one kind of different material powder, a pore former, a binder, and the like is formed on the main surface of the polyester film.
  • the formed body is a sheet-shaped body.
  • the formed molded body is peeled from the polyester film.
  • the polyester film made of polyester may be replaced with a film made of a material different from polyester.
  • a molded article may be produced by a molding method different from tape molding.
  • a molded body may be produced by extrusion molding, press molding, injection molding, cast molding, or the like.
  • a molding slurry, a clay, or the like suitable for the molding method is prepared instead of the molding slurry described above.
  • the exfoliated molded body is fired.
  • a sintered body is manufactured.
  • the produced sintered body is a plate-shaped sintered body.
  • the molded body is preferably fired at a firing temperature of 800 ° C. or more and 2000 ° C. or less for 0.5 hours or more and 20 hours or less, more preferably at a firing temperature of 800 ° C. or more and 1800 ° C. or less and 0.5 hours or more.
  • the firing is performed for a time of 15 hours or less, particularly preferably at a firing temperature of 800 ° C. to 1300 ° C. for a time of 0.5 to 10 hours.
  • the pore former disappears when the molded body is fired. Thereby, a plurality of pores 402 are formed in the manufactured sintered body.
  • a plurality of zirconia particles 410 are generated from the zirconia powder, and a plurality of different material particles 412 are generated from at least one kind of different material powder.
  • at least one kind of different material powder contains two or more kinds of oxide powders that react with each other when the molded body is fired, the composite oxide is formed from the two or more kinds of oxide powders when the molded body is fired. Particles are generated, and the plurality of different material particles 412 include the generated composite oxide particles.
  • the at least one heterogeneous material powder includes at least one oxide powder that reacts with the zirconia powder when the molded body is fired, at least one oxide powder when the molded body is fired; From the zirconia powder, particles of the complex oxide containing a large amount of Zr and particles of the complex oxide containing a large amount of elements other than Zr are generated, and the plurality of zirconia particles 410 contain the generated particles of the complex oxide containing a large amount of Zr.
  • the plurality of different material particles 412 include particles of the generated composite oxide particles containing a large amount of elements other than Zr.
  • the powder of the composite oxide may be included in at least one kind of different material powder included in the slurry for molding.
  • the dense layer contains an oxide of at least one element selected from the group consisting of a metal element and Si, and desirably contains an oxide of Si as a main component.
  • the oxide contained in the dense layer may be the same oxide as the oxide constituting the porous material, or may be an oxide different from the oxide constituting the porous material.
  • a dense layer When a dense layer is produced, a raw material liquid for the dense layer is applied to one main surface of the produced sintered body. Thereby, a coating film made of the raw material liquid for the dense layer is formed on one main surface of the sintered body.
  • the raw material liquid for the dense layer is applied by dipping, spraying, spin coating, roll coating, or the like.
  • the formed coating film is fired or the like. Thereby, cross-linking, sintering, polymerization, etc. in the coating film proceed, a dense layer is formed on one main surface of the sintered body, and the sintered body and the dense layer are provided with the sintered body and the dense layer.
  • a laminated body is produced.
  • the sintered body and the dense layer may be produced in parallel.
  • the laminate provided in the manufactured laminate with the sheet is divided into a plurality of heat-insulating materials 110.
  • the division of the laminated body into the plurality of heat insulating materials 110 may be performed by cutting the laminated body, or forming a groove on at least one main surface of the laminated body, and dividing the laminated body having the groove into a groove. May be performed by dividing along.
  • division may not be necessary in some cases.
  • FIG. 7 is a diagram showing a TEM image obtained by observing a first prototype of the porous material of the first embodiment by TEM.
  • FIG. 8 is a diagram showing a binarized image obtained by binarizing the TEM image shown in FIG. The binarized image shown in FIG. 8 is provided in case the TEM image shown in FIG. 7 cannot be clearly seen due to the restriction of the viewing environment.
  • the porous material 300 has a skeleton 400 as shown in FIG.
  • the skeleton 400 includes a plurality of particles and has a three-dimensional network structure.
  • spaces other than the space occupied by the skeleton 400 are voids. For this reason, a plurality of pores 402 that form voids are formed in the porous material 300.
  • FIG. 9 is a graph showing a pore size distribution of a plurality of pores formed in a second prototype of the porous material of the first embodiment.
  • FIG. 10 is a diagram showing an SEM image obtained by observing a second prototype of the porous material of the first embodiment by SEM.
  • FIG. 11 is a diagram illustrating a graph showing the pore size distribution of a plurality of pores formed in a third prototype of the porous material of the first embodiment.
  • the plurality of pores 402 have a bimodal pore diameter distribution.
  • the plurality of pores 402 have a first pore diameter P1 having a pore diameter of 0.05 ⁇ m or more and 2 ⁇ m or less, the log differential pore volume reaches the first peak value V1, and the pore diameter becomes the first peak value V1.
  • the second pore diameter P2 is larger than the pore diameter P1 and is not less than 0.2 ⁇ m and not more than 50 ⁇ m, the log differential pore volume has a pore diameter distribution reaching the second peak value V2.
  • the plurality of particles include large particles having a particle diameter of several hundred nm or more.
  • REFERENCE SIGNS LIST 100 heat insulating material with sheet 110 heat insulating material 112 sheet 200 heat insulating film 202 base material 204 adhesive layer before curing 206 adhesive layer 210 heat insulating structure 300 porous material 302 dense layer 400 skeleton 402 plural pores 410 zirconia particles 412 heterogeneous material particles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne un matériau poreux présentant une faible conductivité thermique et une faible capacité thermique. Le matériau poreux est équipé d'un squelette pourvu d'une pluralité de particules de zircone comprenant de la zircone. Plusieurs pores sont formés dans le matériau poreux. La pluralité de pores possède une répartition de tailles de pores dans laquelle le volume différentiel logarithmique des pores atteint une première valeur maximale lorsque la taille des pores est une première taille de pores, le volume différentiel logarithmique des pores atteint une seconde valeur maximale lorsque la taille des pores est une seconde taille de pores supérieure à la première taille de pores, la première taille de pores étant de 0,05 à 2 µm, et la seconde taille de pores étant de 0,2 à 50 µm.
PCT/JP2018/025358 2018-07-04 2018-07-04 Matériau poreux et matériau d'isolation thermique WO2020008561A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2018/025358 WO2020008561A1 (fr) 2018-07-04 2018-07-04 Matériau poreux et matériau d'isolation thermique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2018/025358 WO2020008561A1 (fr) 2018-07-04 2018-07-04 Matériau poreux et matériau d'isolation thermique

