US20180156550A1 - Heat insulation material and device using same - Google Patents
Heat insulation material and device using same Download PDFInfo
- Publication number
- US20180156550A1 US20180156550A1 US15/816,229 US201715816229A US2018156550A1 US 20180156550 A1 US20180156550 A1 US 20180156550A1 US 201715816229 A US201715816229 A US 201715816229A US 2018156550 A1 US2018156550 A1 US 2018156550A1
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- US
- United States
- Prior art keywords
- heat insulation
- carbon
- heat
- composite layer
- carbon material
- 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.)
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- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- 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
- F28F21/02—Constructions of heat-exchange apparatus characterised by the selection of particular materials of carbon, e.g. graphite
-
- 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
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/304—Insulating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
- B32B2605/00—Vehicles
- B32B2605/08—Cars
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
- F16L59/029—Shape or form of insulating materials, with or without coverings integral with the insulating materials layered
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/06—Arrangements using an air layer or vacuum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/14—Arrangements for the insulation of pipes or pipe systems
- F16L59/145—Arrangements for the insulation of pipes or pipe systems providing fire-resistance
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2270/00—Thermal insulation; Thermal decoupling
Definitions
- the technical field relates to heat insulation materials, and devices using the same.
- the technical field relates to flame retardant heat insulation materials, and devices using the same.
- flame retardant polyurethanes that include flame retardants have been developed.
- Flame retardant polyurethanes for example brominated flame retardants have been used as flame retardants for resins. These flame retardants are based on a mechanism in which the surfaces are carbonated at the time of combustion, and thus, combustion progression is prevented.
- upper limits for their workable temperatures are around 100° C. They have been problematic when employed in a high temperature range (e.g., 100° C. or higher) (Japanese Patent No. 5785159, Publication).
- Japanese Patent No. 5785159, Publication Japanese Patent No. 5785159, Publication
- silica aerogels are known to serve as heat insulation materials.
- Silica aerogels have network structures in which silica particles on the scale of several tens of nanometers are connected via point contact, and mean pore diameters are equal to or smaller than 68 nm, which is a mean free path of the air. Accordingly, their heat conductivities are lower than the heat conductivity of the still air.
- silica aerogels organic modification groups may be decomposed by heat under a high-temperature environment, and thus, combustible gases may be produced. Therefore, silica aerogels have problems in flame retardancy and heat resistance.
- an object of the disclosure is to provide heat insulation materials that combine high heat, insulation properties realizing effective heat insulation, and flame retardancy realizing prevention of fire spreading, and devices using the same.
- a heat insulation material including: a silica xerogel; a carbon material; unwoven fabric fibers that retains the silica xerogel, and the carbon material.
- a device including the above-described heat insulation material, wherein the heat insulation material serves as a part of a heat-insulation or refrigeration structure, or is placed between a heat-producing component and a casing.
- heat insulation materials according to the disclosure have heat conductivities lower than those exhibited by conventional heat insulation materials, sufficient heat insulation effects can be obtained even in narrower spaces such as inside electronic devices, in-vehicle devices, and industrial equipment. Thus, conduction of heat from heat-producing components to casings can effectively be reduced. Furthermore, since the heat insulation materials according to the disclosure have sufficient flame retardancy, the heat insulation materials possess fire-spreading-prevention effects that make it possible to prevent fire spreading possibly caused in thermal runaway or firing phenomena.
- FIGS. 1A and 1B are cross-section views of flame retardant heat insulation materials according to embodiments.
- FIG. 2 is a diagram that shows a two-component layer including a silica xerogel and a carbon material in an embodiment.
- FIG. 3 is a three-component composite layer including a silica xerogel, a carbon material, and unwoven fabric fibers in an embodiment.
- FIGS. 4A to 4F are diagrams that shows carbon materials in embodiments.
- FIG. 5 is a diagram that describes a method for producing a flame retardant heat insulation material according to an embodiment.
- FIGS. 6A and 6B are diagrams that show a step in which unwoven fabric fibers are impregnated with a carbon material dispersion, in an embodiment.
- FIG. 7 is a diagram that shows detailed conditions and evaluation results for examples and comparative examples.
- FIG. 8 is a diagram that shows an SEM images of cross-sections of heat insulation materials prepared in EXAMPLE 1 and COMPARATIVE EXAMPLE 1.
- FIGS. 1A and 1B shows cross-section views of heat insulation materials 108 according to embodiments.
- the heat, insulation material shown in FIG. 1A includes a three-component composite layer 103 , two-component composite layer 102 , and a one-component single layer 101 .
- the three-component composite layer 103 includes a silica xerogel 115 , a carbon material 114 , and unwoven fabric fibers 116 .
- the two-component composite layer 102 includes no unwoven fabric fibers 116 , and includes a silica xerogel 115 , and a carbon material 114 .
- the two-component composite layer 102 is placed on the three-component composite layer 103 .
- the one-component single layer 101 is formed of the silica xerogel 115 .
- the silica xerogel 115 , the carbon material 114 , and the unwoven fabric fibers included in each of the layers may be the same. However, different types of materials can also be used therefor.
- the three-component composite layer 103 serves as a main layer of the heat insulation material 108 , and is the thickest of the three layers.
- the three-component composite layer 103 includes as a main ingredient the silica xerogel 115 , and determines the heat insulation performance of the heat insulation material 108 .
- the carbon material which is one of the ingredients included in the three-component composite layer 103 contributes to flame retardancy, while the unwoven fabric fibers 116 serve as a support that makes it possible to realize the heat insulation material 108 as a self-standing structure.
- the two-component composite layer 102 determines flame retardancy performance of the heat insulation material 108 .
- the two-component composite layer 102 is thinner than the three-component composite layer 103 .
- the concentration of the carbon material 114 present in the two-component composite layer 102 is higher than the concentration of the carbon material 114 present in the three-component composite layer 103 . Accordingly, the carbon material 114 present in the two-component composite layer 102 reacts with O 2 present in the atmosphere, thereby producing a larger amount of CO 2 .
- the produced CO 2 dilutes combustible gases, and contributes to flame retardancy.
- the one-component single layer 101 includes the silica xerogel 115 , and is thinner than the three-component composite layer 103 .
- the one-component single layer 101 ensures smoothness of the surface of the heat insulation material 108 . If the one-component single layer 101 lacks smoothness, the contact resistance would become larger, and this may influence the heat insulation performance of the heat insulation material 108 .
- the one-component single layer 101 is provided in order to ensure smoothness of the surface of the heat insulation material 108 .
- FIG. 1B shows a heat insulation material 108 that has a three-layer structure in which a three-component composite layer 103 is placed between two-component composite layers 102 .
- the two-component composite layers 102 exist on both sides. Therefore, when either the front side or the backside of the heat insulation material 108 comes into contact with fire, high concentrations of CO 2 will be produced from the either side. Thus, effective flame retardancy can be delivered.
- FIG. 1A a two-component composite layer 102 is present only on one side. In cases where only one side is possibly brought into contact with flames are expected, such a structure as found in FIG. 1A is preferable.
- FIGS. 1A and 1B Components found in FIGS. 1A and 1B are shown in Tables 1 and 2, respectively.
- filling rates of silica xerogels 115 in the three-component composite layers 103 can be increased so as to secure sufficient heat insulation properties.
- Concentrations of carbon materials 114 in the two-component composite layer 102 , the one-component single layer 101 , and the three-component composite layer 103 are different.
- the concentration of carbon materials 114 in the two-component composite layer 102 is the highest, and the concentration of carbon materials 114 in the three-component composite layer 103 is the second-highest.
- the one-component single layer 101 does not include any carbon materials 114 .
- the concentration of carbon materials 114 is preferably varied in the thickness direction as well as inside the three-component composite layer 103 . That is, the concentration of carbon materials 114 may become higher to the top side direction, and may become lower to the bottom side direction, so as to provide a concentration gradient thereof in the vertical direction.
- the top side refers to a surface of the heat insulation material 108 that is possibly brought into contact with flames.
- the carbon material 114 that is located inside the heat insulation material 108 does not contribute to production of carbon dioxide.
- the carbon material 114 is preferably localized to the one side at a higher concentration.
- Heat conductivity of the unwoven fabric fibers may be from 0.030 to 0.060 W/mK.
- Heat conductivity of a composite including the silica xerogel 115 and the carbon material 114 may be from 0.010 to 0.015 W/mK.
- heat conductivity of the heat insulation material 108 may be from 0.014 to 0.024 W/mK.
- Conventional heat insulation materials that include silica xerogel 115 and unwoven fabric fibers 116 have a structure in which only a two-component composite layer including the silica xerogel 115 and the unwoven fabric fibers 116 are present. As a result, cracks can easily form.
- silica particles that form the silica xerogel 115 are organically modified, and therefore, exhibit hydrophobicity.
- the organic modifying groups are thermally discomposed, and thus, trimethyl silanol and the like are dissociated as large amounts of combustible gases.
- conventional heat insulation materials do not include any carbon materials 114 , such combustible gases may act as a combustion improver.
- substrates of glass papers made of C-glass are not combustible by themselves.
- silica xerogels 115 having large specific surface areas 800 m 2 /g or higher
- large amounts of combustible gases produced from the silica xerogels 115 may catch fire, and consequently, the glass papers made of C-glass may be burned.
- C-glass has lower heat resistance compared with E-glass, and will shrink or deform when it is heated to 750° C. or higher, although it depends on the unit weight.
- the structure of the two-component composite layer 102 is shown in FIG. 2 .
- silica secondary particles 112 that are produced through aggregation of silica primary particles 111 are connected with each other by point contact.
- the silica xerogel 115 is formed as a porous structure having pores 113 on the scale of several tens of nanometers.
- the carbon material 114 has been incorporated into a three-dimensional network of the silica xerogel 115 .
- the carbon material 114 may be connected to the silica primary particles 111 or the silica secondary particles 112 , through covalent bonds or based on intramolecular forces.
- FIG. 3 is a perspective view of the three-component composite layer 103 that includes the silica xerogel 115 , the unwoven fabric fibers 116 , and the carbon material 114 .
- the carbon material 114 exists in a state in which the carbon material 114 is adsorbed onto surfaces of the unwoven fabric fibers 116 based on electrostatic interaction.
- the heat insulation material is brought into contact with flames, or is exposed to a high-temperature environment, i.e., 300° C. or higher, the carbon material 114 reacts with O 2 in the atmosphere so as to produce CO 2 , thereby contributing development of flame retardancy. That is, the carbon material 114 serves as a flame retardant.
- the carbon material 114 used in the present embodiment has at least one condensed ring compound having aromaticity, and reacts with O 2 in the atmosphere to produce CO 2 , at high temperature, e.g., 300° C. or higher.
- high temperature e.g. 300° C. or higher.
- the carbon material 114 may be required that any melting, thermodecomposition, and sublimation not occur in the process of the temperature elevation to 300° C. (thermostability), and it may be required that the carbon material 114 include sp carbon (triple bond) and sp2 carbon (double bond), which easily reacts with O 2 in the atmosphere.
- a condensed ring compound having aromaticity and satisfying these conditions is preferably employed for the carbon material 114 .
- a fullerene 118 depicted in FIG. 4A a graphene 119 depicted in FIG. 4B , a carbon nanotube 120 depicted in FIG. 4C
- Types of the carbon materials 114 are not particularly limited. However, carbon black 123 , which has widely been employed for rubber-reinforcing additives and resin coloring agents, is preferably used.
- the carbon material 114 employed in present embodiments is not known to be effective as a flame retardant by itself. Meanwhile, general flame retardants used for resins are not employed in present embodiments.
- Aluminum hydroxide, magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, molybdenum compounds, brominated monomers, brominated epoxies, bromine-type ethers, polystyrene, phosphate esters, melamine cyanurate, triazine compounds, guanidine compounds, and silicone polymers are typical examples of flame retardants used for resins. These materials are not suitable for development of flame retardancy in the heat insulation material 108 in present embodiments.
- the carbon material 114 used in present embodiments may be added to an aqueous material in advance. Therefore, there are no limitations to the carbon material 114 as long as the carbon material 114 has hydrophilic functional groups in terms of water dispersibility.
- the aromatic carbon compounds that has been subjected to an oxidation treatment based on hydroxyl groups, carboxyl groups, sulfonyl groups, etc. are preferable in terms of economic efficiencies and water dispersibility.
- the carbon material 114 that has been subjected to an oxidation treatment is negatively charged, and has self-dispersibility. Therefore, when the carbon material 114 is added to the aqueous material, the carbon material 114 does not easily settle out therein, and thus, can be stored for a relatively longer period of time. Furthermore, when the sol material is impregnated into the unwoven fabric fibers 116 , the negatively-charged carbon material 114 is adsorbed onto surfaces of unwoven fabric fibers 116 due to electrostatic interaction, and thus, is effective in forming a structure in which the concentration of the carbon material 114 is localized in the above-described manner.
- the average particle size distribution of the carbon material 114 is preferably from 50 to 500 nm. If the average particle size distribution is smaller than 50 nm, productivity may deteriorate. On the other hand, if the average particle size distribution is larger than 500 nm, the carbon material 114 may relatively settle out, and is accumulated in the sol material during mass production. Thus, problems such as unexpected changes in the concentration, pipe clogging, and nozzle clogging may occur.
- An amount of the carbon material 114 is preferably from 0.01 wt % to 10.00 wt % relative to gross weight of the heat insulation material 108 . If the amount is smaller than 0.01 wt %, sufficient flame retardancy may not be obtained. If the amount is larger than 10.00% wt, heat conductivity may excessively be increased, and thus, sufficient heat insulation properties may not be secured.
- the proportion thereof in the two-component composite layer 102 is preferably from about 51 wt % to about 99 wt % relative to the gross amount of the carbon materials 114 included in the heat-insulation materials, and the proportion in the three-component composite layer 103 is preferably from approximately about 1 wt % to about 49 wt %.
- the proportion of the carbon materials 114 included in the two-component composite layer 102 is preferably from 5.1 wt % to 9.9 wt %, which is equivalent to 51% to 99% of the gross amount, i.e., 10%, and the proportion of the carbon materials 114 included in the three-component composite layer 103 is from 0.1 wt % to 4.9 wt %, which is equivalent to 1% to 49% of the gross amount, i.e., 10 wt %.
- the carbon material 114 employed in present embodiments has flame retardancy. However, if an excessive amount of the carbon material 114 is added to the heat-insulation material, a heat conduction ⁇ s of solids may excessively be increased, and thus, the heat conductivity of the heat insulation material 108 may become large. Therefore, attention should be paid to an amount of the carbon material 114 included herein, and the manner of distribution of the carbon material 114 .
- a thickness of the heat insulation material 108 may be within a range from 0.03 mm to 5.0 mm.
- the thickness is preferably within a range from 0.05 mm to 3.0 mm. If the thickness of the heat insulation material 108 is smaller than 0.03 mm, the heat insulation effects may be reduced to the thickness direction. Consequently, the heat transfer to the direction from one side to the other side cannot sufficiently be reduced unless there is a very low heat conductivity such as close to the level realized in vacuum. If the thickness is larger than 0.05 mm, sufficient heat-insulation effects can be secured in the thickness direction.
- the thickness of the heat insulation material 108 is larger than 3.0 mm, it becomes difficult to incorporate the heat insulation material into various devices that have increasingly been smaller and slimmed in recent years.
- a thickness of the heat insulation material 108 may be within a range from 0.03 mm to 5.0 mm.
- the thickness is preferably from 0.05 mm to 3.0 mm.
- An optimum range for a weight proportion of the silica xerogel 115 relative to the gross weight will vary depending on weight unit, bulk density and thickness of the unwoven fabric fibers 116 .
- the weight proportion of the silica xerogel 115 is at least 40 wt % or higher. If the proportion is less than 40 wt %, it may become difficult to realize low heat conductivity. Furthermore, it may be sufficient that the proportion is 80 wt % or lower. If the proportion is higher than 80 wt %, flexibility and strength may become insufficient, and loss of the silica xerogel 115 heat conductivity may be caused through repetitive use.
- a unit weight of the unwoven fabric fibers 116 may be from 5 g/m 2 to 500 g/m 2 . The values will be described in the section of EXAMPLES below.
- the weight unit refers to a weight per unit area.
- the bulk density of the unwoven fabric fibers 116 is preferably within a range from 100 kg/m 3 to 500 kg/m 3 in order to increase the content percentage of the silica xerogel 115 in the heat insulation material 108 , and in order to reduce the heat conductivity.
- the bulk density may need to be at least 100 kg/m 3 . Furthermore, if the bulk density of the unwoven fabric fibers 116 is larger than 500 kg/m 3 , volumes of spaces inside unwoven fabric fibers 116 becomes smaller, an amount of the silica xerogel 115 that is filled into the spaces would be reduced, and thus, the heat conductivity may become higher. The values will be described in EXAMPLES below.
- a material of the unwoven fabric fibers 116 includes at least one type of fibers selected from among aramid fibers, polyimide fibers, novoloid fibers, glass fibers, polyphenylene sulfide (PPS) fibers, oxidated acrylic fibers, graphite fibers, and carbon fibers that have a limiting oxygen index (LOI) of 25 or higher.
- aramid fibers polyimide fibers
- novoloid fibers glass fibers
- PPS polyphenylene sulfide
- oxidated acrylic fibers graphite fibers
- carbon fibers that have a limiting oxygen index (LOI) of 25 or higher.
- the heat insulation material 108 includes the silica xerogel 115 and the carbon material 114 in the same layer.
- the silica particle surface that form the silica xerogel 115 are organically modified, and exhibit hydrophobicity.
- the organic modifying groups are thermally decomposed, a large amount of trimethyl silanol and the like are dissociated as a combustible gas.
- the combustible gas possibly acts as a combustion improver.
- a substrate of a glass paper made of C-glass is not combustible by itself.
- the silica xerogel 115 having a large specific surface (800 m 2 /g or higher) is combined with the glass paper, a large amount of the combustible gas produced from the silica xerogel 115 may catch fire, and thus, the glass paper made of C-glass may be burned.
- C-glass has lower heat resistance compared with E-glass, and therefore, will shrink or deform when it is heated to 750° C. or higher, although it depends on the unit weight.
- the heat insulation material 108 oxygen in the atmosphere, and the carbon material 114 react with each other to produce a large amount of carbon dioxide, at a high temperature, e.g., 300° C. or higher, under the atmosphere, releasing a large amount of carbon dioxide. Accordingly, the combustible gas dissociated from the silica xerogel 115 is prevented from burning.
- FIG. 5 An outline of a method for producing the three-component composite layer 103 is shown in FIG. 5 .
- One part by weight of self-dispersible carbon black CB (Aqua-Black (R) 162 supplied from TOKAI CARBON CO., LTD., solid content concentration: 19.2 wt %) may be added to an aqueous water glass solution (TOSO SANGYO Co., Ltd.) to prepare a carbon black CB-dispersed aqueous water glass solution (SiO 2 concentration: 6%, and carbon black CB: 1.3%).
- 3.6 parts by weight of concentrated hydrochloric acid serving as a catalyst is added to the dispersion, and the dispersion is stirred, to prepare a sol solution.
- a material species for silica is not limited to water glass, and alkoxysilanes, high molar ratio silicate soda may be used.
- inorganic acids e.g., hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, chloric acid, chlorous acid, and hypochlorous acid
- acidic phosphates e.g., acidic aluminum phosphate, acidic magnesium phosphate, acidic zinc phosphate
- organic acids such as (e.g., acetic acid, propionic acid, oxalic acid, succinic acid, citric acid, malic acid, adipic acid, and azelaic acid) can be used.
- types of catalysts used herein are not limited, hydrochloric acid is preferable in terms of strength of the gel skeleton, and hydrophobicity of the silica xerogel 115 .
- the sol solution that is obtained by adding an acid catalyst to an aqueous water glass solution is gelatinized.
- Gelatinization of the sol is preferably carried out inside a sealed vessel from which the liquid medium is not volatinized.
- the pH preferably from 4.0 to 8.0. If the pH is less than 4.0 or is larger than 8.0, the high molar ratio silicate solution may not be gelatinized, although it depends on the temperature during the process.
- the sol solution is poured into unwoven fabric fibers 116 (material: glass papers, thickness specification: 600 um, unit weight: 110 g/m 2 , dimension: 12 cm square) so as to impregnate the sol solution into the unwoven fabric fibers 116 .
- An excessive amount of the sol solution impregnated thereinto is employed relative to a theoretical volume of spaces inside the unwoven fabric fibers 116 (>100%).
- the theoretical volume of spaces inside the unwoven fabric fibers 116 is calculated based on a bulk density of the unwoven fabric fibers 116 .
- the material, thickness and bulk density of the unwoven fabric fibers are not limited to the above-described specifications.
- a method in which each roll of unwoven fabrics is soaked in the sol solution, or a method in which the unwoven fabric fibers 116 are delivered at a constant rate in a roll to roll system, and then, the sol solution is coated onto the unwoven fabric fibers 116 based on a dispenser or spray nozzle may be employed.
- the roll to roll system 1 s preferably employed in terms of productivity.
- a process in which a sol material 124 that is obtained by dispersion of the carbon material 114 is dropwise poured onto the unwoven fabric fibers 116 so as to impregnate the sol material 124 into the unwoven fabric fibers 116 is shown.
- Molecular surfaces of the carbon material 114 are negatively charged. Therefore, the unwoven fabric fibers 116 are preferably positively charged, such that the carbon material 114 is adsorbed onto surfaces of the unwoven fabric fibers 116 , thereby forming a structure in which the carbon material 114 is localized to one side or both sides of the heat insulation material 108 at a high density.
- unwoven fabric fibers 116 Use of such a positively charged unwoven fabric fibers 116 is effective in forming a structure in which the concentration of the carbon material 114 is localized in the above manner, based on adsorption of the carbon material 114 onto surfaces of the unwoven fabric fibers 116 due to electrostatic interaction. As a result, unwoven fabric fibers 116 impregnated with the sol solution, as shown in the cross-section view of FIG. 6B , is produced.
- the unwoven fabric fibers 116 impregnated with the sol solution is held between PP films (50 um thick ⁇ 2, dimension: B6), and this is allowed to stand at room temperature (23° C.) for about 3 minutes, thereby gelatinizing the sol solution.
- the gelatinization time, the thickness control, the materials and thicknesses of the films, between which the impregnated unwoven fabrics are placed, and the aging step, are not limited to the above specifications.
- a linear thermal expansion coefficient of 100 ( ⁇ 10 ⁇ 6 /° C.) or lower e.g., polypropylene (PP), and polyethylene terephthalate (PET)
- PP polypropylene
- PET polyethylene terephthalate
- the sol-impregnated unwoven fabric fibers 116 held between the films is caused to pass through a gap between two-shaft rolls where the gap is set to 1.000 mm (including thicknesses of the films) to squeeze out excess gel from the unwoven fabric fibers 116 , thereby controlling the thickness to 1.0 mm.
- a technique for controlling the thickness is not limited to the above-mentioned technique, and the thickness may be controlled based on techniques using a squeegee, press, or the like.
- An aging vessel is taken out of a thermostatic chamber, and is cooled to room, temperature. Then, the aged sample is removed therefrom, and the films are stripped from the sample.
- the gel sheet is immersed in hydrochloric acid (4-12 N), and then, is allowed to stand at ordinary temperature (23° C.) for 5 minutes or more, to incorporate hydrochloric acid into the gel sheet.
- the gel sheet is immersed in, for example, a mixture of octamethyltrisiloxane, serving as a silylating agent, and 2-propanol (IPA), i.e., an alcohol. Then, this is put into a thermostatic bath at 55° C., and is reacted therein for 2 hours.
- IPA 2-propanol
- hydrochloric acid is discharged from, the gel sheet, and two-liquid separation occurs (siloxane in the upper phase, and aqueous hydrochloric acid and 2-propanol in the lower phase).
- the gel sheet is transferred into a thermostatic bath at 150° C., and is dried therein for 2 hours.
- the type and amount of the carbon material 114 in the above-described sol preparation (i) are varied. That is, while the three-component composite layer 103 is produced, the two-component composite layer 102 or the one-component single layer 101 is also prepared.
- the two-component composite layer 102 containing a higher concentration of the carbon material 114 is formed on the side that has been subjected to the impregnation process.
- the one-component, single layer 101 that does not contain any carbon materials 114 is formed on the opposite side.
- a heat insulation material 108 depicted in FIG. 1A is prepared.
- two-component composite layers 102 are formed on both sides of the two-component composite layer 102 .
- an amount of the carbon material 114 included herein is slight, e.g., less than 1 wt % by weight, a structure shown in FIG. 1A is formed, and, in cases where an amount of the carbon material 114 is 1 wt % or higher, a structure shown in FIG. 1B is formed, although it depends on what type of the carbon material is used herein.
- heat insulation materials 108 in which carbon materials 114 are included, and heat insulation materials 110 in which carbon materials 114 are included were prepared, and the heat insulation materials 108 and 110 were subjected to the following measurement s.
- a heat flowmeter HFM 436 Lamda manufactured by NETZCH
- a TIM tester manufactured by Analysys Tech
- UL94 vertical combustion tests were further carried out to evaluate flame retardance of heat insulation materials 108 and 110 .
- “UL” refers to standards for safeness associated with electric equipment, and the standards were established and approved by UNDERWRITERS LABORATORIES INC. in the United States. Accreditation by UL has even been recognized as proof of safeness. UL has been applied to various products such as electric products, fire prevention equipment, plastic materials, lithium batteries, and electric car-associated equipment.
- the category of UL94 refers to “tests for flammability of plastic materials for appliances and parts in devices”, and there are two types of tests, namely the horizontal flammability test and the vertical flammability test.
- DSC Differential scanning calorimetry
- the cone calorie meter exothermic test has been employed as a fire retardant material test provided in the Japanese Building Standards Act. This test has widely been acknowledged as a testing method involving combustion of materials, across the world. According to this test method, various combustion parameters such as heat release rates, and combustion times can be measured, and therefore, combustion phenomena can be quantified.
- a mechanism for measurements in the cone calorimeter-based exothermic test will be described.
- heat release rates and calorific values are obtained based on a method called “oxygen consumption method.”
- Amounts of heat releases that are caused by combustion significantly vary with types of materials in terms of weights of burning materials.
- amounts of heat releases that are caused by combustion is expressed as a constant value regardless of types of materials, when they are considered in terms of weights of consumed oxygen (13.1 MJ per 1 kg of oxygen), and the cone calorimeter-based exothermic test is based on this insight. That is, by accurately measuring amounts of consumed oxygen in combustions, burning phenomena are quantified.
- GO refers to Graphene Oxide
- CB refers to Carbon Black
- SWCNT refers to Single Walled Carbon Nanotube
- PEDOT PSS refers to Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate).
- heat conductivities of heat insulation materials 108 For heat conductivities of heat insulation materials 108 , samples that exhibited heat conductivities of 0.024 W/mK or less were considered as acceptable. It has been recognized that heat conductivity of still air at ordinary temperature is about 0.026 W/mK. Therefore, in order to effectively insulate flows of heat, heat insulation materials 108 need to have heat conductivities smaller than the heat conductivity of still air.
- an acceptance standard for heat conductivities of heat insulation materials 108 was determined to be 0.024 W/mK or lower, where 0.024 W/mK is about 10% lower than the heat conductivity of still air.
- 0.024 W/mK is about 10% lower than the heat conductivity of still air.
- V0 was considered as acceptable. That is, in the UL94 flammability test, V0, which is the strictest criterion, was considered as acceptable, while V1, V2, and flammable were considered as unacceptable.
- the same testing method was employed for three types of criteria, V0, V1 and V2. That is, bottom edges of samples that were vertically retained were brought into contact with flames generated from gas burners for 10 seconds. If burning phenomena stopped within 30 seconds, the samples were further brought into contact with flames for another 10 seconds. Evaluation criteria for V0, V1, and V2 will be shown below.
- EXAMPLES 1 to 8 correspond to heat insulation materials 108 having the structure shown in FIG. 1A or FIG. 1B .
- COMPARATIVE EXAMPLES 1 and 2 correspond to conventional heat insulation materials having a one-layer structure. Conventional heat insulation materials only have one layer made of unwoven fabric fibers 116 and a silica xerogel 115 .
- COMPARATIVE EXAMPLE 3 have only unwoven fabric fibers 116 .
- COMPARATIVE EXAMPLE 3 corresponds to a heat insulation material in which the unwoven fabric fibers 116 are made of glass papers. Concentrations mentioned below refer to percentages by weight.
- unwoven fabric fibers 116 material: glass paper; thickness: 600 um; weight per area: 100 g/m 2 ; dimension: 12 cm square
- the sol solution was impregnated into the unwoven fabric fibers 116 .
- the unwoven fabric fibers 116 impregnated with the sol solution were held between PP films (50 um thick ⁇ 2 pieces), and allowed to stand at room temperature (23° C.) for three minutes, so as to convert the sol into a gel.
- the impregnated unwoven fabric fibers 116 which were placed between the films, into a dual-axis roll in which the gap was set to 1.00 mm (including the film thicknesses), excess gel was squeezed out of the unwoven fabric fibers 116 , and thus, the thickness was controlled so as to be 1.00 mm.
- the films were peeled, and the gel sheet was immersed in aqueous hydrochloric acid (6 N). Then, by allowing the sample to stand at room temperature (23° C.) for 5 minutes, the gel sheet was allowed to absorb the hydrochloric acid. Subsequently, the gel sheet was immersed in a mixture of octamethyltrisiloxane, which serves as a silylating agent, and 2-propanol (IPA). This was put into a thermostatic chamber at 55° C., and was caused to react for 2 hours.
- IPA 2-propanol
- a heat insulation material 108 having a mean thickness of 0.89 mm, and a heat conductivity of 0.019 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 45.5 wt %.
- the sample was graded as V0.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which any carbon materials 114 were not included.
- the combustion time was zero seconds, and the peak heat release rate was 2.5 kW/m 2 in the flame retardant material test for 20 minutes.
- Self-dispersible type oxidated graphene SIGMA-ALDRICH, 4 mg/ml in H 2 O
- water was added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO 2 concentration: 6%; oxidated graphene GO concentration: 0.5%).
- a sheet was prepared based on the same process conditions as EXAMPLE 1 except that the concentration of the oxidated graphene was increased to 0.5%.
- a heat insulation material 108 having a mean thickness of 0.88 mm, and a heat conductivity of 0.020 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 44.6 wt %.
- the sample was graded as V0.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which any carbon materials 114 were not included.
- the combustion time was zero seconds, and the peak heat release rate was 1.36 kW/m 2 in the flame retardant material test for 20 minutes.
- Self-dispersible type carbon black (TOKAI CARBON CO., LTD., Aqua black 162, and 19.2 wt % in H 2 O) and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO 2 concentration: 6%; carbon black CB concentration: 0.1%).
- TOSO SANGYO CO., LTD. water glass aqueous solution
- a sheet was prepared based on the same process conditions as EXAMPLE 1 except that the carbon material was switched to the carbon black.
- a heat insulation material 108 having a mean thickness of 0.88 mm, and a heat conductivity of 0.019 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 45.9 wt %.
- the sample was graded as V0.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which any carbon materials 114 were not included.
- the combustion time was zero seconds, and the peak heat release rate was 1.33 kW/m 2 in the flame retardant material test for 20 minutes.
- Self-dispersible type carbon black (TOKAI CARBON CO., LTD., Aqua black 162, and 19.2 wt % in H 2 O) and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO 2 concentration: 6%; carbon black CB concentration: 0.5%).
- a starting material SiO 2 concentration: 6%; carbon black CB concentration: 0.5%).
- To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution.
- a sheet was prepared based on the same process conditions as EXAMPLE 3 except that the concentration of the carbon black was increased to 0.5%.
- a heat insulation material 108 having a mean thickness of 0.87 mm, and a heat, conductivity of 0.018 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 45.7 wt %.
- the sample was graded as V0.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which any carbon materials 114 were not included.
- the combustion time was zero seconds, and the peak heat release rate was 1.10 kW/m 2 in the flame retardant material test for 20 minutes.
- FIG. 8 shows an observed SEM image of flame retardant heat insulation materials (composites of unwoven fabric fibers 116 made of glass papers and silica xerogels 115 ) prepared in EXAMPLE 4 and COMPARATIVE EXAMPLE 1.
- EXAMPLE 4 an appearance of carbon materials 114 adsorbed on surfaces of the fibers was confirmed.
- Single-walled carbon nanotubes SWCNT SIGMA-ALDRICH
- TOSO SANGYO CO., LTD. water glass aqueous solution
- SiO 2 concentration: 6%; SWCNT concentration: 0.1%) To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution.
- a sheet was prepared based on the same process conditions as EXAMPLE 1 except, that the carbon material was switched to SWCNT.
- a heat insulation material 108 having a mean thickness of 0.85 mm, and a heat conductivity of 0.018 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 45.5 wt %.
- the sample was graded as V0.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which any carbon materials 114 were not included.
- the combustion time was 10 seconds, and the peak heat release rate was 14.06 kW/m 2 in the flame retardant material test for 20 minutes.
- Single-walled carbon nanotubes SWCNT (SIGMA-ALDRICH), which is PEG-modified to enhance dispersibility, served as a carbon material 114 , and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO 2 concentration: 6%; SWCNT concentration: 0.5%).
- a water glass aqueous solution TOSO SANGYO CO., LTD.
- a sheet was prepared based on the same process conditions as EXAMPLE 5 except that the concentration of SWCNT was increased in the above-mentioned manner.
- a heat insulation material 108 having a mean thickness of 0.86 mm, and a heat conductivity of 0.018 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 45.6 wt %.
- the sample was graded as V0.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which any carbon materials 114 were not included.
- the combustion time was 10 seconds, and the peak heat release rate was 13.02 kW/m 2 in the flame retardant material test for 20 minutes.
- PEDOT poly(3,4-ethylenedioxythiophene)/polysulfonate
- PEDOT poly(3,4-ethylenedioxythiophene)/polysulfonate
- TOSO SANGYO CO., LTD. water glass aqueous solution
- a starting material SiO 2 concentration: 6%; PEDOT: PSS concentration: 0.5%).
- To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution.
- a sheet was prepared based on the same process conditions as EXAMPLE 1 except that the carbon material was switched to PEDOT: PSS.
- a heat insulation material 108 having a mean thickness of 0.86 mm, and a heat conductivity of 0.018 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 45.9 wt %.
- the sample was graded as V0.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which any carbon materials 114 were not included.
- the combustion time was zero seconds, and the peak heat release rate was 1.31 kW/m 2 in the flame retardant material test for 20 minutes.
- a heat insulation material 108 having a mean thickness of 1.3 mm, and a heat conductivity of 0.018 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 67.6 wt %.
- the sample was graded as V0.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which any carbon materials 114 were not included.
- the combustion time was 14.7 seconds, and the peak heat release rate was 10.94 kW/m 2 in the flame retardant material test for 20 minutes.
- a sheet was prepared based on the same process conditions as those in EXAMPLE 1 except that no self-dispersible oxidated graphene was added to an aqueous water glass serving as a starting material.
- a heat insulation material 107 having a mean thickness of 0.86 mm, and a heat conductivity of 0.019 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 45.4 wt %.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was low, i.e., 360° C.
- the combustion time was 12.7 seconds, and the peak heat release rate was 16.39 kW/m 2 in the flame retardant material test for 20 minutes. In the comprehensive evaluations, the sample was unacceptable.
- a heat insulation sheet was prepared based on the same process conditions as those in EXAMPLE 8 except that no carbon material 114 was added to an aqueous high molar ratio silicate soda (TOSO SANGYO CO., LTD.).
- a heat insulation material 107 having a mean thickness of 1.03 mm, and a heat conductivity of 0.020 W/mK was obtained.
- a filling rate of the silica xerogel 115 was 63.0 wt %.
- the thermal decomposition temperature (exothermic peak) of organic modifying groups was low, i.e., 380° C.
- the combustion time was 24.8 seconds, and the peak heat release rate was 28.69 kW/m 2 in the flame retardant material test for 20 minutes. In the comprehensive evaluations, the sample was unacceptable.
- FIG. 8 refers to observed scanning electron micrographs of heat insulation materials (composites of unwoven fabric fibers 116 made of glass papers, and silica xerogel 115 ) prepared in EXAMPLE 4 and COMPARATIVE EXAMPLE 1.
- EXAMPLE 1 particles of carbon black are adsorbed onto the surface of unwoven fabric fibers 116 .
- COMPARATIVE EXAMPLE 1 there are no carbon materials 114 that are adsorbed onto the surface of unwoven fabric fibers 116 .
- carbon black, oxidated graphene, single-walled carbon nanotubes, and PEDOT: PSS are effective, and that preferable amounts of these materials are 0.1 wt % to 1.3 wt %.
- the disclosure is not limited to the structures shown in FIGS. 1A and 1B as long as the three-component composite layer 103 can produce effects of heat insulation materials and can solve the above-mentioned objectives.
- the disclosure will be employed in a wide range of fields since the heat insulation material according to the disclosure can produce sufficient heat insulation effects even in narrow spaces inside electronic devices, in-vehicle devices, and industrial devices.
- the disclosure is applicable to all types of products associated with heat (i.e., information devices, portable devices, displays, and electric components).
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Abstract
Description
- The technical field relates to heat insulation materials, and devices using the same. In particular, the technical field relates to flame retardant heat insulation materials, and devices using the same.
- In recent years in the fields of automobile and industrial equipment that control heat flows, safety, and fire prevention of fires capable of spreading to neighboring areas, it has been required that the equipment be confined to limited and narrow spaces. Therefore, there has been growing demands for non-conventional high-performance heat insulation materials that combine excellent heat-insulation properties, flame retardancy, and heat resistance. Thus, effective heat insulation can be realized even if they are shaped into thin forms.
- For this reason, flame retardant polyurethanes that include flame retardants have been developed. Flame retardant polyurethanes, for example brominated flame retardants have been used as flame retardants for resins. These flame retardants are based on a mechanism in which the surfaces are carbonated at the time of combustion, and thus, combustion progression is prevented. However, upper limits for their workable temperatures are around 100° C. They have been problematic when employed in a high temperature range (e.g., 100° C. or higher) (Japanese Patent No. 5785159, Publication). Furthermore, it is difficult to shape them into thin forms having thicknesses equal to or smaller than the foam diameters, since they are foams.
- Meanwhile, silica aerogels are known to serve as heat insulation materials. Silica aerogels have network structures in which silica particles on the scale of several tens of nanometers are connected via point contact, and mean pore diameters are equal to or smaller than 68 nm, which is a mean free path of the air. Accordingly, their heat conductivities are lower than the heat conductivity of the still air.
- However, in silica aerogels, organic modification groups may be decomposed by heat under a high-temperature environment, and thus, combustible gases may be produced. Therefore, silica aerogels have problems in flame retardancy and heat resistance.
- Hence, an object of the disclosure is to provide heat insulation materials that combine high heat, insulation properties realizing effective heat insulation, and flame retardancy realizing prevention of fire spreading, and devices using the same.
- In order to achieve the above-mentioned objectives, according to one aspect of the disclosure, provided is a heat insulation material, including: a silica xerogel; a carbon material; unwoven fabric fibers that retains the silica xerogel, and the carbon material.
- Furthermore, according to another aspect of the disclosure, provided is a device, including the above-described heat insulation material, wherein the heat insulation material serves as a part of a heat-insulation or refrigeration structure, or is placed between a heat-producing component and a casing.
- Since heat insulation materials according to the disclosure have heat conductivities lower than those exhibited by conventional heat insulation materials, sufficient heat insulation effects can be obtained even in narrower spaces such as inside electronic devices, in-vehicle devices, and industrial equipment. Thus, conduction of heat from heat-producing components to casings can effectively be reduced. Furthermore, since the heat insulation materials according to the disclosure have sufficient flame retardancy, the heat insulation materials possess fire-spreading-prevention effects that make it possible to prevent fire spreading possibly caused in thermal runaway or firing phenomena.
-
FIGS. 1A and 1B are cross-section views of flame retardant heat insulation materials according to embodiments. -
FIG. 2 is a diagram that shows a two-component layer including a silica xerogel and a carbon material in an embodiment. -
FIG. 3 is a three-component composite layer including a silica xerogel, a carbon material, and unwoven fabric fibers in an embodiment. -
FIGS. 4A to 4F are diagrams that shows carbon materials in embodiments. -
FIG. 5 is a diagram that describes a method for producing a flame retardant heat insulation material according to an embodiment. -
FIGS. 6A and 6B are diagrams that show a step in which unwoven fabric fibers are impregnated with a carbon material dispersion, in an embodiment. -
FIG. 7 is a diagram that shows detailed conditions and evaluation results for examples and comparative examples. -
FIG. 8 is a diagram that shows an SEM images of cross-sections of heat insulation materials prepared in EXAMPLE 1 and COMPARATIVE EXAMPLE 1. - Next, embodiments according to the disclosure will be described with reference to one preferable embodiment.
-
FIGS. 1A and 1B shows cross-section views ofheat insulation materials 108 according to embodiments. - The heat, insulation material shown in
FIG. 1A includes a three-component composite layer 103, two-component composite layer 102, and a one-componentsingle layer 101. - The three-
component composite layer 103 includes asilica xerogel 115, acarbon material 114, andunwoven fabric fibers 116. - The two-
component composite layer 102 includes nounwoven fabric fibers 116, and includes asilica xerogel 115, and acarbon material 114. The two-component composite layer 102 is placed on the three-component composite layer 103. - The one-component
single layer 101 is formed of thesilica xerogel 115. - The
silica xerogel 115, thecarbon material 114, and the unwoven fabric fibers included in each of the layers may be the same. However, different types of materials can also be used therefor. - The role of each layer will be described below.
- The three-
component composite layer 103 serves as a main layer of theheat insulation material 108, and is the thickest of the three layers. The three-component composite layer 103 includes as a main ingredient thesilica xerogel 115, and determines the heat insulation performance of theheat insulation material 108. Additionally, the carbon material, which is one of the ingredients included in the three-component composite layer 103 contributes to flame retardancy, while theunwoven fabric fibers 116 serve as a support that makes it possible to realize theheat insulation material 108 as a self-standing structure. - The two-
component composite layer 102 determines flame retardancy performance of theheat insulation material 108. The two-component composite layer 102 is thinner than the three-component composite layer 103. However, the concentration of thecarbon material 114 present in the two-component composite layer 102 is higher than the concentration of thecarbon material 114 present in the three-component composite layer 103. Accordingly, thecarbon material 114 present in the two-component composite layer 102 reacts with O2 present in the atmosphere, thereby producing a larger amount of CO2. The produced CO2 dilutes combustible gases, and contributes to flame retardancy. - The one-component
single layer 101 includes thesilica xerogel 115, and is thinner than the three-component composite layer 103. The one-componentsingle layer 101 ensures smoothness of the surface of theheat insulation material 108. If the one-componentsingle layer 101 lacks smoothness, the contact resistance would become larger, and this may influence the heat insulation performance of theheat insulation material 108. The one-componentsingle layer 101 is provided in order to ensure smoothness of the surface of theheat insulation material 108. - On the other hand,
FIG. 1B shows aheat insulation material 108 that has a three-layer structure in which a three-component composite layer 103 is placed between two-component composite layers 102. - In
FIG. 1B , the two-component composite layers 102 exist on both sides. Therefore, when either the front side or the backside of theheat insulation material 108 comes into contact with fire, high concentrations of CO2 will be produced from the either side. Thus, effective flame retardancy can be delivered. -
FIG. 1A , a two-component composite layer 102 is present only on one side. In cases where only one side is possibly brought into contact with flames are expected, such a structure as found inFIG. 1A is preferable. - Components found in
FIGS. 1A and 1B are shown in Tables 1 and 2, respectively. -
TABLE 1 Layer Components Two-component Including no unwoven fabric fibers 116, butcomposite layer 102including a silica xerogel 115 and acarbon material 114 Three-component Including a silica xerogel 115, acarbon composite layer 103 material 114, andunwoven fabric fibers 116One-component Including no unwoven fabric fibers 116, butmonolayer 101including a silica xerogel 115 -
TABLE 2 Layer Components Two-component Including no unwoven fabric fibers 116, butcomposite layer 102including a silica xerogel 115 and acarbon material 114 Three-component Including a silica xerogel 115, acarbon composite layer 103 material 114, andunwoven fabric fibers 116One-component Including no unwoven fabric fibers 116, butmonolayer 101including a silica xerogel 115 - According to the above structures, filling rates of silica xerogels 115 in the three-component composite layers 103 can be increased so as to secure sufficient heat insulation properties.
- Concentrations of
carbon materials 114 in the two-component composite layer 102, the one-componentsingle layer 101, and the three-component composite layer 103 are different. The concentration ofcarbon materials 114 in the two-component composite layer 102 is the highest, and the concentration ofcarbon materials 114 in the three-component composite layer 103 is the second-highest. In principle, the one-componentsingle layer 101 does not include anycarbon materials 114. - Furthermore, the concentration of
carbon materials 114 is preferably varied in the thickness direction as well as inside the three-component composite layer 103. That is, the concentration ofcarbon materials 114 may become higher to the top side direction, and may become lower to the bottom side direction, so as to provide a concentration gradient thereof in the vertical direction. In addition, the top side refers to a surface of theheat insulation material 108 that is possibly brought into contact with flames. - If a high concentration of the
carbon material 114 is evenly dispersed therein, carbon particles would be connected with each other along the thickness direction, and thus, heat conduction paths may be formed, thereby increasing the heat conductivity. In such a case, heat insulation properties of theheat insulation material 108 would be inferior, and therefore is not preferable. - Furthermore, the
carbon material 114 that is located inside theheat insulation material 108 does not contribute to production of carbon dioxide. - For this reason, in order to combine sufficient heat insulation properties (heat conductivity) and flame retardancy, instead of evenly dispersing the
carbon material 114 therein, thecarbon material 114 is preferably localized to the one side at a higher concentration. - Heat conductivity of the unwoven fabric fibers may be from 0.030 to 0.060 W/mK. Heat conductivity of a composite including the
silica xerogel 115 and thecarbon material 114 may be from 0.010 to 0.015 W/mK. As a result, heat conductivity of theheat insulation material 108 may be from 0.014 to 0.024 W/mK. - Conventional heat insulation materials that include
silica xerogel 115 andunwoven fabric fibers 116 have a structure in which only a two-component composite layer including thesilica xerogel 115 and theunwoven fabric fibers 116 are present. As a result, cracks can easily form. - Surfaces of silica particles that form the
silica xerogel 115 are organically modified, and therefore, exhibit hydrophobicity. However, when thesilica xerogel 115 is heated to a high temperature, i.e., 300° C. or higher, the organic modifying groups are thermally discomposed, and thus, trimethyl silanol and the like are dissociated as large amounts of combustible gases. - Since conventional heat insulation materials do not include any
carbon materials 114, such combustible gases may act as a combustion improver. For example, substrates of glass papers made of C-glass are not combustible by themselves. However, when silica xerogels 115 having large specific surface areas (800 m2/g or higher) are combined with the glass papers, large amounts of combustible gases produced from thesilica xerogels 115 may catch fire, and consequently, the glass papers made of C-glass may be burned. C-glass has lower heat resistance compared with E-glass, and will shrink or deform when it is heated to 750° C. or higher, although it depends on the unit weight. - The structure of the two-
component composite layer 102 is shown inFIG. 2 . - In the
silica xerogel 115, silicasecondary particles 112 that are produced through aggregation of silicaprimary particles 111 are connected with each other by point contact. Thus, thesilica xerogel 115 is formed as a porousstructure having pores 113 on the scale of several tens of nanometers. Thecarbon material 114 has been incorporated into a three-dimensional network of thesilica xerogel 115. Thecarbon material 114 may be connected to the silicaprimary particles 111 or the silicasecondary particles 112, through covalent bonds or based on intramolecular forces. -
FIG. 3 is a perspective view of the three-component composite layer 103 that includes thesilica xerogel 115, theunwoven fabric fibers 116, and thecarbon material 114. As shown inFIG. 3 , in the three-component composite layer 103, thecarbon material 114 exists in a state in which thecarbon material 114 is adsorbed onto surfaces of theunwoven fabric fibers 116 based on electrostatic interaction. When the heat insulation material is brought into contact with flames, or is exposed to a high-temperature environment, i.e., 300° C. or higher, thecarbon material 114 reacts with O2 in the atmosphere so as to produce CO2, thereby contributing development of flame retardancy. That is, thecarbon material 114 serves as a flame retardant. - The
carbon material 114 used in the present embodiment has at least one condensed ring compound having aromaticity, and reacts with O2 in the atmosphere to produce CO2, at high temperature, e.g., 300° C. or higher. With regards to conditions for thecarbon material 114 producing CO2 at 300° C. or higher, for example, it may be required that any melting, thermodecomposition, and sublimation not occur in the process of the temperature elevation to 300° C. (thermostability), and it may be required that thecarbon material 114 include sp carbon (triple bond) and sp2 carbon (double bond), which easily reacts with O2 in the atmosphere. A condensed ring compound having aromaticity and satisfying these conditions is preferably employed for thecarbon material 114. -
FIGS. 4A to 4F shows examples of structures ofcarbon materials 114 that can be employed in the present embodiments. That is, afullerene 118 depicted inFIG. 4A , agraphene 119 depicted inFIG. 4B , acarbon nanotube 120 depicted inFIG. 4C , an electrically-conductive polymer 121 (e.g., polypyrroles, polyanilines, polythiophenes, and polyacetylenes) depicted inFIG. 4D , apolyacene 122 depicted inFIG. 4E (e.g., polyacene where n=1, naphthacene where n=2, and pentacene where n=3), andcarbon black 123 depicted inFIG. 4F can be employed therefor. - Types of the
carbon materials 114 are not particularly limited. However,carbon black 123, which has widely been employed for rubber-reinforcing additives and resin coloring agents, is preferably used. - The
carbon material 114 employed in present embodiments is not known to be effective as a flame retardant by itself. Meanwhile, general flame retardants used for resins are not employed in present embodiments. Aluminum hydroxide, magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, molybdenum compounds, brominated monomers, brominated epoxies, bromine-type ethers, polystyrene, phosphate esters, melamine cyanurate, triazine compounds, guanidine compounds, and silicone polymers are typical examples of flame retardants used for resins. These materials are not suitable for development of flame retardancy in theheat insulation material 108 in present embodiments. - Furthermore, the
carbon material 114 used in present embodiments may be added to an aqueous material in advance. Therefore, there are no limitations to thecarbon material 114 as long as thecarbon material 114 has hydrophilic functional groups in terms of water dispersibility. However, the aromatic carbon compounds that has been subjected to an oxidation treatment based on hydroxyl groups, carboxyl groups, sulfonyl groups, etc. are preferable in terms of economic efficiencies and water dispersibility. - The
carbon material 114 that has been subjected to an oxidation treatment is negatively charged, and has self-dispersibility. Therefore, when thecarbon material 114 is added to the aqueous material, thecarbon material 114 does not easily settle out therein, and thus, can be stored for a relatively longer period of time. Furthermore, when the sol material is impregnated into theunwoven fabric fibers 116, the negatively-chargedcarbon material 114 is adsorbed onto surfaces ofunwoven fabric fibers 116 due to electrostatic interaction, and thus, is effective in forming a structure in which the concentration of thecarbon material 114 is localized in the above-described manner. - The average particle size distribution of the
carbon material 114 is preferably from 50 to 500 nm. If the average particle size distribution is smaller than 50 nm, productivity may deteriorate. On the other hand, if the average particle size distribution is larger than 500 nm, thecarbon material 114 may relatively settle out, and is accumulated in the sol material during mass production. Thus, problems such as unexpected changes in the concentration, pipe clogging, and nozzle clogging may occur. - An amount of the
carbon material 114 is preferably from 0.01 wt % to 10.00 wt % relative to gross weight of theheat insulation material 108. If the amount is smaller than 0.01 wt %, sufficient flame retardancy may not be obtained. If the amount is larger than 10.00% wt, heat conductivity may excessively be increased, and thus, sufficient heat insulation properties may not be secured. - With regards to proportions (distributions) of the
carbon materials 114 included in the respective layers, the proportion thereof in the two-component composite layer 102 is preferably from about 51 wt % to about 99 wt % relative to the gross amount of thecarbon materials 114 included in the heat-insulation materials, and the proportion in the three-component composite layer 103 is preferably from approximately about 1 wt % to about 49 wt %. That is, when 10 wt % of thecarbon materials 114 is included in the heat-insulation material, the proportion of thecarbon materials 114 included in the two-component composite layer 102 is preferably from 5.1 wt % to 9.9 wt %, which is equivalent to 51% to 99% of the gross amount, i.e., 10%, and the proportion of thecarbon materials 114 included in the three-component composite layer 103 is from 0.1 wt % to 4.9 wt %, which is equivalent to 1% to 49% of the gross amount, i.e., 10 wt %. - The
carbon material 114 employed in present embodiments has flame retardancy. However, if an excessive amount of thecarbon material 114 is added to the heat-insulation material, a heat conduction λs of solids may excessively be increased, and thus, the heat conductivity of theheat insulation material 108 may become large. Therefore, attention should be paid to an amount of thecarbon material 114 included herein, and the manner of distribution of thecarbon material 114. - A thickness of the
heat insulation material 108 may be within a range from 0.03 mm to 5.0 mm. The thickness is preferably within a range from 0.05 mm to 3.0 mm. If the thickness of theheat insulation material 108 is smaller than 0.03 mm, the heat insulation effects may be reduced to the thickness direction. Consequently, the heat transfer to the direction from one side to the other side cannot sufficiently be reduced unless there is a very low heat conductivity such as close to the level realized in vacuum. If the thickness is larger than 0.05 mm, sufficient heat-insulation effects can be secured in the thickness direction. - On the other hand, if the thickness of the
heat insulation material 108 is larger than 3.0 mm, it becomes difficult to incorporate the heat insulation material into various devices that have increasingly been smaller and slimmed in recent years. - A thickness of the
heat insulation material 108 may be within a range from 0.03 mm to 5.0 mm. The thickness is preferably from 0.05 mm to 3.0 mm. An optimum range for a weight proportion of thesilica xerogel 115 relative to the gross weight will vary depending on weight unit, bulk density and thickness of theunwoven fabric fibers 116. - It may be sufficient that the weight proportion of the
silica xerogel 115 is at least 40 wt % or higher. If the proportion is less than 40 wt %, it may become difficult to realize low heat conductivity. Furthermore, it may be sufficient that the proportion is 80 wt % or lower. If the proportion is higher than 80 wt %, flexibility and strength may become insufficient, and loss of thesilica xerogel 115 heat conductivity may be caused through repetitive use. - A unit weight of the
unwoven fabric fibers 116 may be from 5 g/m2 to 500 g/m2. The values will be described in the section of EXAMPLES below. In addition, the weight unit refers to a weight per unit area. - The bulk density of the
unwoven fabric fibers 116 is preferably within a range from 100 kg/m3 to 500 kg/m3 in order to increase the content percentage of thesilica xerogel 115 in theheat insulation material 108, and in order to reduce the heat conductivity. - In order to form
unwoven fabric fibers 116 that possess sufficient mechanical strength as a continuous body, the bulk density may need to be at least 100 kg/m3. Furthermore, if the bulk density of theunwoven fabric fibers 116 is larger than 500 kg/m3, volumes of spaces insideunwoven fabric fibers 116 becomes smaller, an amount of thesilica xerogel 115 that is filled into the spaces would be reduced, and thus, the heat conductivity may become higher. The values will be described in EXAMPLES below. - A material of the
unwoven fabric fibers 116 includes at least one type of fibers selected from among aramid fibers, polyimide fibers, novoloid fibers, glass fibers, polyphenylene sulfide (PPS) fibers, oxidated acrylic fibers, graphite fibers, and carbon fibers that have a limiting oxygen index (LOI) of 25 or higher. - A mechanism for development of flame retardancy will be described. The
heat insulation material 108 includes thesilica xerogel 115 and thecarbon material 114 in the same layer. The silica particle surface that form thesilica xerogel 115 are organically modified, and exhibit hydrophobicity. However, when thesilica xerogel 115 is heated to a high temperature, e.g., 300° C. or higher, the organic modifying groups are thermally decomposed, a large amount of trimethyl silanol and the like are dissociated as a combustible gas. The combustible gas possibly acts as a combustion improver. - For example, a substrate of a glass paper made of C-glass is not combustible by itself. However, when the
silica xerogel 115 having a large specific surface (800 m2/g or higher) is combined with the glass paper, a large amount of the combustible gas produced from thesilica xerogel 115 may catch fire, and thus, the glass paper made of C-glass may be burned. C-glass has lower heat resistance compared with E-glass, and therefore, will shrink or deform when it is heated to 750° C. or higher, although it depends on the unit weight. - To the contrary, in the
heat insulation material 108 according to the present, disclosure, oxygen in the atmosphere, and thecarbon material 114 react with each other to produce a large amount of carbon dioxide, at a high temperature, e.g., 300° C. or higher, under the atmosphere, releasing a large amount of carbon dioxide. Accordingly, the combustible gas dissociated from thesilica xerogel 115 is prevented from burning. - An outline of a method for producing the three-
component composite layer 103 is shown inFIG. 5 . - One part by weight of self-dispersible carbon black CB (Aqua-Black (R) 162 supplied from TOKAI CARBON CO., LTD., solid content concentration: 19.2 wt %) may be added to an aqueous water glass solution (TOSO SANGYO Co., Ltd.) to prepare a carbon black CB-dispersed aqueous water glass solution (SiO2 concentration: 6%, and carbon black CB: 1.3%). 3.6 parts by weight of concentrated hydrochloric acid serving as a catalyst is added to the dispersion, and the dispersion is stirred, to prepare a sol solution. However, a material species for silica is not limited to water glass, and alkoxysilanes, high molar ratio silicate soda may be used.
- With regards to types of usable acids: inorganic acids (e.g., hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, chloric acid, chlorous acid, and hypochlorous acid), acidic phosphates (e.g., acidic aluminum phosphate, acidic magnesium phosphate, acidic zinc phosphate), organic acids such as (e.g., acetic acid, propionic acid, oxalic acid, succinic acid, citric acid, malic acid, adipic acid, and azelaic acid) can be used. Although types of catalysts used herein are not limited, hydrochloric acid is preferable in terms of strength of the gel skeleton, and hydrophobicity of the
silica xerogel 115. - Then, the sol solution that is obtained by adding an acid catalyst to an aqueous water glass solution is gelatinized. Gelatinization of the sol is preferably carried out inside a sealed vessel from which the liquid medium is not volatinized.
- When the high molar ratio silicate solution is gelatinized by adding the acid thereto, the pH preferably from 4.0 to 8.0. If the pH is less than 4.0 or is larger than 8.0, the high molar ratio silicate solution may not be gelatinized, although it depends on the temperature during the process.
- (ii) Impregnation of the Sol Solution into Unwoven Fabrics
- The sol solution is poured into unwoven fabric fibers 116 (material: glass papers, thickness specification: 600 um, unit weight: 110 g/m2, dimension: 12 cm square) so as to impregnate the sol solution into the
unwoven fabric fibers 116. An excessive amount of the sol solution impregnated thereinto is employed relative to a theoretical volume of spaces inside the unwoven fabric fibers 116 (>100%). The theoretical volume of spaces inside theunwoven fabric fibers 116 is calculated based on a bulk density of theunwoven fabric fibers 116. Furthermore, as mentioned above, the material, thickness and bulk density of the unwoven fabric fibers are not limited to the above-described specifications. With regards to usable impregnation techniques, a method in which each roll of unwoven fabrics is soaked in the sol solution, or a method in which theunwoven fabric fibers 116 are delivered at a constant rate in a roll to roll system, and then, the sol solution is coated onto theunwoven fabric fibers 116 based on a dispenser or spray nozzle may be employed. However, the roll to roll system 1s preferably employed in terms of productivity. - In the cross-section view of
FIG. 6A , a process in which asol material 124 that is obtained by dispersion of thecarbon material 114 is dropwise poured onto theunwoven fabric fibers 116 so as to impregnate thesol material 124 into theunwoven fabric fibers 116 is shown. Molecular surfaces of thecarbon material 114 are negatively charged. Therefore, theunwoven fabric fibers 116 are preferably positively charged, such that thecarbon material 114 is adsorbed onto surfaces of theunwoven fabric fibers 116, thereby forming a structure in which thecarbon material 114 is localized to one side or both sides of theheat insulation material 108 at a high density. Use of such a positively chargedunwoven fabric fibers 116 is effective in forming a structure in which the concentration of thecarbon material 114 is localized in the above manner, based on adsorption of thecarbon material 114 onto surfaces of theunwoven fabric fibers 116 due to electrostatic interaction. As a result,unwoven fabric fibers 116 impregnated with the sol solution, as shown in the cross-section view ofFIG. 6B , is produced. - (iii) Placing the Unwoven Fabric Fibers Between Films
- The
unwoven fabric fibers 116 impregnated with the sol solution is held between PP films (50 um thick×2, dimension: B6), and this is allowed to stand at room temperature (23° C.) for about 3 minutes, thereby gelatinizing the sol solution. The gelatinization time, the thickness control, the materials and thicknesses of the films, between which the impregnated unwoven fabrics are placed, and the aging step, are not limited to the above specifications. For materials of the films, a resin material having a maximum working temperature of 100° C. or higher and a linear thermal expansion coefficient of 100 (×10−6/° C.) or lower (e.g., polypropylene (PP), and polyethylene terephthalate (PET)) is preferable, since a heating process is required in the aging step. - After it is confirmed that the gelatinization is completed, the sol-impregnated
unwoven fabric fibers 116 held between the films is caused to pass through a gap between two-shaft rolls where the gap is set to 1.000 mm (including thicknesses of the films) to squeeze out excess gel from theunwoven fabric fibers 116, thereby controlling the thickness to 1.0 mm. In addition, a technique for controlling the thickness is not limited to the above-mentioned technique, and the thickness may be controlled based on techniques using a squeegee, press, or the like. - An aging vessel is taken out of a thermostatic chamber, and is cooled to room, temperature. Then, the aged sample is removed therefrom, and the films are stripped from the sample.
- The gel sheet is immersed in hydrochloric acid (4-12 N), and then, is allowed to stand at ordinary temperature (23° C.) for 5 minutes or more, to incorporate hydrochloric acid into the gel sheet.
- (vii) Second Hydrophobization (Siloxane Treatment)
- The gel sheet is immersed in, for example, a mixture of octamethyltrisiloxane, serving as a silylating agent, and 2-propanol (IPA), i.e., an alcohol. Then, this is put into a thermostatic bath at 55° C., and is reacted therein for 2 hours. When formation of trimethylsiloxane bonds is started, hydrochloric acid is discharged from, the gel sheet, and two-liquid separation occurs (siloxane in the upper phase, and aqueous hydrochloric acid and 2-propanol in the lower phase).
- (viii) Drying
- The gel sheet is transferred into a thermostatic bath at 150° C., and is dried therein for 2 hours.
- An example of producing a three-
component composite layer 103 is described above with reference toFIG. 6 , However, production of the three-component composite layer 103 is not limited to this example. - To produce a
heat insulation material 108, in the above-described method for producing a three-component composite layer 103, the type and amount of thecarbon material 114 in the above-described sol preparation (i) are varied. That is, while the three-component composite layer 103 is produced, the two-component composite layer 102 or the one-componentsingle layer 101 is also prepared. - Due to interaction between negatively charged molecular surfaces of the
carbon material 114 and positively charged surfaces of theunwoven fabric fibers 116, the two-component composite layer 102 containing a higher concentration of thecarbon material 114 is formed on the side that has been subjected to the impregnation process. The one-component,single layer 101 that does not contain anycarbon materials 114 is formed on the opposite side. As a result, aheat insulation material 108 depicted inFIG. 1A is prepared. - On the other hand, in a case where an amount of the
carbon material 114 is increased, two-component composite layers 102 are formed on both sides of the two-component composite layer 102. In cases where an amount of thecarbon material 114 included herein is slight, e.g., less than 1 wt % by weight, a structure shown inFIG. 1A is formed, and, in cases where an amount of thecarbon material 114 is 1 wt % or higher, a structure shown inFIG. 1B is formed, although it depends on what type of the carbon material is used herein. - Hereinafter, the disclosure will further be described with reference working examples. However, the disclosure is not limited
- to the working example described below. All of reactions described below were carried out under the atmosphere.
- In EXAMPLES,
heat insulation materials 108 in whichcarbon materials 114 are included, and heat insulation materials 110 in whichcarbon materials 114 are included were prepared, and theheat insulation materials 108 and 110 were subjected to the following measurement s. - For measurement of heat conductivity, a heat flowmeter HFM 436 Lamda (manufactured by NETZCH), and a TIM tester (manufactured by Analysys Tech) were employed.
- UL94 vertical combustion tests were further carried out to evaluate flame retardance of
heat insulation materials 108 and 110. “UL” refers to standards for safeness associated with electric equipment, and the standards were established and approved by UNDERWRITERS LABORATORIES INC. in the United States. Accreditation by UL has even been recognized as proof of safeness. UL has been applied to various products such as electric products, fire prevention equipment, plastic materials, lithium batteries, and electric car-associated equipment. The category of UL94 refers to “tests for flammability of plastic materials for appliances and parts in devices”, and there are two types of tests, namely the horizontal flammability test and the vertical flammability test. In the UL94 vertical combustion test, which were carried out for EXAMPLES, samples prepared in predetermined sizes are vertically retained, the tips of the samples are then burned with a burner for a predetermined period of time, and pass/fail is determined based on afterflame times. - Differential scanning calorimetry (DSC) was carried out for
silica xerogels 115, includingcarbon materials 114, present in surface layers ofheat insulation materials 108, and silica xerogels 115 present in surface layers of heat insulation materials 110, and pyrolysis temperatures of organic modifying groups were compared. - The cone calorie meter exothermic test has been employed as a fire retardant material test provided in the Japanese Building Standards Act. This test has widely been acknowledged as a testing method involving combustion of materials, across the world. According to this test method, various combustion parameters such as heat release rates, and combustion times can be measured, and therefore, combustion phenomena can be quantified.
- In the test, while samples 10 cm square are exposed to radiation heat of 50 kW/m2, the samples were burned using an electric spark serving as an ignition source. Heat release rates over time, gross calorific values from start to completion of combustion, combustion times, etc. are obtained, and these parameters were evaluated.
- Specifically, with regards to technical standards for fire retardant materials defined in the Order for Enforcement of the Building Standards Act, an exothermic test using a cone calorimeter complying with ISO5660-1ISO5660, ASTM E1354, and NFPA 264A were carried out.
- A mechanism for measurements in the cone calorimeter-based exothermic test will be described. In this test, heat release rates and calorific values are obtained based on a method called “oxygen consumption method.” Amounts of heat releases that are caused by combustion significantly vary with types of materials in terms of weights of burning materials. However, amounts of heat releases that are caused by combustion is expressed as a constant value regardless of types of materials, when they are considered in terms of weights of consumed oxygen (13.1 MJ per 1 kg of oxygen), and the cone calorimeter-based exothermic test is based on this insight. That is, by accurately measuring amounts of consumed oxygen in combustions, burning phenomena are quantified.
- Detailed conditions for examples and comparative examples will be described below. Also, the conditions and evaluation results were shown in
FIG. 7 . InFIG. 7 , GO refers to Graphene Oxide; CB refers to Carbon Black; SWCNT refers to Single Walled Carbon Nanotube; and PEDOT: PSS refers to Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate). - For heat conductivities of
heat insulation materials 108, samples that exhibited heat conductivities of 0.024 W/mK or less were considered as acceptable. It has been recognized that heat conductivity of still air at ordinary temperature is about 0.026 W/mK. Therefore, in order to effectively insulate flows of heat,heat insulation materials 108 need to have heat conductivities smaller than the heat conductivity of still air. - Therefore, an acceptance standard for heat conductivities of
heat insulation materials 108 was determined to be 0.024 W/mK or lower, where 0.024 W/mK is about 10% lower than the heat conductivity of still air. When the heat conductivity is higher than 0.024 W/mK, the heat conductivity is not very different from the heat conductivity of still air, and therefore, superiority to the air heat insulation will be deteriorated. - For thermal decomposition temperatures, 400° C. or higher was considered as acceptable. If decomposition temperature of organic modifying groups were lower than 400° C., large amounts of trimethyl silanol serving as a flammable gas were easily produced, and this could cause ignition.
- (iii) Evaluations on Flame Retardancy
- In the UL94 vertical flammability test, V0 was considered as acceptable. That is, in the UL94 flammability test, V0, which is the strictest criterion, was considered as acceptable, while V1, V2, and flammable were considered as unacceptable. The same testing method was employed for three types of criteria, V0, V1 and V2. That is, bottom edges of samples that were vertically retained were brought into contact with flames generated from gas burners for 10 seconds. If burning phenomena stopped within 30 seconds, the samples were further brought into contact with flames for another 10 seconds. Evaluation criteria for V0, V1, and V2 will be shown below.
-
- After any of occasions of flame contact, there are no samples that continue to burn for 10 seconds or more.
- For ten flame contacts of five samples, the total combustion times do not exceed 50 seconds.
- There are no samples that burn to positions where the fixing clamps are present.
- There are no samples that drop burning particles causing ignition of absorbent cottons placed below the samples.
- After second flame contact, there are not samples that continue to glow for 30 second or more.
- Samples satisfying these conditions were graded as V-0.
-
- After any of occasions of flame contact, there are no samples that continue to burn for 30 seconds or more.
- For ten flame contacts of five samples, the total combustion times do not exceed 250 seconds.
- There are no samples that burn to positions where the fixing clamps are present.
- There are no samples that drop burning particles causing ignition of absorbent cottons placed below the samples.
- After second flame contact, there are not samples that continue to glow for 60 second or more.
- Samples satisfying these conditions were graded as V-1.
-
- After any of occasions of flame contact, there are no samples that continue to burn for 30 seconds or more.
- For ten flame contacts of five samples, the total combustion times do not exceed 250 seconds.
- There are no samples that burn to positions where the fixing clamps are present.
- Dropping of burning particles are tolerated.
- After second flame contact, there are not samples that continue to glow for 60 second or more.
- Samples satisfying these conditions were graded as V-2.
- For the cone calorimeter-based exothermic test, samples that exhibited combustion times of 10 seconds or less, and peak heat release rates (HRR) of 15 kW/m2 or less in the flame retardant material test (20 minutes) were considered as acceptable.
- Samples that satisfied all of the conditions were considered as acceptable in the comprehensive evaluations.
- EXAMPLES 1 to 8 correspond to heat
insulation materials 108 having the structure shown inFIG. 1A orFIG. 1B . COMPARATIVE EXAMPLES 1 and 2 correspond to conventional heat insulation materials having a one-layer structure. Conventional heat insulation materials only have one layer made ofunwoven fabric fibers 116 and asilica xerogel 115. COMPARATIVE EXAMPLE 3 have onlyunwoven fabric fibers 116. COMPARATIVE EXAMPLE 3 corresponds to a heat insulation material in which theunwoven fabric fibers 116 are made of glass papers. Concentrations mentioned below refer to percentages by weight. - Self-dispersible type oxidated graphene (SIGMA-ALDRICH, 4 mg/ml in H2O) and water were added to water glass (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO2 concentration: 6%, oxidative graphene GO concentration: 0.1%). To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the resulting mixture was stirred to prepare a sol solution.
- Subsequently, by pouring the sol solution into unwoven fabric fibers 116 (material: glass paper; thickness: 600 um; weight per area: 100 g/m2; dimension: 12 cm square), the sol solution was impregnated into the
unwoven fabric fibers 116. Theunwoven fabric fibers 116 impregnated with the sol solution were held between PP films (50 um thick×2 pieces), and allowed to stand at room temperature (23° C.) for three minutes, so as to convert the sol into a gel. After it was confirmed that the sol was gelatinized, the impregnatedunwoven fabric fibers 116, which were placed between the films, into a dual-axis roll in which the gap was set to 1.00 mm (including the film thicknesses), excess gel was squeezed out of theunwoven fabric fibers 116, and thus, the thickness was controlled so as to be 1.00 mm. - Then, the films were peeled, and the gel sheet was immersed in aqueous hydrochloric acid (6 N). Then, by allowing the sample to stand at room temperature (23° C.) for 5 minutes, the gel sheet was allowed to absorb the hydrochloric acid. Subsequently, the gel sheet was immersed in a mixture of octamethyltrisiloxane, which serves as a silylating agent, and 2-propanol (IPA). This was put into a thermostatic chamber at 55° C., and was caused to react for 2 hours. When trimethylsiloxane bonds started to form, aqueous hydrochloric acid was discharged from the gel sheet, and a state of two liquid separation was observed (siloxane in the upper phase, and aqueous hydrochloric acid/2-propanol in the lower phase.) The gel sheet was transferred into a thermostatic chamber 150° C., and was dried in the atmosphere for 2 hours to obtain the sheet.
- As a result, a
heat insulation material 108 having a mean thickness of 0.89 mm, and a heat conductivity of 0.019 W/mK was obtained. In this case, a filling rate of thesilica xerogel 115 was 45.5 wt %. In the UL94 vertical combustion test, the sample was graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which anycarbon materials 114 were not included. For the cone calorimeter-based exothermic test, the combustion time was zero seconds, and the peak heat release rate was 2.5 kW/m2 in the flame retardant material test for 20 minutes. - Self-dispersible type oxidated graphene (SIGMA-ALDRICH, 4 mg/ml in H2O) and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO2 concentration: 6%; oxidated graphene GO concentration: 0.5%). A sheet was prepared based on the same process conditions as EXAMPLE 1 except that the concentration of the oxidated graphene was increased to 0.5%.
- As a result, a
heat insulation material 108 having a mean thickness of 0.88 mm, and a heat conductivity of 0.020 W/mK was obtained. In this case, a filling rate of thesilica xerogel 115 was 44.6 wt %. In the UL94 vertical combustion test, the sample was graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which anycarbon materials 114 were not included. For the cone calorimeter-based exothermic test, the combustion time was zero seconds, and the peak heat release rate was 1.36 kW/m2 in the flame retardant material test for 20 minutes. - Self-dispersible type carbon black (TOKAI CARBON CO., LTD., Aqua black 162, and 19.2 wt % in H2O) and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO2 concentration: 6%; carbon black CB concentration: 0.1%). To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution. A sheet was prepared based on the same process conditions as EXAMPLE 1 except that the carbon material was switched to the carbon black.
- As a result, a
heat insulation material 108 having a mean thickness of 0.88 mm, and a heat conductivity of 0.019 W/mK was obtained. In this case, a filling rate of thesilica xerogel 115 was 45.9 wt %. In the UL94 vertical combustion test, the sample was graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which anycarbon materials 114 were not included. For the cone calorimeter-based exothermic test, the combustion time was zero seconds, and the peak heat release rate was 1.33 kW/m2 in the flame retardant material test for 20 minutes. - Self-dispersible type carbon black (TOKAI CARBON CO., LTD., Aqua black 162, and 19.2 wt % in H2O) and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO2 concentration: 6%; carbon black CB concentration: 0.5%). To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution. A sheet was prepared based on the same process conditions as EXAMPLE 3 except that the concentration of the carbon black was increased to 0.5%.
- As a result, a
heat insulation material 108 having a mean thickness of 0.87 mm, and a heat, conductivity of 0.018 W/mK was obtained. In this case, a filling rate of thesilica xerogel 115 was 45.7 wt %. In the UL94 vertical combustion test, the sample was graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which anycarbon materials 114 were not included. For the cone calorimeter-based exothermic test, the combustion time was zero seconds, and the peak heat release rate was 1.10 kW/m2 in the flame retardant material test for 20 minutes. -
FIG. 8 shows an observed SEM image of flame retardant heat insulation materials (composites ofunwoven fabric fibers 116 made of glass papers and silica xerogels 115) prepared in EXAMPLE 4 and COMPARATIVE EXAMPLE 1. In EXAMPLE 4, an appearance ofcarbon materials 114 adsorbed on surfaces of the fibers was confirmed. - Single-walled carbon nanotubes SWCNT (SIGMA-ALDRICH), which is PEG-modified to enhance dispersibility, and that served as a
carbon material 114, and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material. (SiO2 concentration: 6%; SWCNT concentration: 0.1%). To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution. A sheet was prepared based on the same process conditions as EXAMPLE 1 except, that the carbon material was switched to SWCNT. - As a result, a
heat insulation material 108 having a mean thickness of 0.85 mm, and a heat conductivity of 0.018 W/mK was obtained. In this case, a filling rate of thesilica xerogel 115 was 45.5 wt %. In the UL94 vertical combustion test, the sample was graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which anycarbon materials 114 were not included. For the cone calorimeter-based exothermic test, the combustion time was 10 seconds, and the peak heat release rate was 14.06 kW/m2 in the flame retardant material test for 20 minutes. - Single-walled carbon nanotubes SWCNT (SIGMA-ALDRICH), which is PEG-modified to enhance dispersibility, served as a
carbon material 114, and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO2 concentration: 6%; SWCNT concentration: 0.5%). To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution. A sheet was prepared based on the same process conditions as EXAMPLE 5 except that the concentration of SWCNT was increased in the above-mentioned manner. - As a result, a
heat insulation material 108 having a mean thickness of 0.86 mm, and a heat conductivity of 0.018 W/mK was obtained. In this case, a filling rate of thesilica xerogel 115 was 45.6 wt %. In the UL94 vertical combustion test, the sample was graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which anycarbon materials 114 were not included. For the cone calorimeter-based exothermic test, the combustion time was 10 seconds, and the peak heat release rate was 13.02 kW/m2 in the flame retardant material test for 20 minutes. - poly(3,4-ethylenedioxythiophene)/polysulfonate (PEDOT: PSS) (SEPLEGYDA AS-Q09 supplied from SHIN-ETSU POLYMER CO., LTD.) that served as a
carbon material 114, and water were added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO2 concentration: 6%; PEDOT: PSS concentration: 0.5%). To 20.5 g of this dispersion was added 3.6 parts by weight (0.74 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution. A sheet was prepared based on the same process conditions as EXAMPLE 1 except that the carbon material was switched to PEDOT: PSS. - As a result, a
heat insulation material 108 having a mean thickness of 0.86 mm, and a heat conductivity of 0.018 W/mK was obtained. In this case, a filling rate of thesilica xerogel 115 was 45.9 wt %. In the UL94 vertical combustion test, the sample was graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which anycarbon materials 114 were not included. For the cone calorimeter-based exothermic test, the combustion time was zero seconds, and the peak heat release rate was 1.31 kW/m2 in the flame retardant material test for 20 minutes. - One part by weight of self-dispersible type carbon black (TOKAI CARBON CO., LTD., Aqua black 162, and 19.2 wt % in H2O) was added to a water glass aqueous solution (TOSO SANGYO CO., LTD.) to prepare a starting material (SiO2 concentration: 14%; carbon black CB concentration: 1.3%). To 20.5 g of this dispersion was added 1.6 parts by weight (0.33 g) of concentrated hydrochloric acid serving as an acid catalyst, and the mixture was stirred to prepare a sol solution.
- Conditions for the impregnation and thickness control were the same as those in EXAMPLE 1, and the sample was heated to 90° C. for five minutes to reinforce the gel skeleton. A sheet was prepared based on the same process conditions as EXAMPLE 1, except that the concentration of hydrochloric acid was changed to 12 N.
- As a result, a
heat insulation material 108 having a mean thickness of 1.3 mm, and a heat conductivity of 0.018 W/mK was obtained. In this case, a filling rate of thesilica xerogel 115 was 67.6 wt %. In the UL94 vertical combustion test, the sample was graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was above 550° C., and thus, the high temperature side was shifted by more than 190° C., compared with cases in which anycarbon materials 114 were not included. For the cone calorimeter-based exothermic test, the combustion time was 14.7 seconds, and the peak heat release rate was 10.94 kW/m2 in the flame retardant material test for 20 minutes. - A sheet was prepared based on the same process conditions as those in EXAMPLE 1 except that no self-dispersible oxidated graphene was added to an aqueous water glass serving as a starting material.
- As a result, a heat insulation material 107 having a mean thickness of 0.86 mm, and a heat conductivity of 0.019 W/mK was obtained. In this case, a filling rate of the
silica xerogel 115 was 45.4 wt %. In the UL94 vertical combustion test, the sample was burned, and thus, was not graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was low, i.e., 360° C. With regards to a reason why the sample was burned in the combustion test, it was considered that a large amount of flammable gases was produced around 360° C., and this caused ignition. For the cone calorimeter-based exothermic test, the combustion time was 12.7 seconds, and the peak heat release rate was 16.39 kW/m2 in the flame retardant material test for 20 minutes. In the comprehensive evaluations, the sample was unacceptable. - A heat insulation sheet was prepared based on the same process conditions as those in EXAMPLE 8 except that no
carbon material 114 was added to an aqueous high molar ratio silicate soda (TOSO SANGYO CO., LTD.). - As a result, a heat insulation material 107 having a mean thickness of 1.03 mm, and a heat conductivity of 0.020 W/mK was obtained. In this case, a filling rate of the
silica xerogel 115 was 63.0 wt %. In the UL94 vertical combustion test, the sample was burned, and thus, was not graded as V0. As a result of the DSC measurement, the thermal decomposition temperature (exothermic peak) of organic modifying groups was low, i.e., 380° C. With regards to a reason why the sample was burned in the combustion test, it was considered that a large amount of flammable gases was produced around 380° C., and this caused ignition. For the cone calorimeter-based exothermic test, the combustion time was 24.8 seconds, and the peak heat release rate was 28.69 kW/m2 in the flame retardant material test for 20 minutes. In the comprehensive evaluations, the sample was unacceptable. - Without combining any
silica xerogels 115 withunwoven fabric fibers 116 that had a thickness of 0.600 mm, and a unit weight of 100 g/m2 and that were made of glass paper, the heat conductivity was measured. As a result, the heat conductivity was 0.033 W/mK. Furthermore, in the UL94 vertical combustion test, the sample was not burned, and thus, was graded as V0. However, since the heat conductivity was higher than 0.024 W/mK, the sample was unacceptable in the comprehensive evaluations. -
FIG. 8 refers to observed scanning electron micrographs of heat insulation materials (composites ofunwoven fabric fibers 116 made of glass papers, and silica xerogel 115) prepared in EXAMPLE 4 and COMPARATIVE EXAMPLE 1. In EXAMPLE 1, particles of carbon black are adsorbed onto the surface ofunwoven fabric fibers 116. To the contrary, in COMPARATIVE EXAMPLE 1, there are nocarbon materials 114 that are adsorbed onto the surface ofunwoven fabric fibers 116. - In EXAMPLES 1 to 8,
heat insulation materials 108 in whichcarbon materials 114 were localized to around the surfaces were prepared. Thus, the decomposition temperatures were shifted above 400° C. Also, the samples were graded V0 in the UL94 vertical flammability test, and also, it was revealed that their heat, conductivities were very low, i.e., below 0.024 W/mK. - Furthermore, the samples were subjected to flame retardant material test (20 minutes) in the cone calorimeter-based exothermic test.
- As a result, the heat insulation materials in COMPARATIVE EXAMPLES 1 and 2 in which any carbon materials were included exhibited a peak heat release rate (HRR) higher than 15 kW/m2, or a combustion time exceeding 15 seconds, and did not satisfy both of these requirements. To the contrary, EXAMPLES 1 to 8 in which 0.1 wt % or more of carbon materials were included exhibited peak heat release rates (HRR) lower than 15 kW/m2, and combustion times less than 15 seconds, and thus, satisfied both of these requirements. With regards to types of
carbon materials 114, it was revealed that carbon black, oxidated graphene, single-walled carbon nanotubes, and PEDOT: PSS are effective, and that preferable amounts of these materials are 0.1 wt % to 1.3 wt %. - It should be noted that the disclosure is not limited to the structures shown in
FIGS. 1A and 1B as long as the three-component composite layer 103 can produce effects of heat insulation materials and can solve the above-mentioned objectives. - The disclosure will be employed in a wide range of fields since the heat insulation material according to the disclosure can produce sufficient heat insulation effects even in narrow spaces inside electronic devices, in-vehicle devices, and industrial devices. The disclosure is applicable to all types of products associated with heat (i.e., information devices, portable devices, displays, and electric components).
Claims (10)
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JP2017170791A JP6998504B2 (en) | 2016-12-05 | 2017-09-06 | Insulation material and equipment using the insulation material |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050192366A1 (en) * | 2004-01-06 | 2005-09-01 | Aspen Aerogels, Inc. | Ormosil aerogels containing silicon bonded polymethacrylate |
US20050192367A1 (en) * | 2004-01-06 | 2005-09-01 | Aspen Aerogels, Inc. | Ormosil aerogels containing silicon bonded linear polymers |
US20090029147A1 (en) * | 2006-06-12 | 2009-01-29 | Aspen Aerogels, Inc. | Aerogel-foam composites |
WO2011061286A1 (en) * | 2009-11-19 | 2011-05-26 | BSH Bosch und Siemens Hausgeräte GmbH | Method for producing a porous sio2-xerogel with a characteristic pore size by means of a top-down method using a precursor with pores filled with an organic component or with a carbon component |
US20140252263A1 (en) * | 2011-10-14 | 2014-09-11 | Enersens | Process for manufacturing xerogels |
US20140287641A1 (en) * | 2013-03-15 | 2014-09-25 | Aerogel Technologies, Llc | Layered aerogel composites, related aerogel materials, and methods of manufacture |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5785159A (en) | 1980-11-17 | 1982-05-27 | Fujitsu Ltd | Control method of electronic computer system |
JP3888262B2 (en) * | 2002-08-26 | 2007-02-28 | 松下電器産業株式会社 | Insulation and equipment using it |
JP2005061544A (en) * | 2003-08-15 | 2005-03-10 | Oji Paper Co Ltd | Heat insulating material and heat insulating sheet |
JP2006043603A (en) * | 2004-08-05 | 2006-02-16 | Matsushita Electric Ind Co Ltd | Gas adsorption material and heat-insulation body |
CN101948296B (en) * | 2010-09-28 | 2013-08-21 | 航天特种材料及工艺技术研究所 | High-performance thermal insulation material and preparation method thereof |
CN103466998B (en) * | 2013-09-16 | 2016-02-17 | 成都亚恩科技实业有限公司 | A kind of Carbon aerogel thermal insulation material and preparation method thereof |
JP6435507B2 (en) * | 2014-07-18 | 2018-12-12 | パナソニックIpマネジメント株式会社 | COMPOSITE SHEET, ITS MANUFACTURING METHOD, AND ELECTRONIC DEVICE USING COMPOSITE SHEET |
JP6738990B2 (en) * | 2014-08-26 | 2020-08-12 | パナソニックIpマネジメント株式会社 | Heat insulating sheet and method of manufacturing the same |
CN106457749B (en) * | 2015-03-30 | 2018-09-14 | 松下知识产权经营株式会社 | A kind of heat Insulation film, using its electronic equipment and heat Insulation film manufacturing method |
CN105733260A (en) * | 2016-03-02 | 2016-07-06 | 廖彩芬 | Graphene/conducive macromolecular polymer aerogel and preparation method thereof |
-
2017
- 2017-11-10 CN CN201711103727.2A patent/CN108146028B/en not_active Expired - Fee Related
- 2017-11-17 US US15/816,229 patent/US20180156550A1/en not_active Abandoned
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050192366A1 (en) * | 2004-01-06 | 2005-09-01 | Aspen Aerogels, Inc. | Ormosil aerogels containing silicon bonded polymethacrylate |
US20050192367A1 (en) * | 2004-01-06 | 2005-09-01 | Aspen Aerogels, Inc. | Ormosil aerogels containing silicon bonded linear polymers |
US20090029147A1 (en) * | 2006-06-12 | 2009-01-29 | Aspen Aerogels, Inc. | Aerogel-foam composites |
WO2011061286A1 (en) * | 2009-11-19 | 2011-05-26 | BSH Bosch und Siemens Hausgeräte GmbH | Method for producing a porous sio2-xerogel with a characteristic pore size by means of a top-down method using a precursor with pores filled with an organic component or with a carbon component |
US20140252263A1 (en) * | 2011-10-14 | 2014-09-11 | Enersens | Process for manufacturing xerogels |
US20140287641A1 (en) * | 2013-03-15 | 2014-09-25 | Aerogel Technologies, Llc | Layered aerogel composites, related aerogel materials, and methods of manufacture |
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