JP6487494B2 - Flexible insulating structure and method for making and using the same - Google Patents

Description

  Many applications benefit from the use of materials that are relatively lightweight and are good insulation materials. For example, airgel typically exhibits very low density and very low thermal conductivity and is found in various insulating articles. For example, airgel blankets can be used for pipes, aircraft, automobiles, buildings, clothing, footwear, and other types of insulation.

  Lee et al. US Pat. No. 7,399,439, issued July 15, 2008, incorporated herein by reference in its entirety, forms a catalytic sol by continuously combining sols and gel inducers. An airgel blanket that is formed using a process for continuously forming a gel sheet material filled with a solvent is described. The gel sheet is generated by dispensing the catalyst sol on the moving element at a predetermined ratio, and can effectively cause gelation of the catalyst sol on the moving element. The catalyst is extracted by drying the supercritical fluid.

  Lee et al. US Pat. No. 6,989,123, issued January 24, 2006, which is incorporated herein by reference in its entirety, is formed using a process for forming gel sheets. The airgel blanket is described, and the process involves providing a large amount of fibrous batting material and separating a large amount of fibrous batting material into a fiber roll matrix having multiple fiber layers. Introducing a permeable material, injecting a large amount of catalyst sol into the fiber roll matrix, gelling the catalyst sol in the fiber roll matrix, and removing the impermeable material to leave the gel material intact Introducing a large amount of permeable material to separate the gel material into multiple layers. The interstitial solvent phase is usually removed by supercritical fluid extraction.

  Rouanet et al. US Pat. No. 7,635,411, issued Dec. 22, 2009, which is incorporated herein by reference in its entirety, describes a blanket produced by preparing an aqueous slurry. The aqueous slurry includes hydrophobic airgel particles, fibers, and at least one infiltrant. Preferably, the hydrophobic airgel particles form a homogeneous mixture with the fibers at least temporarily. The mixture can then be substantially dehydrated, compressed and dried to form a web, which can be further processed, for example by calendering, to form a blanket.

  Given the vast number of applications that require thermal insulation, there is a continuing need for flexible insulating articles having attractive properties, and methods for producing and using them.

  In one embodiment, the flexible insulating structure includes a mixture of batting and airgel-containing particles and a binder. The airgel-containing particles are impregnated into at least one layer of batting.

  In another embodiment, a method for preparing a flexible insulating structure comprises applying a mixture comprising airgel-containing particles and a binder to a batting having one or more batting layers, and drying the binder. Or it can be dried, thereby forming a flexible insulating structure.

  The articles described herein have low thermal conductivity and provide many advantages. For example, a flexible insulating structure can have improved flame characteristics and can withstand elevated temperatures. In many implementations, the structure can perform well under compressive loads and have soundproofing properties and / or electrical insulation characteristics.

  The method of manufacturing the flexible insulating structure described herein uses widely available materials, such as industrial production relatively directly using airlaid and / or roll-to-roll technology. There is a tendency to expand the process. The use of off-the-shelf airgel particles eliminates the need for in-situ gelling that is required by many existing methods for preparing airgel blankets. Batting options provide the opportunity and flexibility to fine tune properties such as thermal conductivity, elevated temperature behavior, behavior under compressive load, tensile strength and thickness.

  Other advantages associated with embodiments of the present invention include the addition of other additives to modify, eg improve, flame properties, high and / or low temperature, eg, thermal insulation performance at cryogenic temperatures, water and water vapor adsorption properties, etc. Regarding flexibility.

  In the accompanying drawings, reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.

3 is a photograph of an insulating flexible material according to one aspect of the present invention. FIG. 3 shows the formation of a sandwich structure that includes all two fiber layers. FIG. 3 shows the formation of a sandwich structure that includes all two fiber layers. FIG. 3 shows the formation of a sandwich structure that includes all two fiber layers. FIG. 5 shows the formation of a sandwich structure including all four fiber layers. FIG. 5 shows the formation of a sandwich structure including all four fiber layers. FIG. 5 shows the formation of a sandwich structure including all four fiber layers.

  These and other features and other advantages of the present invention, including various details and combinations of parts of the structure, will now be more particularly described with reference to the accompanying drawings and pointed out in the claims. It will be understood that the specific methods and devices embodying the invention are shown by way of illustration and not as limitations of the invention. The principles and features of the invention may be utilized in a number of different embodiments without departing from the scope of the invention.

  The present invention relates generally to an insulating article (structure) comprising a fibrous component, generally in the form of one or more layers, and comprising nanoporous material, such as airgel-containing particles, a method for producing the article or structure, and a method for using the same.

Generally, the layer takes the form of a lofty fibrous structure (ie, batting) and is often a nonwoven fabric. In non-woven materials, the fibers are held together by mechanical engagement in a random web (mesh) or mat, and the bond is a medium such as starch, adhesives, casein, rubber, latex, synthetic resins, cellulose derivatives, etc. Can be achieved by dissolving the fibers and / or by other means such as are known in the art. In some cases, the nonwoven layer is made from crimped fibers that can range in length from about 0.75 to about 4.5 inches. The diameter of the fibers can be in the range of about 0.1 to about 10,000 microns. Other fiber dimensions can be selected.

  Woven fiber layers can also be utilized using entangled weave, plain weave or other textile techniques known in the art, for example.

  In some embodiments, the batting has an insulating property. For example, the batting is about 80 mW / m-K or less at 23 ° C., for example in the range of about 20 mW / m-K to about 60 mW / m-K, often about 25 mW / m-K to about 50 mW / m- It can have a thermal conductivity in the range of K.

  In other embodiments, batting is suitable for high temperature applications. For example, the batting utilized can withstand without degradation at temperatures above about 200 ° C., eg, above about 300 ° C., and above about 600 ° C. In other embodiments, the batting has flame retardancy and / or fire resistance, low flame propagation and desirable surface combustion characteristics.

  The batting can be flexible, and in particular embodiments the batting is provided in a rolled up form.

  Batting can be any suitable material such as metal oxide fibers such as glass fibers, mineral cotton fibers such as stone or slag fibers, biosoluble ceramic fibers, carbon fibers, polymeric fibers such as polyester, aramid, polyolefin, polyethylene It can be made from metal fibers, cellulose fibers, plant-derived fibers, other suitable fibers or combinations of fibers, such as terephthalate, polymer blends and copolymers.

  In a specific implementation, the batting is entirely or partially glass fiber, for example A-glass (high alkali glass with 25% soda and lime, provides good resistance to chemicals but has electrical properties. Relatively low), C-glass (a specific mixture with high chemical resistance), E-glass (electric grade with low alkali content), S-glass (high strength with 33% higher tensile strength than E-glass) Glass), D-glass (a low dielectric constant material with superior electrical properties but less mechanical properties than E-glass or S-glass), or others as known in the art, for example Created using the type of glass fiber.

  In other specific implementations, batting is based on, for example, Thinsulate ™ manufactured by 3M Corporation and advertised to provide 1 to 1.5 times the duck down insulation, or synthetic microfiber. A material that is often a viable alternative to goose down, consisting essentially of an insulating rigid polymeric material, such as PrimaLoft® (registered trademark of Albany International Corporation). Or comprises an insulating rigid polymeric material. In many cases, the polymeric material used for batting comprises polyethylene terephthalate or a mixture of polyethylene terephthalate and polypropylene. In other cases, the batting polymeric material comprises a polyethylene terephthalate-polyethylene isophthalate copolymer and / or acrylic. Other macromolecules such as polyesters, polymer blends and copolymers can be utilized to form the batting.

A batting material can be characterized by its density. Suitable batting materials can have a concentration in the range of about 1 kg / m ³ to about 20 kg / m ³ , for example 4 kg / m ³ . Web or mesh-like batting, such as batting made from fiberglass, is another method suitable by the number of meshes as known in the art or for describing the (average) opening size present in the web Can be characterized by: Usually, a larger mesh number indicates a smaller opening and a smaller mesh number indicates a larger opening.

Thickness and weight are other characteristics that are usually specified for a particular batting. For example, the batting layer can have a thickness appropriate for the desired application. In a specific example, the batting can be as thin as about 0.5 mm, or as thick as about 110 mm. In specific examples, the batting is 4, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 102 mm. Thinner batting can be wound more easily, for example, thinner batting can be wrapped around a smaller radius, while thicker batting provides mechanical strength such as tensile strength and other properties. Can be added. Suitable batting layers can have, for example, a weight of at least 50 g / m ² , such as 100 g / m ² , 150 g / m ² , 200 g / m ² , 250 g / m ² or even higher.

  Presented as an illustrative example, Table 1 shows the characteristics of several commercial grades of Thinsulate ™ Ultra Lite Loft.

  The batting can be made from two or more layers, for example arranged in multiple layers. In many implementations, the multilayers are essentially all made from the same material, and can be the same or different with respect to layer thickness, density, number of meshes, and / or other parameters related to batting. . Layers made from different materials can also be utilized, and such layers can have the same or different layer thickness, density, mesh number, and / or other parameters related to batting.

  At least one of the layers present in the structures described herein comprises a nanoporous material. As used herein, the term “nanoporous” refers to a material having pores less than about 1 micron, such as less than 0.1 microns. Examples of suitable nanoporous materials include, but are not limited to, metal oxides such as silicon, aluminum, zirconium, titanium, hafnium, vanadium and yttrium, and / or mixtures thereof.

  In an exemplary embodiment, the nanoporous material is an airgel. Aerogels are low density porous bodies with large intraparticle pore volume and are usually produced by removing pore fluid from wet gels. However, the drying process can be complicated by capillary forces within the gel pores, which can cause gel shrinkage or densification. In one manufacturing approach, the collapse of the three-dimensional structure is essentially eliminated by using supercritical drying. Wet gels can also be dried using ambient pressure and are also referred to as non-supercritical drying processes. For example, when applied to silica-based wet gels, surface modifications performed prior to drying, such as end capping, permanently prevent shrinkage in the dried product. Although the gel may still shrink during drying, it is pushed back to restore the previous porosity of the gel.

  Products called “xerogels” are also obtained from wet gels from which the liquid has been removed. The term often refers to a dried gel that has been compressed by capillary forces during drying, and is characterized by permanent changes and solid reticulation.

  For convenience, the term “aerogel” is used herein in a generic sense and refers to both “aerogel” and “xerogel”.

Aerogels usually have a low bulk density (about 0.15 g / cm ³ or less, often about 0.03 to 0.3 g / cm ³ ), a very high surface area (typically about 300 to about 1,000 square meters per gram). (M ² / g) or more, eg, about 600 to about 1000 m ² / g), high porosity (about 90% or more, eg, greater than about 95%), and relatively large pore volume (eg, about 3 per gram Millimeter (mL / g), such as about 3.5 mL / g or more, such as 7 mL / g. The airgel can have a nanoporous structure with pores less than 1 micron (μm). Often, airgel has an average pore size of about 20 nanometers (nm). The combination of these properties in an amorphous structure gives the lowest thermal conductivity value (e.g., 9-16 mW / m · K at 1 atmosphere at an average temperature of 37 ° C.) for any coherent solid material. The airgel can be substantially transparent or translucent, which scatters blue light, or can be opaque.

  A common type of airgel is silica-based. Airgels based on metal oxides other than silicon, such as aluminum, zirconium, titanium, hafnium, vanadium and yttrium, or mixtures thereof can also be utilized.

  Also known are organic aerogels such as resorcinol or melamine in combination with formaldehyde and dendritic polymers, and the present invention can also be practiced using these materials.

  Suitable airgel materials and processes for their preparation are described, for example, in US Patent Application No. 2001 / 0034375A1, published Oct. 25, 2001 by Schwertfeger et al., The teachings of which are incorporated herein by reference. The entirety of which is incorporated herein.

  In many implementations, the airgel utilized is hydrophobic. As used herein, the terms “hydrophobic” and “hydrophobized” refer to partially and fully hydrophobized aerogels. The hydrophobicity of the partially hydrophobized airgel can be further increased. A fully hydrophobized aerogel has the highest degree of coverage and basically modifies all chemically accessible groups.

  Hydrophobicity can be determined by methods known in the art, such as by contact angle measurement or by methanol (MeOH) wettability. Hydrophobic studies on aerogels are described, for example, in Hrubesh et al. In US Pat. No. 6,709,600B2, issued Mar. 23, 2004, the teachings of which are hereby incorporated by reference in their entirety.

  Hydrophobic aerogels are hydrophobizing agents such as silylating agents, halogen-containing compounds and fluorine-containing compounds such as fluorine-containing alkoxylanes or alkoxyloxanes, such as trifluoropropyltrimethoxysilane (TEPTMOS), and in the art. It can be produced by using other known hydrophobizing compounds.

  Silylated compounds such as silane, halosilane, haloalkylsilane, alkoxysilane, alkoxyalkylsilane, alkoxyhalosilane, disiloxane and disilazane are often utilized. Examples of suitable silylating agents include diethyldichlorosilane, allylmethyldichlorosilane, ethylphenyldichlorosilane, phenylethyldiethoxysilane, trimethylalkoxysilane, such as trimethylbutoxysilane, 3,3,3-trifluoropropylmethyl Dichlorosilane, shimdiphenyltetramethyldisiloxane, trivinyltrimethylcyclotrisiloxane, hexaethyldisiloxane, pentylmethyldichlorosilane, divinyldipropoxysilane, vinyldimethylchlorosilane, vinylmethyldichlorosilane, vinyldimethylmethoxysilane, trimethylchlorosilane, hexa Methyldisiloxane, hexenylmethyldichlorosilane, hexenyldimethylchlorosilane, dimethylchlorosilane, dimethyldichlorosilane Mercaptopropylmethyldimethoxysilane, bis {3- (triethoxysilyl) propyl} tetrasulfide, including but hexamethyldisilazane and their combinations, but is not limited thereto.

  The hydrophilizing agent can be used during airgel formation and / or in subsequent processing steps, such as surface treatment.

  In some examples, the airgel has a hydrophilic surface, or shell obtained, for example, by treating the hydrophilic airgel with a surface active agent, also referred to herein as a surfactant, dispersant, or wetting agent.

  Increasing the amount of surfactant tends to increase the depth that the aqueous phase can penetrate, and thus the thickness of the hydrophilic coating that surrounds the core of the hydrophilic airgel.

  The insulating structures described herein can include additives such as fibers, opacifiers, color pigments, dyes or mixtures, and in some cases, these additives are present in the airgel compound. For example, silica aerogels can be prepared to contain fibers and / or one or more metals or compounds thereof. Specific examples include aluminum, tin, titanium, zirconium or other non-quartz metals and their oxides. Non-limiting examples of opacifiers include carbon black, titanium oxide, silicon carbide, zirconium silicate, and mixtures thereof. Additives can be provided in any suitable amount, for example depending on the desired properties and / or specific application.

  In general, the nanoporous materials utilized, such as the silica aerogels described herein, are pre-manufactured during the manufacture of the insulating structure as opposed to being formed in situ. Certain embodiments utilize, for example, airgel-containing particles, such as granules, pellets, beads, powders, or other types of airgel-containing particulate materials. Suitable particulate materials consist of aerogels, for example quartz-based aerogels, consist essentially of aerogels or comprise aerogels.

  The particles can have any particle size suitable for the intended application. For example, the airgel particles can range from about 0.01 microns (μm) to about 10.0 millimeters (mm), for example having an average particle size in the range of 0.3 to 5.0 mm. Can do. In many instances, the average particle size is in the range of about 1 micron to 100 μm, such as in the range of 8 to 10 μm. Other suitable particle sizes are in the range of about 0.3 to about 1 μm, about 1 to about 3, 5 or 8 μm, about 10 to about 15 or about 20 μm, about 20 to about 35 μm, or about 35 to about 50 μm. It is. A combination of particle sizes can also be used. In a specific example, the particle size takes into account factors such as the desired degree of penetration through the batting, the type of batting utilized, the size of the mesh openings in the batting layer (s) and the thickness of the batting or bashing layer. Selected.

  An example of a particular form of commercially available airgel material is that supplied by the Cabot Corporation of Billerica, Mass., USA under the trade name Nanogel®. Nanogel® airgel granules have a high surface area, are more than about 90% porous, and are available in a wide range of particle sizes, such as the ranges described above. Specific grades of translucent Nanogel® airgel include, for example, those named TLD302, TLD301, TLD201, or TLD100, and specific grades of IR opaque Nanogel® airgel include, for example, RGD303. Or a specific grade of opaque Nanogel® airgel, including the name of CBTLD103, includes, for example, the name of OGD303.

  The airgel-containing material can also be extracted from monolithic airgel or airgel-based compositions, sheets and blankets, preferably in the form of particles. For example, airgel particles can be obtained from airgel monoliths, compositions, blankets, sheets and other such precursors by breaking, chopping, grinding or through such pieces of airgel material. Can be obtained by other appropriate techniques.

  Examples of materials that can be processed to produce particles or pieces of airgel-containing material include aerogels and fibers (e.g., fiber reinforced aerogels), and optionally airgel-based compositions containing at least one binder. An airgel composition is included. The fibers can have any suitable structure. For example, the fibers can be oriented in a parallel direction, a vertical direction, a common direction, or a random direction. The fibers can vary with respect to the composition, size or structure of the fibers. Within the composition, one type of fiber can be of different dimensions (length and diameter) and the fiber orientation can be different. For example, long fibers are aligned in-plane while shorter fibers are randomly distributed. Specific examples include, for example, Frank et al. In US Pat. No. 6,887,563, issued May 3, 2005, the teachings of which are hereby incorporated by reference in their entirety. Other examples include at least one airgel and at least one syntactic foam. For example, the teachings may be coated with an airgel as described in WO2007047970, named airgel-based composition, which is incorporated herein by reference in its entirety, so that the polymer is pores of the airgel. Can be prevented from entering. In yet another example, airgel can be extracted from a blanket, for example, in an arrangement where blanket sheets are laminated together to form a multilayer structure. Cracked monoliths are described in Frank et al., The teachings of which are incorporated herein in their entirety by reference. In U.S. Pat. No. 5,789,075 issued Aug. 4, 1998, which are also suitable precursors in the production of the free-standing rigid compositions disclosed herein. Can also work as. In a further example, the airgel utilized is described by Frank et al., For example, the teachings of which are incorporated herein by reference in their entirety. As described in US Pat. No. 6,887,563, issued May 3, 2005, comprising an airgel material, a binder and a composition of at least one fiber material. Other suitable examples of airgel materials that can be used are described by Frank et al., The teachings of which are incorporated herein in their entirety by reference. Is a fiber web / aerogel composition comprising a composite fiber as disclosed in US Pat. No. 5,786,059, issued July 28, 1998 to the United States. Airgel particles can also be incorporated, for example, by reference to the teachings of Lee et al. As described in US Patent Application Publication No. 2005 / 0046086A1 published March 3, 2005, and US Patent Application Publication No. 2005 / 0167891A1 published August 4, 2005. Or from a sheet or blanket produced from the wet gel structure. On the market, airgel-type blankets or sheets are available from Cabot Corporation, Billerica, Mass., USA, or Aspen Aerogels, Inc., Northborough, Massachusetts. Is available from

  Combinations of airgel-containing materials can also be used. For example, different types of aerogel-containing materials, eg, combinations or mixtures of particulate airgels having different particle sizes, acoustic and / or light transmission properties. Examples include, but are not limited to, microspheres such as fumed silica, colloidal silica or precipitated silica, carbon black, titanium oxide, perlite, glass, ceramic or polymeric microspheres, silicates, copolymers, tensides, mineral powders and fibers, etc. Mixtures of airgel with other materials, such as non-aerogel nanoporous metal oxides, such as silica, can also be used.

  Nanoporous materials are usually provided in combination with other components, for example in the form of pre-manufactured airgel particles. In many embodiments, a nanoporous material, such as a pre-prepared airgel-containing material, is provided in combination with a binder. In many instances, the binder is a material that hardens, hardens, or hardens under certain conditions. For convenience, these and similar such processes are referred to herein as “drying”. Preferably, these “drying” processes are irreversible.

  In many implementations, the binder comprises a material based on calcium sulfate hemihydrate (CaSO4 · 0.5H20), including gypsum, consisting essentially of gypsum, or consisting of gypsum. Usually calcined gypsum (calcium sulfate) is used in the form of an aqueous slurry, and the drying-induced crystallization combines the crystals of calcium sulfate with which the calcium sulfate crystals combine to provide mechanical properties to the binder. Bring about formation. In the case of lime plaster (based on calcium oxide), the aqueous slurry forms calcium hydroxide that forms calcium carbonate under the influence of carbon dioxide in the atmosphere.

  Other suitable binders include one or more materials such as, for example, cement, lime, mixed magnesium salts, silicates such as sodium silicate, plaster and / or other minerals or mineral-containing compositions. Essentially consisting of one or more materials or consisting of one or more materials. For example, cement often contains hydrated silicates of limestone, clay and other components such as alumina. For example, hydraulic cement is a material that hardens and hardens after combination with water as a result of a chemical reaction with mixed water and maintains strength and stability even in water after hardening. An important requirement for this strength and stability is that the hydrate formed in the immediate reaction with water is essentially insoluble in water. Hardening and hardening of the hydraulic cement is effected by the formation of a hydrous compound, which is produced as a result of the reaction between the cement component and water. The reaction and reaction product are called hydration and hydrate or hydrated phase, respectively. As a result of starting the reaction immediately, curing can be observed with a slight initial increase but with time. The point at which stiffness reaches a certain level is called the start of condensation. Further compaction is called condensation, and after setting, the curing phase begins. The compressive strength of the material then increases steadily, ranging from a few days for “superfast” cements to a few years for ordinary cements.

  The binder may also include one or more of, for example, acrylates, other latex compositions, epoxy polymers, polyurethanes, polyethylene polypropylene, and polytetrafluoroethylene polymers (eg, commercially available under the name Teflon ™). It consists of an organic material, consists essentially of one or more organic materials, or contains one or more organic materials. Many organic binders can harden or cure through polymerization or a curing process such as is known in the art.

  The binder can be combined with the airgel component in any suitable proportion. Examples include, but are not limited to, an airgel to binder weight ratio in the range of 100: 5 to 100: 30. Other ratios of airgel and binder can be selected. In specific examples, the weight ratio of airgel to binder is 100: 10, 100: 15, 100: 20, or 100: 25.

  Some embodiments of the present invention utilize one or more surfactants. Suitable surfactants that can be used with airgel (eg airgel particles) and binders are ionic (anionic and cationic) surfactants, amphoteric surfactants, nonionic surfactants, polymeric surfactants And a polymer compound. Combinations of different types of surfactants can also be used.

  Anionic surfactants can include, for example, alkyl sulfates and higher alkyl ether sulfates, and more specifically ammonium lauryl sulfate and sodium polyoxyethylene lauryl ether sulfate. Cationic surfactants include, for example, aliphatic ammonium salts and amine salts, more specifically, for example, alkyl trimethyl ammonium and polyoxyethylene alkyl amines. The amphoteric surfactant may be, for example, a betaine type such as alkyldimethylbetaine or an oxide type such as alkyldimethylamine oxide. Nonionic surfactants include glycerol fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol tetraoleate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, It includes oxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene alkyl ether, polyethylene glycol fatty acid ester, higher fatty acid alcohol ester, polyhydric alcohol fatty acid ester and the like.

  Specific examples of the surfactants that can be used include Pluronic P84, PE6100, PE6800, L121, Emulan EL, Lutensol FSA10, Lutensol XP89, Michelman MP5490, and AEROSOL OT (di-2-ethylhexylsulfosuccinate) manufactured by BASF. TWEEN surfactants such as BORLOX 12i (branched alkyl dimethylamine oxide), LAS (linear alkylbenzene sulfonate) and TRITON 100 (octylphenoxypolyethoxy (9-10) ethanol), TWEEN 100 surfactant, As well as, but not limited to, BASF pluronic surfactants. General classes include glycols, alkoxylate polyoxyalkylene fatty ethers such as polyoxyethylene fatty ethers, sorbitan esters, mono and diglycerides, polyoxyethylene sorbitol esters, polymeric surfactants such as Hypermen polymeric surfactants, coconut oil Alkyl PG dimonium sodium chloride and coamidopropyl PG dimonium chloride, phosphoric acid esters, polyoxyethylene (POE) fatty acid esters, Renex nonionic surfactants (ethylene oxide and unsaturated fatty acids and heterocyclic resins) Nonionic esters formed by the reaction of acids), alcohol ethoxylates, alcohol alkoxylates, ethylene oxide / propylene oxide block copolymers, sols Polyoxyethylene derivatives or combinations thereof of sorbitan esters.

  The specific amount of surfactant can be selected by considering factors such as particle size, surfactant type and / or other suitable criteria. In many cases, the weight ratio of surfactant to the amount of airgel-containing particles and binder is at least about 1: 100, such as from about 10: 100 to about 30: 100. Exemplary ratios that can be utilized include 5: 100, 15: 100, 20: 100 or 25: 100, 35: 100.

  It is possible that other inclusions are present. As used herein, the term “another inclusion”, “other inclusion” or “additional inclusion (s)” refers to a pre-prepared nanoporous material (eg, airgel containing) Compound or material outside the particle). For example, when utilizing Nanogel® airgel particles, the term “other inclusions” is used to refer to Nanogel® rather than the inclusions already present in or on the Nanogel® airgel particles. Refers to inclusions that can be combined with airgel particles. Render the composition to stick with a particular batting material to provide these other inclusions to provide reinforcement to the final product, to wet the outer surface of the airgel particles, to increase adhesion to the batting substrate Can be used to provide or enhance the desired other characteristics in the composition or finished insulating article, or for other reasons.

