WO2020145365A1 - 放熱部材 - Google Patents

放熱部材 Download PDF

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Publication number
WO2020145365A1
WO2020145365A1 PCT/JP2020/000540 JP2020000540W WO2020145365A1 WO 2020145365 A1 WO2020145365 A1 WO 2020145365A1 JP 2020000540 W JP2020000540 W JP 2020000540W WO 2020145365 A1 WO2020145365 A1 WO 2020145365A1
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WO
WIPO (PCT)
Prior art keywords
inorganic porous
porous layer
base material
heat dissipation
dissipation member
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/000540
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
恵実 藤▲崎▼
崇弘 冨田
裕亮 尾下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to JP2020565215A priority Critical patent/JP7431176B2/ja
Priority to DE112020000384.1T priority patent/DE112020000384T5/de
Priority to CN202080008368.6A priority patent/CN113272474A/zh
Publication of WO2020145365A1 publication Critical patent/WO2020145365A1/ja
Priority to US17/305,409 priority patent/US20210341234A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B1/08—Tubular products
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    • B32B15/02—Layer formed of wires, e.g. mesh
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    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/021—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles in a direct manner, e.g. direct copper bonding [DCB]
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    • 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
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    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/04—Constructions of heat-exchange apparatus characterised by the selection of particular materials of ceramic; of concrete; of natural stone
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F3/00—Plate-like or laminated elements; Assemblies of plate-like or laminated elements
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    • F28F2013/001—Particular heat conductive materials, e.g. superconductive elements

Definitions

  • This specification discloses the technology regarding a heat dissipation member.
  • Patent Document 1 discloses a heat dissipation member in which a heat insulation layer is provided on the surface of a heat dissipation layer (base material). Specifically, in the heat dissipation member of Patent Document 1, a heat insulating layer obtained by impregnating a nonwoven fabric with silica aerosol is bonded to a surface of a graphite layer (base material) using an adhesive layer (resin).
  • the heat dissipation member having such a structure can dissipate the heat generated by the heat source and suppress the transfer of the heat generated by the heat source to the space around the heat dissipation member. That is, the heat dissipation member of Patent Document 1 can dissipate the heat generated by the heat source without raising the environmental temperature around the heat source.
  • the heat dissipation member of Patent Document 1 is used in electronic devices such as smartphones.
  • the heat source (electronic component) arranged in the electronic device rises up to about 100°C.
  • the heat radiating member of Patent Document 1 has a sufficient function of radiating the heat of the heat source whose temperature rises to about 100° C., but it is difficult to use it for a heat source whose temperature rises to a higher temperature.
  • the heat dissipation member of Patent Document 1 when used for a heat source whose temperature rises to 500° C. or higher, the heat dissipation member itself deteriorates (deterioration of the graphite layer itself, separation of the graphite layer and the heat insulating layer, etc.) and a sufficient function is obtained.
  • the heat dissipation member disclosed in this specification dissipates heat generated by a heat source.
  • This heat dissipation member is provided on the surface of the base material having a porosity of 5% by volume or less, and has a porosity of 25% by volume or more and 85% by volume or less, and has a lower thermal conductivity than the substrate. It may have an inorganic porous layer.
  • the inorganic porous layer contains ceramic fibers, and 15% by mass or more of the constituent components of the inorganic porous layer may be alumina.
  • the form of a heat dissipation member is shown with a perspective view.
  • the sectional view of the example of use of a heat dissipation member is shown.
  • the perspective view which shows the modification of a heat dissipation member is shown.
  • the perspective view which shows the modification of a heat dissipation member is shown.
  • the perspective view which shows the modification of a heat dissipation member is shown.
  • the perspective view which shows the modification of a heat dissipation member. The perspective view which shows the modification of a heat dissipation member.
  • the perspective view which shows the modification of a heat dissipation member The raw material compounding quantity of the sample used in the experimental example is shown.
  • the result of an experimental example is shown.
  • the heat dissipation member disclosed in this specification can be used, for example, to dissipate heat generated by a heat source to a position away from the heat source.
  • the heat dissipation member includes a base material and an inorganic porous layer which is provided on the surface of the base material and has a thermal conductivity lower than that of the base material.
  • the base material functions as a heat dissipation plate itself that dissipates the heat generated by the heat source, or as a heat transfer material that transfers the heat generated by the heat source to a heat dissipation plate provided at a position distant from the heat source.
  • the inorganic porous layer functions as a heat insulating material that thermally cuts off the heat source and the space around the heat source.
  • the heat dissipation member disclosed in the present specification is provided with the inorganic porous layer on the surface of the base material, it can be suitably used as a heat dissipation member for a heat source that rises to a high temperature of 1000° C. or higher.
  • the base material only needs to have a thermal conductivity capable of exhibiting a function as a heat radiating material, and depending on the purpose of use, for example, the thermal conductivity may be 10 W/mK or more and 400 W/mK or less.
  • the thermal conductivity of the base material may be 50 W/mK or higher, 100 W/mK or higher, 150 W/mK or higher, and 200 W/mK or higher.
  • the thermal conductivity of the base material 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 base material may have a dense structure, specifically, a porosity of 5% by volume or less, in order to ensure high thermal conductivity.
  • the base material may be formed of a material having a relatively low coefficient of thermal expansion.
  • the dimensional change (expansion/contraction) of the heat dissipation member (base material) due to the temperature change of the heat source is suppressed, and the durability of the heat dissipation member is improved. That is, by lowering the coefficient of thermal expansion of the base material, deterioration of the base material and/or the inorganic porous layer due to dimensional change, separation of the base material and the inorganic porous layer, and the like can be suppressed.
  • the coefficient of thermal expansion of the base material may be 11 ⁇ 10 ⁇ 6 /K or less.
  • the thermal expansion coefficient of the base material can be appropriately selected according to the temperature of the heat source to which the heat dissipation member is applied and the thermal expansion coefficient of the inorganic porous layer.
  • the thermal expansion coefficient of the base material is 10 ⁇ 10 ⁇ 6 /K or less, 8 ⁇ 10 ⁇ 6 /K or less, 6 ⁇ 10 ⁇ 6 /K or less, 5.5 ⁇ 10 ⁇ 6 /K or less, 5 ⁇ 10 -6 / K may be less, may be less 4.5 ⁇ 10 -6 / K, may be not more than 4 ⁇ 10 -6 / K.
  • the coefficient of thermal expansion of the base material depends on the coefficient of thermal expansion of the inorganic porous layer, but may be, for example, 1 ⁇ 10 ⁇ 6 /K or more.
  • the material of the base material is not particularly limited, but may be metal, alloy, ceramics, or the like.
  • metals include molybdenum, tungsten, iron and the like.
  • alloys include Kovar, Invar, carbon steel, chrome steel, nickel steel, stainless steel and the like.
  • ceramics include AlN, SiC, SiO 2 , BN, Si 3 N 4 , MgO, BeO, Al 2 O 3 and the like.
  • the material of the base material is preferably AlN, SiC or Si 3 N 4 .
  • the base material made of these materials can satisfy the above-mentioned characteristics (heat conductivity is 10 W/mK or more and 400 W/mK or less, porosity is 5 vol% or less). In addition, all of the above materials have a coefficient of thermal expansion of 11 ⁇ 10 ⁇ 6 /K or less.
  • the base material may be a composite material using a plurality of the above materials as long as the thermal expansion coefficient is 11 ⁇ 10 ⁇ 6 /K or less.
  • the inorganic porous layer may be provided only on one surface (front surface) of the base material, or may be provided on both surfaces (front surface and back surface) of the base material.
  • the inorganic porous layer may cover both surfaces of two base materials facing each other with a space.
  • the base material first base material, second base material
  • the base material may be bonded to both surfaces of one inorganic porous layer.
  • the heat of the second device can be prevented from being applied to the first device, and the heat generated by the second device can be radiated by the second base material. That is, by bonding the base material to both surfaces of one inorganic porous layer, in addition to the function as a heat dissipation member for a plurality of devices (heat sources), it also functions as a partition plate for insulating the devices.
  • the shape of the heat dissipation member (the shape of the base material) is not particularly limited, but may be linear (wire-like) or plate-like (sheet-like).
  • the inorganic porous layer may cover the outer peripheral surface of the substrate.
  • the inorganic porous layer may cover the entire exposed surface of the base material, or may cover the end surface in the thickness direction (front surface and/or back surface). The surface (side surface) of the width direction end may be covered, or the surface of the length direction end may be covered.
  • the inorganic porous layer covers both the front surface of the first plate-shaped base material (first base material) and the back surface of the second plate-shaped base material (second base material). It may be coated.
  • the inorganic porous layer may cover the entire surface of the base material, or may cover a part of the surface of the base material.
  • the inorganic porous layer may cover a portion of the base material excluding the end portions (one end or both ends).
  • the inorganic porous layer covers the front and back surfaces of the plate-shaped substrate (the surface of the end in the thickness direction)
  • the inorganic porous layer is a part of the front and back surface (for example, one or both ends in the longitudinal direction).
  • the inorganic porous layer may cover the entire back surface and cover the front surface, for example, a portion excluding both ends in the longitudinal direction.
  • the inorganic porous layer may have a thermal conductivity capable of exerting a function as a heat insulating layer that insulates the heat source (base material exposed to the heat source) and the space around the heat source.
  • the thermal conductivity of the inorganic porous layer may be lower than that of the substrate, and may be, for example, 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 higher, 0.2 W/mK or higher, 0.3 W/mK or higher, 0.5 W/mK. It may be above, may be 1 W/mK or above, and may be 2 W/mK or above.
  • the thermal conductivity of the inorganic porous layer may be 2 W/mK or less, 1 W/mK or less, 0.5 W/mK or less, and 0.3 W/mK or less. It may be 0.2 W/mK or less, and may be 0.1 W/mK or less.
  • the heat dissipation member radiates the heat generated by the heat source by the base material, and the heat source (or the base material) and the space around the heat source are insulated by the inorganic porous layer. Therefore, it is preferable that the substrate and the inorganic porous layer have a large difference in thermal conductivity.
  • the thermal conductivity of the base material may be 100 times or more the thermal conductivity of the inorganic porous layer.
  • the thermal conductivity of the base material may be 300 times or more the thermal conductivity of the inorganic porous layer, and may be 500 times or more the thermal conductivity of the inorganic porous layer.
  • the conductivity may be 600 times or more, and the thermal conductivity of the inorganic porous layer may be 1000 times or more.
  • the inorganic porous layer may be made of a uniform material in the thickness direction (from the surface in contact with the surface of the base material to the surface exposed to the external environment). 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 multilayer structure in which a plurality of layers are laminated. Alternatively, the inorganic porous layer may have a graded structure in which the composition gradually changes in the thickness direction. When the inorganic porous layer is a single layer, the heat dissipation member can be easily manufactured (step of molding the inorganic porous layer on the surface of the base material).
  • the inorganic porous layer has a multilayer structure or a gradient structure
  • the characteristics of the inorganic porous layer can be changed in the thickness direction.
  • the structure of the inorganic porous layer (single layer, multilayer, inclined structure) can be appropriately selected according to the usage environment to which the heat dissipation member is applied.
  • the inorganic porous layer may include ceramic fibers. That is, the inorganic porous layer may be composed of a matrix (matrix) and ceramic fibers. The ceramic fiber suppresses a decrease in strength (mechanical strength) of the inorganic porous layer.
  • the inorganic porous layer contains the ceramic fiber, the inorganic porous layer itself can absorb the influence of the difference in thermal expansion coefficient between the base material and the inorganic porous layer. Specifically, since the inorganic porous layer can be deformed following the dimensional change (thermal expansion, thermal contraction) of the base material, it is possible to prevent the inorganic porous layer from peeling from the base material. ..
  • the inorganic porous layer may contain 15% by mass or more of an alumina component. That is, 15% by mass or more of the constituent components of the inorganic porous layer may be alumina. By including 15% by mass or more of the alumina component, the melting point of the inorganic porous layer can be maintained high, and the shape of the heat dissipation member (inorganic porous layer) can be maintained even when the heat source is at a high temperature. The durability can be improved.
  • Alumina has a relatively small coefficient of thermal expansion (7.2 ⁇ 10 ⁇ 6 /K), and the inorganic porous layer contains 15% by mass or more of the alumina component, so that the heat dissipation member ( The dimensional change of the inorganic porous layer) is suppressed, and the durability of the heat dissipation member is improved.
  • the alumina component may be 15% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more of the constituent components of the inorganic porous layer. Good.
  • the alumina component may form a matrix or a ceramic fiber (alumina fiber).
  • the inorganic porous layer may contain a material having a coefficient of thermal expansion of less than 5 ⁇ 10 ⁇ 6 /K as a matrix.
  • materials include mullite (Al 6 O 13 Si 2 ), silicon dioxide (SiO 2 ), silicon carbide (SiC), aluminum nitride (AlN), low thermal expansion glass, aluminum titanate (TiO 2 ⁇ Al 2 O 3 ). , Zirconium phosphate, spodumene (LiAlSi 2 O 6 ), eucryptite (LiAlSiO 4 ), and the like.
  • the inorganic porous layer may include at least one of the above materials as a matrix.
  • the thermal expansion coefficient of the material contained in the matrix of the inorganic porous layer may be less than 3 ⁇ 10 ⁇ 6 /K or less than 2 ⁇ 10 ⁇ 6 /K.
  • cordierite is suitable as the matrix of the inorganic porous layer.
  • Cordierite has high heat resistance and a small coefficient of thermal expansion (less than 0.1 ⁇ 10 ⁇ 6 /K). Therefore, when the matrix contains cordierite, the dimensional change of the heat dissipation member (inorganic porous layer) due to the temperature change of the heat source is suppressed, and the durability of the heat dissipation member is improved.
  • the material having a thermal expansion coefficient of less than 5 ⁇ 10 ⁇ 6 /K may be 30% by mass or more, and may be 40% by mass or more of the entire inorganic porous layer (ceramic fiber+matrix). , 50 mass% or more, 60 mass% or more, 70 mass% or more, and 80 mass% or more. Further, the material having a coefficient of thermal expansion of less than 5 ⁇ 10 ⁇ 6 /K may be 60% by mass or more, 70% by mass or more, and 80% by mass or more of the matrix of the inorganic porous layer. It may be 90% by mass or more, and may be 100% by mass. That is, the inorganic porous layer may be one in which ceramic fibers are contained in a matrix containing a material having a thermal expansion coefficient of less than 5 ⁇ 10 ⁇ 6 /K.
  • the porosity of the inorganic porous layer may be 25% by volume or more and 85% by volume or less. When the porosity is 25% by volume or more, the inorganic porous layer can sufficiently exhibit the function as the heat insulating layer. When the porosity is 85% by volume or less, the strength of the inorganic porous layer is sufficiently secured, and the durability of the heat dissipation member (inorganic porous layer) can be improved.
  • the porosity of the inorganic porous layer may be 30% by volume or more, 40% by volume or more, 50% by volume or more, 60% by volume or more, and 62% by volume. Or more, 64% by volume or more, 68% by volume or more, and 70% by volume or more.
  • the porosity of the inorganic porous layer may be 80% by volume or less, 70% by volume or less, 68% by volume or less, 66% by volume or less, and 64% by volume. It may be less than or equal to 62% by volume, or less than or equal to 60% by volume.
  • the porosity of the inorganic porous layer may be 25% by volume or more and 85% by volume or less as a whole, and the porosities may be different in the thickness direction. .. In this case, a portion having a porosity of less than 25% by volume or a portion having a porosity of more than 85% by volume may be partially present.
  • the coefficient of thermal expansion of the inorganic porous layer may be adjusted according to the coefficient of thermal expansion of the substrate and is not particularly limited, but may be 1 ⁇ 10 ⁇ 6 /K or more and 6 ⁇ 10 ⁇ 6 /K or less.
  • the coefficient of thermal expansion of the inorganic porous layer is 1 ⁇ 10 ⁇ 6 /K or more, the influence of the difference in coefficient of thermal expansion between the base material and the inorganic porous layer can be reduced.
  • the coefficient of thermal expansion of the inorganic porous layer is 6 ⁇ 10 ⁇ 6 /K or less, the dimensional change of the inorganic porous layer due to the temperature change of the heat source is suppressed, and the durability of the heat dissipation member is improved.
  • the coefficient of thermal expansion of the inorganic porous layer may be 2 ⁇ 10 ⁇ 6 /K or more, 3 ⁇ 10 ⁇ 6 /K or more, and 3.5 ⁇ 10 ⁇ 6 /K or more. 4 ⁇ 10 ⁇ 6 /K or more, 4.5 ⁇ 10 ⁇ 6 /K or more, 5 ⁇ 10 ⁇ 6 /K or more, 5.5 ⁇ 10 ⁇ 6 /K It may be K or more.
  • the thermal expansion coefficient of the inorganic porous layer may be 4.5.5 ⁇ 10 ⁇ 6 /K or less, 5 ⁇ 10 ⁇ 6 /K or less, and 4.5 ⁇ 10 ⁇ 6 /K. It may be K or less and may be 4 ⁇ 10 ⁇ 6 /K or less.
  • the thermal expansion coefficient of the inorganic porous layer is ⁇ 1 and the thermal expansion coefficient of the base material is ⁇ 2, the thermal expansion coefficients of both may be adjusted so as to satisfy the following formula 1.
  • the value of “ ⁇ 1/ ⁇ 2” may be 0.55 or more, may be 0.6 or more, may be 0.7 or more, may be 0.8 or more, and may be 0.9 or more.
  • the thickness of the inorganic porous layer may be 1 mm or more, depending on the purpose of use (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 an inorganic porous layer in which ceramic fibers are 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 process). Since the inorganic porous layer disclosed in the present specification contains the ceramic fiber, the shrinkage in the manufacturing process is suppressed, and the 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, 100 mm or less, or 5 mm or less.
  • the inorganic porous layer may include granular particles of 0.1 ⁇ m or more and 10 ⁇ m or less. When the inorganic porous layer is molded (fired), the ceramic fibers are bonded to each other through the granular particles to obtain a high-strength inorganic porous layer.
  • the ceramic particles may be used as a bonding material for bonding together the aggregates that form the skeleton of the inorganic porous layer such as plate-shaped ceramic particles and ceramic fibers described below.
  • the ceramic particles may be granular particles of 0.1 ⁇ m or more and 10 ⁇ m or less. It should be noted that the ceramic particles may have a large particle size due to sintering or the like in the manufacturing process (for example, a firing process). That is, as a raw material for producing the inorganic porous layer, the ceramic particles may be granular particles 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 5 ⁇ m or less.
  • the material of the ceramic particles one having a small coefficient of thermal expansion (less than 5 ⁇ 10 ⁇ 6 /K) may be used.
  • materials having a low thermal expansion coefficient include mullite, silicon dioxide, silicon carbide, aluminum nitride, low thermal expansion glass, aluminum titanate, zirconium phosphate, spodumene, and eucryptite.
  • a metal oxide may be used as the material of the ceramic particles.
  • metal oxides include alumina (Al 2 O 3 ), spinel (MgAl 2 O 4 ), titania (TiO 2 ), zirconia (ZrO 2 ), magnesia (MgO), mullite, cordierite (MgO.Al 2 O). 3 ⁇ SiO 2 ) and the like.
  • plate-like ceramic particles may be included in the inorganic porous layer.
  • the plate-shaped ceramic particles By using the plate-shaped ceramic particles, a part of the ceramic fibers can be replaced with the plate-shaped ceramic particles.
  • the length (size in the longitudinal direction) of the plate-shaped ceramic particles is shorter than the length of the ceramic fibers. Therefore, by using the plate-like ceramic particles, the heat transfer path in the inorganic porous layer is divided, and heat transfer in the inorganic porous layer does not easily occur. As a result, the heat insulating performance of the inorganic porous layer is further improved.
  • the “plate-like ceramic particles” mean ceramic particles having an aspect ratio of 5 or more and a longitudinal size of 5 ⁇ m or more and 100 ⁇ m or less.
  • the plate-shaped ceramics can function as an aggregate and a reinforcing material in the inorganic porous layer. That is, the plate-like ceramics improve the strength of the inorganic porous layer, like the ceramic fibers, and further suppress the shrinkage of the inorganic porous layer in the manufacturing process.
  • the plate-shaped ceramic particles By using the plate-shaped ceramic particles, the heat transfer path in the inorganic porous layer can be divided. Therefore, as compared with the case where only the ceramic fiber is used as the aggregate, the heat generated by the heat source is less likely to be transferred in the inorganic porous layer, and the environment around the heat source and the heat dissipation member can be further insulated.
  • the plate-shaped ceramic particles may have a rectangular plate shape or a needle shape, and may have a longitudinal size of 5 ⁇ m or more and 100 ⁇ m or less.
  • the size in the longitudinal direction is 5 ⁇ m or more, excessive sintering of ceramic particles can be suppressed.
  • 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 a heat dissipation member used in a high temperature environment.