Publications (1)

Publication Number Publication Date
WO2020008561A1 true WO2020008561A1 (fr) 2020-01-09

Family

ID=69060479

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/025358 WO2020008561A1 (fr) 2018-07-04 2018-07-04 Matériau poreux et matériau d'isolation thermique

Country Status (1)

Country Link
WO (1) WO2020008561A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112067531A (zh) * 2020-10-15 2020-12-11 西安特种设备检验检测院 一种多孔材料孔径分布测试方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008102801A1 (fr) * 2007-02-21 2008-08-28 National Institute Of Advanced Industrial Science And Technology Corps poreux céramique avec des macropores en communication et procédé de fabrication du corps poreux céramique
JP2009500286A (ja) * 2005-07-11 2009-01-08 リフラクトリー・インテレクチュアル・プロパティー・ゲー・エム・ベー・ハー・ウント・コ・カーゲー 焼成された耐火セラミック生成物
JP2016117622A (ja) * 2014-12-22 2016-06-30 クアーズテック株式会社 断熱材

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009500286A (ja) * 2005-07-11 2009-01-08 リフラクトリー・インテレクチュアル・プロパティー・ゲー・エム・ベー・ハー・ウント・コ・カーゲー 焼成された耐火セラミック生成物
WO2008102801A1 (fr) * 2007-02-21 2008-08-28 National Institute Of Advanced Industrial Science And Technology Corps poreux céramique avec des macropores en communication et procédé de fabrication du corps poreux céramique
JP2016117622A (ja) * 2014-12-22 2016-06-30 クアーズテック株式会社 断熱材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112067531A (zh) * 2020-10-15 2020-12-11 西安特种设备检验检测院 一种多孔材料孔径分布测试方法

Similar Documents

Publication Publication Date Title
JP6562841B2 (ja) 多孔質板状フィラー
EP2865722B1 (fr) Charge poreuse en forme de plaque, composition de revêtement, film thermo-isolant, et structure de film thermo-isolant
CN105764872B (zh) 多孔材料及绝热膜
KR101749883B1 (ko) 무기 산화물 분말, 및 이것을 함유하는 슬러리, 그리고 비수 전해액 이차 전지 및 그 제조 방법
US9764990B2 (en) Honeycomb structure
WO2015159838A1 (fr) Charge de type plaque poreuse, film d'isolation thermique et procédé de production de charge de type plaque poreuse
JP2023510157A (ja) 電池用の高グリーン密度セラミック
US20210341234A1 (en) Heat dissipation member
US20180141872A1 (en) Porous ceramic structure
CN104659397A (zh) 固体氧化物型燃料电池用氧化锆片和包含该片的固体氧化物型燃料电池用单电池
WO2020008561A1 (fr) Matériau poreux et matériau d'isolation thermique
US6551369B1 (en) Ceramic flat membrane and method for producing the same
US20160096775A1 (en) Heat-resistant member and method for producing the same
WO2020008562A1 (fr) Matériau poreux et matériau d'isolation thermique
WO2015115668A1 (fr) Remplissage en forme de plaque poreuse et film d'isolation thermique
JP5877821B2 (ja) 複合耐火断熱材
WO2015087888A1 (fr) Charge sous forme de plaque poreuse et film d'isolation thermique
JP6453234B2 (ja) 断熱膜
US10590004B2 (en) Porous ceramic particles
US20220149412A1 (en) Electrolyte sheet for solid oxide fuel battery, production method of electrolyte sheet for solid oxide fuel battery, and single cell for solid oxide fuel battery
WO2015163249A1 (fr) Charge en forme de plaque poreuse, son procédé de fabrication et film d'isolation thermique
CN109642696B (zh) 隔热部件
MX2008008875A (en) Fuel cell components having porous electrodes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18925411

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18925411

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP