WO2019044028A1 - Matériau d'isolation thermique - Google Patents

Matériau d'isolation thermique Download PDF

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Publication number
WO2019044028A1
WO2019044028A1 PCT/JP2018/016411 JP2018016411W WO2019044028A1 WO 2019044028 A1 WO2019044028 A1 WO 2019044028A1 JP 2018016411 W JP2018016411 W JP 2018016411W WO 2019044028 A1 WO2019044028 A1 WO 2019044028A1
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WO
WIPO (PCT)
Prior art keywords
porous body
thermal conductivity
foam
fiber
heat insulating
Prior art date
Application number
PCT/JP2018/016411
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English (en)
Japanese (ja)
Inventor
和貴 村山
塚原　啓二
ひかり 佐々木
慧 塚田
小出　仁
直毅 阿部
安藤　大介
Original Assignee
ニチアス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017164764A external-priority patent/JP2019039554A/ja
Application filed by ニチアス株式会社 filed Critical ニチアス株式会社
Publication of WO2019044028A1 publication Critical patent/WO2019044028A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/14—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having thermal insulation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/16—Selection of particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general

Definitions

  • the present invention relates to a heat insulating material having a heat insulating performance at normal temperature and a heat releasing performance at high temperature.
  • the transmission be heated in a short time from normal temperature to around 100 ° C. in a short time from the viewpoint of improving fuel consumption when the engine is started.
  • a high temperature of 100 ° C. or more heat dissipation is required from the viewpoint of the heat resistance of parts.
  • members that thermally insulate at normal temperature and dissipate heat at high temperature are not known and used for engines and the like.
  • Patent Document 1 shows that a foam is obtained by foaming an inorganic fiber having a charged surface, using a surfactant having a hydrophilic group of the opposite sign.
  • An object of the present invention is to provide a heat insulating material having a heat insulating performance at normal temperature and a heat dissipation performance at high temperature.
  • an inorganic fibrous porous body has a large ratio of thermal conductivity at normal temperature and high temperature, and can dissipate heat by radiation at the time of temperature rise, thus completing the present invention.
  • the thermal insulation material which consists of a porous body containing inorganic fiber, and whose thermal conductivity in 400 degreeC of the said porous body is 3.8 times or more of the thermal conductivity in 25 degreeC.
  • the thermal insulation material according to 1 wherein the thermal conductivity of the porous body at 300 ° C is 2.9 times or more the thermal conductivity at 25 ° C.
  • the heat insulating material according to 1 or 2 wherein the thermal conductivity of the porous body at 200 ° C is 2.1 or more times the thermal conductivity at 25 ° C. 4.
  • the thermal conductivity of the porous body at 25 ° C. is 0.050 W / (m ⁇ K) or less, and the thermal conductivity of the porous body at 400 ° C. is 0.120 W / (m ⁇ K) or more 1 to 3 Insulation according to any of the. 5.
  • the thermal conductivity of the porous body at 25 ° C. is 0.050 W / (m ⁇ K) or less, and the thermal conductivity of the porous body at 300 ° C. is 0.085 W / (m ⁇ K) or more 1-4 Insulation according to any of the. 6.
  • the thermal conductivity of the porous body at 25 ° C. is 0.050 W / (m ⁇ K) or less, and the thermal conductivity of the porous body at 200 ° C.
  • ADVANTAGE OF THE INVENTION According to this invention, it has thermal insulation performance in normal temperature, and can provide the thermal insulation material which has thermal radiation performance in high temperature.
  • FIG. 1 It is a sectional view showing an example of a section of cell structure. It is a graph which shows the change of the heat conductivity to the temperature of the member obtained by Example 1-5 and the comparative example 1.
  • FIG. 1 It is a sectional view showing an example of a section of cell structure. It is a graph which shows the change of the heat conductivity to the temperature of the member obtained by Example 1-5 and the comparative example 1.
  • the heat insulating material of the present invention comprises a porous body composed of inorganic fibers.
  • a foam having a cell structure can be used as the porous body.
  • the cell structure is shown in FIG.
  • the cell structure is a structure in which a large number of pores (cells) and cell walls surrounding them are connected. The cells are surrounded by cell walls made of inorganic fibers.
  • the member of the present invention functions as a heat dissipation material at high temperatures (for example, 200 ° C., 300 ° C. or 400 ° C.). At normal temperature, it functions as a heat insulator.
  • the ratio of the thermal conductivity at 25 ° C. to the thermal conductivity at 400 ° C. is 3.8 or more. This ratio is preferably 4.0 or more, more preferably 4.5 or more.
  • the upper limit can be, for example, 10.0 or less. The higher the ratio, the higher the heat dissipation at high temperatures.
  • the ratio of the thermal conductivity at 25 ° C. to the thermal conductivity at 300 ° C. is 2.9 or more.
  • the ratio is more preferably 3.0 or more, still more preferably 3.3 or more.
  • the upper limit can be, for example, 8.0 or less.
  • the ratio of the thermal conductivity at 25 ° C. to the thermal conductivity at 200 ° C. is 2.1 or more.
  • the ratio is more preferably 2.2 or more, still more preferably 2.3 or more.
  • the upper limit can be, for example, 6.0 or less.
  • the thermal conductivity of the porous body at 25 ° C. is preferably 0.050 W / (m ⁇ K) or less, more preferably 0.045 W / (m ⁇ K) or less, and further preferably It is 0.040 W / (m ⁇ K) or less.
  • the lower limit can be, for example, 0.030 W / (m ⁇ K) or more.
  • the thermal conductivity at 400 ° C. of the porous body is preferably 0.120 W / (m ⁇ K) or more, more preferably 0.125 W / (m ⁇ K) or more, still more preferably 0.140 W / ( m ⁇ K) or more.
  • the upper limit can be, for example, 0.430 W / (m ⁇ K) or less.
  • the thermal conductivity at 300 ° C. of the porous body is preferably 0.085 W / (m ⁇ K) or more, more preferably 0.090 W / (m ⁇ K) or more, still more preferably 0.095 W / ( m ⁇ K) or more.
  • the upper limit can be, for example, 0.320 W / (m ⁇ K) or less.
  • the thermal conductivity of the porous body at 200 ° C. is preferably 0.062 W / (m ⁇ K) or more, more preferably 0.065 W / (m ⁇ K) or more, still more preferably 0.070 W / ( m ⁇ K) or more.
  • the upper limit can be, for example, 0.240 W / (m ⁇ K) or less.
  • the bulk density of the porous body is preferably 30 kg / m 3 or less, more preferably 20 kg / m 3 or less. More preferably, it is 15 kg / m 3 or less.
  • the lower limit can be, for example, 1 kg / m 3 or more or 3 kg / m 3 or more.
  • the porous body is a foam having a cell structure
  • increasing the cell diameter tends to reduce the bulk density. Therefore, the bulk density of the porous body of the cell structure is influenced by the thickness of the cell wall.
  • the average cell diameter is usually 100 to 1500 ⁇ m, for example 130 to 1000 ⁇ m or 150 to 800 ⁇ m.
  • the recovery ratio when compressed at a compression ratio of 30% is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.
  • Bulk density, thermal conductivity, average cell diameter, restitution ratio and average fiber diameter can be measured by the methods described in the examples.
  • the bulk density can be adjusted (controlled) by, for example, the method of surface activation treatment to inorganic fibers, the concentration (content ratio) of inorganic fibers, the expansion ratio, the amount of cells, the cell diameter, etc. in the method for producing foam described later.
  • inorganic fiber used in the present invention one or more selected from, for example, ceramic fiber, bio-soluble fiber (alkali earth silicate fiber, rock wool, etc.) and glass fiber can be used. It is desirable not to use asbestos fibers.
  • the biosoluble inorganic fiber is, for example, an inorganic fiber having a physiological saline dissolution rate of 1% or more at 40 ° C.
  • the physiological saline dissolution rate is measured, for example, as follows. That is, first, 1 g of a sample prepared by crushing inorganic fibers to 200 mesh or less and 150 mL of physiological saline are put in an Erlenmeyer flask (volume 300 mL) and placed in an incubator at 40 ° C. Next, a horizontal vibration of 120 revolutions per minute is continuously applied to the Erlenmeyer flask for 50 hours.
  • the concentration (mg / L) of each element (may be a main element) contained in the filtrate obtained by filtration is measured by an ICP emission analyzer. Then, based on the measured concentration of each element and the content (% by mass) of each element in the inorganic fiber before dissolution, the physiological saline dissolution rate (%) is calculated.
  • a1, a2, a3 and a4 are the measured concentrations of silicon, magnesium, calcium and aluminum (mg / L) respectively, and b1, b2, b3 and b4 are each in the inorganic fiber before dissolution Content (mass%) of silicon, magnesium, calcium and aluminum.
  • the biosoluble fiber has, for example, the following composition.
  • a total of 50% by weight to 82% by weight of SiO 2 , ZrO 2 , Al 2 O 3 and TiO 2 Total of 18 wt% to 50 wt% of alkali metal oxide and alkaline earth metal oxide
  • the biosoluble fiber can also be configured, for example, with the following composition. SiO 2 50 to 82% by weight 10 to 43% by weight of total of CaO and MgO
  • porous body (foam etc.) used by this invention can contain organic components, such as a coupling agent, besides an inorganic component.
  • the porous body used in the present invention can be produced by the following method.
  • the production method includes the production of an inorganic fibrous foam
  • the foam production method includes a production step of producing an inorganic fiber dispersion, a foaming step of foaming an inorganic fiber dispersion, and a dehydration step of drying the foam.
  • the binder may be previously added to the dispersion for foaming and heat treated after foam formation.
  • the surface of the inorganic fiber is brought into contact with an alkaline or acidic treatment liquid to charge the dispersion step by charging negatively or positively and adding a surfactant to the charged inorganic fiber. And a surfactant addition step to be created.
  • a surfactant addition step to be created.
  • the surface of the inorganic fiber is negatively charged, it is preferable to add a cationic surfactant, or when the surface of the inorganic fiber is positively charged, an anionic surfactant is added.
  • the zeta potential of the surface of the inorganic fiber is controlled by pH adjustment using an alkaline or acidic treatment liquid. Specifically, the zeta potential of the surface of the inorganic fiber is made negative or positive.
  • a surfactant having a hydrophilic group of the opposite sign is added to the charged inorganic fiber, and the hydrophilic group side of the surfactant is adsorbed on the surface of the inorganic fiber to form a hydrophobic group.
  • the inorganic fiber (the outermost surface) is hydrophobized.
  • the inorganic fibers ceramic fibers, bio-soluble fibers (alkali earth silicate fibers, rock wool, etc.), glass fibers, etc. can be used.
  • the treatment liquid may be any solution that can be dissolved in water to change the pH, and an acid or a base of an inorganic compound or an acid or a base of an organic compound can be used.
  • the zeta potential of the surface of the inorganic fiber is not zero, for example, ⁇ 5 mV to ⁇ 70 mV, ⁇ 7 mV to ⁇ 60 mV, ⁇ 10 mV to ⁇ 45 mV, +5 mV to +65 mV, +7 mV to +60 mV, or +10 mV to +45 mV.
  • the pH for achieving a predetermined zeta potential differs depending on the type of fiber, the pH can not be uniquely determined.
  • a fiber having a pH of 7 at which the zeta potential is 0 isoelectricity The point pH is 7
  • it can be negatively charged at pH higher than pH 2 and positively charged at pH lower than pH 2 .
  • the zeta potential is obtained by dispersing the fiber in an aqueous dispersion medium adjusted to a predetermined pH and measuring the fiber using a general-purpose zeta potentiometer (for example, Model FPA, manufactured by AFG Analytik).
  • a general-purpose zeta potentiometer for example, Model FPA, manufactured by AFG Analytik.
  • the charging step and the surfactant addition step in the preparation step may be performed sequentially or simultaneously. If the charging step and the surfactant addition step are performed simultaneously, the processing solution, inorganic fibers and surfactant can be mixed together. On the other hand, when the charging step and the surfactant addition step are performed over time, the inorganic fibers can be previously opened, dispersed and charged with the treatment liquid, and then mixed with the surfactant.
  • an amphiphilic substance, a silane coupling agent having a hydrophobic functional group, a titanium coupling agent having a hydrophobic functional group or the like may be used without using a surfactant.
  • the coupling agent in this step is to render it hydrophobic to form a foam.
  • the coupling agent used in the subsequent binder application step is for preventing the foam form from collapsing when it gets wet with water.
  • the amount of surfactant in the dispersion can be adjusted more appropriately than the inorganic fiber, but for example, the surfactant may be 0.01 to 1.0 part by weight with respect to 100 parts by weight of glass fiber.
  • the surfactant may be preferably 0.1 to 0.8 parts by weight, more preferably 0.2 to 0.7 parts by weight. If the amount of surfactant added is too small, the surface of the inorganic fibers may not be sufficiently hydrophobized and the foamability may be reduced. If the amount of surfactant is too large, the surfactants may adhere to each other. It can be adjusted in view of the possibility that the surface of the inorganic fiber may not be sufficiently hydrophobized.
  • the dispersion may also be composed free of organic binders (resin emulsions, rubber (elastomer) components (such as gum arabic) or magnesium oxides or hydroxides.
  • organic binders resin emulsions, rubber (elastomer) components (such as gum arabic) or magnesium oxides or hydroxides.
  • air bubbles
  • air (bubbles) is supplied from an air bubble supply device to the inorganic fiber dispersion liquid obtained by mixing the treatment liquid, the inorganic fibers, and the surfactant to cause foaming.
  • air (bubbles) may be supplied to the inorganic fiber dispersion liquid by stirring without using a bubble supply device to cause foaming.
  • the cell diameter and the bulk density can be adjusted by adjusting the bubble diameter or the bubble amount by the bubble supply device.
  • the foam is dewatered by drying (including natural drying) the dispersion medium contained in the dispersion for a predetermined time (for example, 4 hours) at a normal temperature or a predetermined temperature outside the normal temperature.
  • the foam is fired at a high temperature (eg, 450 ° C.) to remove the surfactant.
  • a high temperature eg, 450 ° C.
  • bonds fibers can be used, for example, a coupling agent, an inorganic binder, etc.
  • the coupling agent is used, the foam, the coupling agent and the water vapor are reacted to be applied. Specifically, the coupling agent is heated to cause the generated vapor to adhere to the foam and react with the water vapor.
  • the coupling agent is hydrolyzed, dehydrated and condensed to adhere to the foam.
  • the foam and the coupling agent vapor are brought into contact in a closed container (a closed container which does not mix gas into the container from the outside but the pressure can be increased by internal heating).
  • the foam After contact, water is placed in a closed vessel to generate water vapor and react with the coupling agent.
  • the foam may be directly impregnated with the coupling agent and heated instead of or in addition to the above-mentioned treatment. It is then contacted with steam.
  • SiO 2 series SiO 2 particles, water glass (sodium silicate), Al 2 O 3 series (Al 2 O 3 particles, basic acid aluminum such as polyaluminum chloride, etc.), phosphate as an inorganic binder And clay minerals (synthetic and natural).
  • Examples of coupling agents include silane coupling agents, titanium coupling agents and the like.
  • silane coupling agent methyl triethoxysilane etc. are mentioned.
  • the amount of the binder is not particularly limited and may be limited depending on the inorganic fiber, and is about 1 to 10% by weight, for example.
  • the porous body may consist essentially of, or consist of, inorganic fibers, surfactants and binders, or inorganic fibers and binders.
  • "essentially” means that 95% by weight or more, 98% by weight or more or 99% by weight or more consists of these.
  • the porous material of this invention can remove the composite material of an airgel or an airgel and an inorganic fiber.
  • the heat insulating material of the present invention may be composed only of a porous body, but may include members having other appropriate functions.
  • Examples 1 to 5 A micro glass fiber with an average fiber diameter of 0.22 ⁇ m (melting point of 400 ° C. or higher) was dispersed in ammonia water of pH 10 so as to have a concentration of 0.5% by weight to adjust the zeta potential of the fiber surface to -55 mV. .
  • a cationic surfactant (lauryl trimethyl ammonium chloride (trade name; Cortamine 24P, manufactured by Kao Corporation)) is added to 100 parts by weight of the fiber in terms of solids of the surfactant.
  • the mixture was stirred and mixed. At this time, air was taken in and bubbled using a nozzle. The bulk density of the foam was changed by changing the amount of foam leaving the nozzle.
  • the obtained wet foam was dried and treated at 450 ° C. for 1 hour using an electric furnace to remove the surfactant attached to the foam.
  • a coupling agent was applied.
  • the coupling agent is methyltriethoxysilane (trade name: KBE-13, manufactured by Shin-Etsu Chemical Co., Ltd.), and the silane coupling agent is placed in a closed container and heated to about 160 ° C. to generate a vapor of the silane coupling agent And the foam was treated for 4 hours.
  • 8 g of water was added to the closed vessel, steam was generated, and the foam was treated for 2 hours.
  • the following characteristics of the inorganic fiber and the foam were measured by the following method. Average fiber diameter The fiber diameter was measured for 400 fibers randomly selected, and the average value was determined.
  • Recovery Ratio After compressing the sample to 70% of the thickness, measure the thickness of the sample after compression release, and determine the recovery ratio from the following equation.
  • the restoration rate is 80% or more.
  • Recovery rate (%) thickness after compression test ⁇ ⁇ thickness before test ⁇ 100
  • Comparative Example 1 It evaluated similarly to the Example using glass mat-GE (brand name, Nichias Co., Ltd. product made) instead of foam. The results are shown in Table 1 and FIG. 2 as in the example. The cell diameter was not measured because the glass mat is not a cell structure.
  • Glass Mat-GE is a product manufactured by cutting glass fiber to a certain length, finishing it in a felt shape, and then processing it by needle.
  • the heat insulating material of the present invention is installed or installed around a member which reaches a high temperature of 400 ° C. during use, for example, a power generator (eg, engine) and / or a power transmission (eg, transmission) of a transportation vehicle such as a car. It can be used by covering it.
  • a power generator eg, engine
  • a power transmission eg, transmission

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

L'invention concerne un matériau d'isolation thermique qui comprend un corps poreux comprenant des fibres inorganiques, la conductivité thermique dudit corps poreux à 400 °C étant au moins 3,8 fois la conductivité thermique à 25° C.
PCT/JP2018/016411 2017-08-28 2018-04-23 Matériau d'isolation thermique WO2019044028A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017163689 2017-08-28
JP2017-163689 2017-08-28
JP2017164764A JP2019039554A (ja) 2017-08-28 2017-08-29 断熱材
JP2017-164764 2017-08-29

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WO2019044028A1 true WO2019044028A1 (fr) 2019-03-07

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PCT/JP2018/016411 WO2019044028A1 (fr) 2017-08-28 2018-04-23 Matériau d'isolation thermique

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60141684A (ja) * 1983-12-28 1985-07-26 ニチアス株式会社 無機繊維質弾性発泡体の製造法
WO2016121400A1 (fr) * 2015-01-28 2016-08-04 ニチアス株式会社 Mousse
WO2017208930A1 (fr) * 2016-06-02 2017-12-07 ニチアス株式会社 Matériau d'insonorisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60141684A (ja) * 1983-12-28 1985-07-26 ニチアス株式会社 無機繊維質弾性発泡体の製造法
WO2016121400A1 (fr) * 2015-01-28 2016-08-04 ニチアス株式会社 Mousse
WO2017208930A1 (fr) * 2016-06-02 2017-12-07 ニチアス株式会社 Matériau d'insonorisation

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