  • the plate-like ceramic particles may have an aspect ratio of 5 or more and 100 or less.
  • the aspect ratio is 5 or more, it is possible to excellently suppress the sintering of the ceramic particles, and when the aspect ratio is 100 or less, the strength reduction of the plate-shaped ceramic particles themselves is suppressed.
  • the material for the plate-shaped ceramic particles in addition to the metal oxide used as the material for the ceramic particles, talc (Mg 3 Si 4 O 10 (OH) 2 ), minerals such as mica, kaolin, clay, glass, etc. Can also be used.
  • the inorganic porous layer includes ceramic fibers.
  • the ceramic fiber can function as an aggregate and a reinforcing material in the inorganic porous layer. That is, the ceramic fibers improve the strength of the inorganic porous layer and further suppress 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. Further, the diameter (average diameter) of the ceramic fibers may be 1 to 20 ⁇ m.
  • the volume ratio of the ceramic fibers in the inorganic porous layer (the volume ratio of the ceramic fibers in the material forming the inorganic porous layer) may be 5% by volume or more and 25% by volume or less.
  • the ceramic fiber By including 5% by volume or more of the ceramic fiber, 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. Further, by setting the volume ratio of the ceramic fibers to be 25% by volume or less, the heat transfer path in the inorganic porous layer can be divided, and it can be suitably applied to a heat dissipation member used in a high temperature environment.
  • the material of the ceramic fiber the same material as the material of the plate-like ceramic particles described above can be used.
  • the content of the aggregate and the reinforcing material (ceramic fibers, plate-like ceramic particles, etc., hereinafter simply referred to as aggregate) in the inorganic porous layer may be 15% by mass or more and 50% by mass or less.
  • the content of the aggregate in the inorganic porous layer 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 inorganic porous layer is 50% by mass or less, the aggregate is favorably bonded to each other by the ceramic particles.
  • the content of the aggregate in the inorganic porous layer may be 20% by mass or more, 30% by mass or more, and 40% by mass or more.
  • the content of the aggregate in the inorganic porous layer may be 40% by mass or less, and may be 30% by mass or less.
  • both the ceramic fibers and the plate-like ceramic particles can function as an aggregate and a reinforcing material in the inorganic porous layer.
  • the inorganic porous layer can be surely prevented from shrinking after the production of the heat dissipation member (after firing).
  • the content of ceramic fibers in the layer may be at least 5% by weight or more.
  • the content of the ceramic fibers may be adjusted in the range of 5% by mass to 50% by mass.
  • the ratio (weight ratio) of the plate-like ceramic particles in the whole aggregate may be 90% or less. That is, in terms of mass ratio, at least 10% or more of the aggregate may be ceramic fibers.
  • the proportion of the plate-shaped ceramic particles in the entire aggregate may be 60% or less, 50% or less, 40% or less, or 34% or less. Further, the proportion of the plate-shaped ceramic particles in the entire aggregate may be 33% or more, 40% or more, 50% or more, and 60% or more.
  • the content of the plate-like ceramic particles in the inorganic porous layer may be 10% by mass or more, 20% by mass or more, and 30% by mass or more.
  • the content of the plate-shaped ceramic particles may be 30% by mass or less, 20% by mass or less, and 10% by mass or less.
  • the inorganic porous layer may be made of at least one material selected from ceramic particles (granular particles), plate-like ceramic particles, and ceramic fibers.
  • the ceramic particles, the plate-shaped ceramic particles, and the ceramic fibers may contain alumina, cordierite, titania, etc. as constituent components.
  • the ceramic particles, the plate-shaped ceramic particles, and the ceramic fibers may be formed of alumina, cordierite, titania, or the like.
  • the inorganic porous layer may include the alumina component in an amount of 15% by mass or more in the entire constituent material (constituent substance).
  • the inorganic porous layer contains at least ceramic fibers, though the constituent components of the matrix and the ceramic fibers are arbitrary.
  • SiO 2 contained in the inorganic porous layer may be 25% by mass or less. Formation of an amorphous layer in the inorganic porous layer is suppressed, and heat resistance (durability) of the inorganic porous layer is improved.
  • a raw material obtained by mixing a binder, a pore-forming material, and a solvent may be used.
  • An inorganic binder may be used as the binder.
  • 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.
  • the pore-forming material polymer-based pore-forming material, carbon-based powder or the like may be used. Specific examples thereof include acrylic resin, melamine resin, polyethylene particles, polystyrene particles, carbon black powder, and graphite powder.
  • the pore-forming material may have various shapes depending on the purpose, and may have, for example, a spherical shape, a plate shape, or a fibrous shape.
  • the porosity and pore size of the inorganic porous layer can be adjusted by selecting the addition amount, size and shape of the pore-forming material. Any solvent can be used as long as it can adjust the viscosity of the raw material without affecting other raw materials, and for example, water, ethanol, isopropyl alcohol (IPA) or the like can be used.
  • IPA isopropyl alcohol
  • the above-mentioned inorganic binder is also a constituent material of the inorganic porous layer. Therefore, when using alumina sol, titania sol, or the like when forming the inorganic porous layer, the inorganic porous layer only needs to contain 15% by mass or more of the alumina component in the entire constituent material including the inorganic binder.
  • the above-mentioned raw material may be applied to the surface of the base material, and the inorganic porous layer may be formed on the surface of the base material through drying and firing.
  • a method for applying the raw material dip coating, spin coating, spray coating, slit die coating, thermal spraying, aerosol deposition (AD) method, printing, brush coating, iron coating, mold cast molding or the like can be used.
  • AD aerosol deposition
  • the target inorganic porous layer has a large thickness, or when the inorganic porous layer has a multilayer structure, coating of the raw material and drying of the raw material are repeated multiple times to adjust the target thickness or the multilayer structure. You may.
  • the above coating method can also be applied as a coating method for forming a coating layer described later.
  • a coating layer may be provided on the surface of the inorganic porous layer opposite to the surface on which the base material is provided. That is, the inorganic porous layer may be sandwiched between the base material and the coating layer.
  • the coating layer may be provided on the entire surface of the base material of the inorganic porous layer (the surface opposite to the surface on which the base material is provided) or may be provided on a part of the surface of the inorganic porous layer. It may be.
  • the inorganic porous layer can be protected (reinforced) by providing the coating layer.
  • the material of the coating layer may be porous or dense ceramics.
  • porous ceramics used in the coating layer include zirconia (ZrO 2 ), partially stabilized zirconia, and stabilized zirconia.
  • 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 or the like to YSZ, ZrO 2 —HfO 2 —Y 2 O 3 , ZrO 2 --Y 2 O 3 --La 2 O 3 , ZrO 2 --HfO 2 --Y 2 O 3 --La 2 O 3 , HfO 2 --Y 2 O 3 , CeO 2 --Y 2 O 3 , Gd 2 Zr 2 O 7 , Sm 2 Zr 2 O 7 , LaMnAl 11 O 19 , YTa 3 O 9 , Y 0.7 La 0.3 Ta 3 O 9 , Y 1.08 Ta 2.
  • Examples of dense ceramics used in the coating layer include alumina, silica, zirconia, and the like. Further, by removing the ceramic fibers from the above-mentioned constituent material of the inorganic porous layer, a low porosity (denseness) is obtained, and therefore, it may be used as a coating layer. Alternatively, the coating layer may be made of the same material as the inorganic porous layer without using a pore-forming material. By using porous or dense ceramics as the coating layer, it is possible to reinforce the inorganic porous layer and prevent the inorganic porous layer from peeling off from the surface of the substrate.
  • a dense ceramic used as the coating layer, for example, high temperature gas can be prevented from passing through the inorganic porous layer, or high temperature gas can be prevented from staying in the inorganic porous layer. As a result, the effect of suppressing the heat of the high temperature gas from being transferred to the base material can be expected.
  • the use of dense ceramics as the coating layer improves the effect of electrically insulating the base material from the external environment.
  • the material of the coating layer may be porous or dense glass.
  • the use of porous or dense glass as the coating layer also reinforces the inorganic porous layer and can prevent the inorganic porous layer from peeling off from the surface of the substrate.
  • the material of the coating layer may be metal. By providing the metal layer on the surface of the inorganic porous layer, radiant heat from the outside can be reflected, and heat applied to the base material can be further suppressed.
  • the heat dissipation member 10 includes a base material 2 made of aluminum nitride, and a porous protective layer 4 provided on both surfaces of the base material 2 (both surfaces of the end face in the thickness direction).
  • the porous protective layer 4 is an example of an inorganic porous layer.
  • the porous protective layer 4 is bonded to the entire surface of one surface (back surface) of the base material 2, and the other surface (front surface) excludes end portions (both end portions) 2a and 2b in the longitudinal direction of the base material 2. It is joined to the middle part.
  • the porous protective layer 4 is also provided on the side surfaces (four surfaces) of the base material 2.
  • the heat radiating member 10 is a heat conducting member that transfers heat from one end 2a (heat generating part side) to the other end 2b (heat radiating part side).
  • the heat dissipating member 10 was manufactured by immersing the base material 2 in the raw material slurry, drying and firing it while masking a part of the surface of the base material 2 (portions corresponding to the ends 2a and 2b).
  • the raw material slurry had a total of 50% by mass of alumina fibers (average fiber length 140 ⁇ m) 20% by mass and plate-like alumina particles (longitudinal size 10 ⁇ m) 30% by mass as the main raw material of the alumina component, and cordierite particles (average particle size 1 0.5 ⁇ m), 50% by mass, 10% by mass of alumina sol (1.1% by mass of alumina contained in alumina sol), 40% by mass of acrylic resin (average particle size 8 ⁇ m), and ethanol were mixed to prepare.
  • the alumina sol, acrylic resin, and ethanol were externally added to the alumina fibers and cordierite particles.
  • the raw material slurry was adjusted so that the viscosity was 2000 mPa ⁇ s.
  • the base material 2 After immersing the base material 2 in the raw material slurry to apply the raw materials to the front and back surfaces of the base material 2, the base material 2 was put into a dryer and dried at 200° C. (atmosphere atmosphere) for 1 hour. As a result, a porous protective layer having a thickness of about 300 ⁇ m was formed on the front and back surfaces of the base material 2. After that, the step of immersing the base material 2 in the raw material slurry and drying it was repeated three times to form a 1.2 mm porous protective layer on the front and back surfaces of the base material 2. Then, the base material 2 was placed in an electric furnace and baked at 800° C. (atmosphere atmosphere) for 3 hours to prepare the heat dissipation member 10.
  • the porosity of the porous protective layer 4 was 67% by volume and the thermal expansion coefficient was 4.5 ⁇ 10 ⁇ 6 /K.
  • the cordierite particles are present between the front surface (front and back surfaces) of the base material 2 and the aggregate (alumina fiber and the like), so that the surface of the base material 2 and the aggregate are separated. It was confirmed that they were joined. It was also confirmed from the results of X-ray diffraction that cordierite was contained in the porous suture layer 4.
  • FIG. 2 shows a state in which the heat dissipation member 10 is joined to the heat generating part 20 and the heat dissipation part (heat dissipation plate) 22.
  • One end 2 a of the heat dissipation member 10 is joined to the heat generating part 20, and the other end 2 b is joined to the heat dissipation part 22.
  • the heat received by the heat generating portion 20 moves through the base material 2 and is radiated by the heat radiating portion 22. Since the porous protective layer 4 is bonded to the front surface (intermediate portion) and the back surface of the heat conducting member 10, heat radiation from the base material 2 is suppressed between the heat generating portion (heat source) 20 and the heat radiating portion 22. Therefore, it is possible to prevent heat from being applied to devices and the like provided in the space 30 near the front surface of the heat conduction member 10 and the space 32 near the back surface of the heat dissipation member 10.
  • the heat dissipating members 10a to 10e differ from the heat dissipating member 10 in the shape of the base material, the formation position of the porous protective layer, and the presence or absence of the coating layer.
  • the heat radiating members 10a to 10e were adjusted according to the purpose such as the masking position, the conditions for forming the porous protective layer, and the firing conditions after forming the porous protective layer. It was manufactured through the same process. In the following description, description of features common to the heat dissipation member 10 may be omitted.
  • the porous protective layer 4 is provided only on the surface of the base material 2 (one of the end faces in the thickness direction).
  • one end 2a of the back surface of the base material 2 is joined to the heat generating part, and the other end 2b is joined to the heat dissipation part (heat dissipation plate).
  • one end of the heat dissipation member 10a is suppressed while the heat of the heat generating portion is suppressed from being dissipated to the surface side of the heat dissipation member 10a (the side where the porous protection layer 4 is provided) by the porous protection layer 4.
  • the heat of 2a can be transferred to the other end 2b.
  • the porous protection layer 4 may be provided in an intermediate portion of the base member 2 except for the longitudinal end portions (both ends) 2a and 2b, similarly to the heat dissipation member 10 (see also FIG. 1). ).
  • the heat generating portion and/or the heat radiating portion may be bonded to the surface of the base material 2.
  • the heat dissipation member 10b shown in FIG. 4 is a modification of the heat dissipation member 10a.
  • the coating layer 6 is provided on the surface of the porous protective layer 4 (the surface opposite to the surface on which the base material 2 is provided).
  • the coating layer 6 was formed by forming the porous protective layer 4 on the surface of the base material 2, applying a raw material slurry on the surface of the porous protective layer 4 using a spray, and then drying and firing.
  • the raw material slurry used for forming the coating layer 6 was 20% by mass of alumina fibers (average fiber length 140 ⁇ m), 30% by mass of plate-like alumina particles (longitudinal size 10 ⁇ m), and a total of 50% by mass, and cordierite particles ( 50 mass% of the average particle diameter of 1.5 ⁇ m, 10 mass% of alumina sol (1.1 mass% of alumina contained in the alumina sol), and ethanol were mixed to prepare. That is, the raw material slurry used for forming the coating layer 6 is obtained by removing the pore-forming material (acrylic resin) from the raw material slurry used for forming the porous protective layer 4.
  • the coating layer 6 has a denser structure than the porous protective layer 4, and thus functions as a reinforcing material for the porous protective layer 4.
  • the material of the coating layer 6 can be appropriately changed to, for example, the above-mentioned material according to the purpose.
  • the porous protective layer 4 may be provided at an intermediate portion of the base material 2 excluding the longitudinal end portions (both end portions) 2a and 2b. In that case, the heat generating portion and/or the heat radiating portion may be bonded to the surface of the base material 2.
  • the heat dissipation member 10c shown in FIG. 5 is a modified example of the heat dissipation member 10b.
  • the coating layer 6 is intermittently (partially) provided on the surface of the porous protective layer 4 in the longitudinal direction of the heat dissipation member 10c.
  • the coating layer 6 is peeled from the porous protective layer 4 by intermittently providing the coating layer 6 on the surface of the porous protective layer 4. Can be suppressed.
  • the porous protective layer 4 may be provided at an intermediate portion of the base material 2 excluding the longitudinal end portions (both end portions) 2a and 2b. In that case, the heat generating portion and/or the heat radiating portion may be bonded to the surface of the base material 2.
  • the characteristics of the heat dissipation members 10b and 10c (providing a coating layer on the surface of the porous protective layer) can also be applied to the heat dissipation members 10 and 10a.
  • first base material 2X, second base material 2Y are bonded to both surfaces (front and back surfaces) of the porous protective layer 4.
  • one porous protective layer 4 is connected to two base materials (first base material 2X and second base material 2Y) that face each other with a space.
  • a first device (not shown), which is a heat source arranged on the first base material 2X side, is joined to the first base material 2X, and the first base material 2Y is arranged on the second base material 2Y side.
  • a second device (not shown) that is a heat source is joined.
  • the first base material 2X and the second base material 2Y can radiate heat generated from each device.
  • the porous protective layer 4 can suppress the heat of one device (for example, the first device) from being applied to the other device (the second device). That is, the heat dissipation member 410 functions as a heat dissipation plate for two devices and also as a partition plate for insulating between the two devices.
  • the base material 2 is formed of a linear metal.
  • end portions (both end portions) 2a and 2b in the longitudinal direction of the linear base material 2 are exposed. That is, in the heat dissipation member 10e, the porous protective layer 4 is bonded to the intermediate portion of the base material 2 excluding the end portions 2a and 2b.
  • the heat radiating member 10e like the heat radiating members 10 to 10d, has one end 2a joined to the heat generating portion and the other end 2b joined to the heat radiating portion, so that the heat of the heat generating portion (heat source) is radiated. It can dissipate heat.
  • the porous protective layer 4 is provided in the intermediate portion in the longitudinal direction of the heat dissipation member 10e, it is possible to prevent heat from being applied to the components existing around the intermediate portion.
  • the porous protective layer is prepared by mixing the alumina main component (alumina fiber and plate-like alumina particles), cordierite particles, alumina sol, acrylic resin and ethanol to prepare a raw material slurry, and using the base material (aluminum nitride, metal). ) Was dipped in the raw material slurry, and then dried and fired to prepare.
  • the ratio of the alumina component and the cordierite particles was changed and the state of the porous protective layer after firing was confirmed.
  • the compounding amounts of alumina fibers, plate-like alumina particles, titania particles and cordierite particles are changed as shown in FIG. 8 so that the total amount of alumina fibers, plate-like alumina particles, titania particles and cordierite particles is 100.
  • 10% by mass of alumina sol (1.1% by mass of alumina contained in alumina sol) and 40% by mass of acrylic resin are added by external coating, and the slurry viscosity is adjusted with ethanol to prepare a raw material slurry. It was created. Note that Samples 6 and 9 to 13 did not use plate-like alumina particles, and Samples 1 and 7 to 12 did not use titania particles.
  • the raw material slurry was applied to an aluminum nitride plate (base material), dried at 200° C. in the air for 1 hour, and then baked at 800° C. in the air for 3 hours.
  • the number of times the raw material slurry was applied to each sample was adjusted so that a porous protective layer of about 1.2 mm was formed on the aluminum nitride plate.
  • the sample 10 used the silicon carbide board as a base material instead of the aluminum nitride board.
  • a silicon nitride plate was used as the base material instead of the aluminum nitride plate.
  • the appearance of the fired sample was evaluated. For appearance evaluation, the presence or absence of cracks, peeling, etc. was visually observed. In FIG. 9, “ ⁇ ” is assigned to the sample in which cracks and peeling did not occur, and “x” was assigned to the sample in which cracks and peeling occurred.
  • the proportion (mass %) of the alumina component in the porous protective layer was measured. Further, the porosity (volume %), the thermal conductivity and the thermal expansion coefficient of the porous protective layer and the substrate were measured. The porosity, thermal conductivity and thermal expansion coefficient were measured separately for the porous protective layer and the substrate.
  • the amount of aluminum was measured using an ICP emission spectrometer (PS3520UV-DD, manufactured by Hitachi High-Tech Science Co., Ltd.), and the results are shown as oxide conversion (Al 2 O 3 ).
  • the porosity was measured by using a mercury porosimeter in accordance with JIS R1655 (a method for testing the pore size distribution of a molded body by the mercury intrusion method for fine ceramics), and the total pore volume (unit: cm 3 /g) and the gas substitution formula
  • the apparent density (unit: g/cm 3 ) measured with a densitometer (Acupic 1330, manufactured by Micromeritics) was used to calculate from the following formula (2).
  • the thermal conductivity was calculated by multiplying the thermal diffusivity, the specific heat capacity and the bulk density.
  • the thermal diffusivity was measured using a laser flash method thermal constant measuring device, and the specific heat capacity was measured using a DSC (differential scanning calorimeter) according to JIS R1611 (thermal diffusivity/specific heat capacity/thermal conductivity test by laser flash method of fine ceramics). According to the method), the measurement was performed at room temperature.
  • the bulk density (unit: cm 3 /g) was calculated from the following formula (3).
  • the thermal diffusivity was obtained by forming the raw material slurry described above into a bulk body having a diameter of 10 mm and a thickness of 1 mm
  • the specific heat capacity was obtained by forming the raw material slurry described above into a bulk body having a diameter of 5 mm and a thickness of 1 mm.
  • a sample for thermal diffusivity and specific heat capacity measurement was prepared by firing at °C and measured.
  • the above raw material slurry was molded into a bulk body of 3 mm x 4 mm x 20 mm, and then the bulk body was fired at 800°C to prepare a measurement sample. 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 measurement result is shown in FIG.
  • sample 12 has an alumina component ratio of less than 15% by mass, so that the bonding force between the ceramics (particles and fibers) is reduced and cracks are generated in the porous protective layer. ..
  • This result shows that when the thermal expansion coefficient ratio ( ⁇ 1/ ⁇ 2) of the porous protective layer to the substrate is out of the predetermined range (0.5 ⁇ 1/ ⁇ 2 ⁇ 1.2), the substrate has an inorganic porous layer
  • the porous protective layer was easily separated from the base material based on the difference in thermal expansion. From the above, it was confirmed that by making 15% by mass or more of the constituent components of the porous protective layer an alumina component, deterioration such as cracks and peeling is less likely to occur in the porous protective layer after firing.

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