  Examples of other inclusions that may be used include opacifiers, viscosity modifiers, curing agents, agents that increase or decrease the rate at which the binder cures, agents or materials that increase mechanical strength, viscosity modifiers, pH modifiers, plasticizers Agents, lubricants, reinforcing agents, flame retardants (eg halogen-containing compounds, bromates, borates, aluminum trihydroxide, magnesium hydroxide, other oxides and / or fibers, plastics and compositions) Other known compounds) are included, but are not limited thereto. Other combinations of inclusions can also be used.

  In specific examples, other inclusions include microspheres such as fibers, fumed silica, colloidal silica or precipitated silica, opacifiers including but not limited to carbon black and titanium dioxide, perlite, glass or polymeric microspheres, Silica, such as calcium silicate, copolymer, tenside, mineral powder, film building ingredient, surfactant, and any combination thereof.

  For example, the fibers typically have an elongated, eg cylindrical shape, with an aspect ratio of length to diameter of greater than 1, preferably greater than 5, more preferably greater than 8. In many instances, suitable fibers have a length to diameter ratio of at least 20. The fibers can be woven, non-woven, short fibers, or long fibers. The fibers can comprise a single component, a composite component, eg, a core made from one material, and a sheath made from another material, or can be multicomponent. The fibers may be hollow or solid and may have a flat, rectangular, cylindrical or irregular cross section. The fibers may be relaxed, chopped, bundled, or connected together in a web or scrim.

  Examples of fibers that can be added include mineral cotton fibers, such as glass, stone or slag fibers, biosoluble ceramic fibers, or engraved forms of woven, non-woven or continuously made glass or stone fibers. included. Carbon fiber, polymer fiber, metal fiber such as steel fiber, cellulose fiber, plant-derived fiber such as cotton, wood or hemp fiber. A combination of fibers can also be used.

  The amount of other inclusions added may depend on the particular application and other factors. Accordingly, other content is greater than 0%, such as greater than 2%, such as greater than 5%, such as greater than 5%, greater than 10%, greater than 15%, greater than 20% by weight of the total weight of the mixture or It can be present in an amount greater than 25% by weight. Other inclusions can be present in the component in an amount of less than about 90% by weight, such as less than about 75% by weight or less than 50% by weight.

  Dry mixing or wet mixing techniques can be utilized to combine nanoporous materials (such as pre-prepared airgel-containing particles), binders, and surfactants and / or other ingredients, if used. Two or more or all components can be added simultaneously. The inclusions can also be combined sequentially using any suitable order.

  In many embodiments, the one or more starting materials include a liquid and mixing produces a slurry. In other embodiments, the dry starting material can be combined with the liquid in any suitable order, and mixing can be used to produce a slurry.

  Mixing can be performed manually (eg, by manual stirring or vibration). In a specific implementation, the slurry is formed with the aid of a mixer or mixer, such as a cement mixer, handheld or industrial impeller. Ribbon mixers, double ribbon blades, planetary mixers, and other suitable mixing devices such as are known in the art can also be utilized. In some cases, increased blade design and / or characteristics, such as increased blade sharpness, can reduce the time required to complete the mixing process and, in some cases, the final product characteristics. In a specific example, light particles, such as airgel particles, are forced into the liquid phase. In other examples, the droplets are moved to lighter particles.

  Parameters such as mixing speed, temperature, degree of shear, liquid and / or solid material order and / or addition rate can be adjusted, depending on the scale of operation, the physical and / or chemical nature of the components, etc. May be.

  A mixing technique can be selected to change (usually reduce) the actual size of the airgel particles. In a specific example, the selected mixing technique improves, for example, the penetration of the airgel material into and / or through the utilized batting to reduce the size of at least a portion of the airgel particles. In order to provide sufficient shear force. In other examples, a slower mixing technique can be utilized, for example, where the starting airgel particles have a particle size appropriate for a particular batting. In yet another example, a mixing technique is selected to modify the size distribution of the airgel particles. The change in particle size distribution can then be used to improve particle packing efficiency.

  Mixing can occur at room temperature or other suitable temperature. Normally, the components are combined in the ambient atmosphere, but can provide a specific gas atmosphere and / or pressure.

  In many cases, the slurry is aqueous, ie its liquid phase contains more than 50% by volume of water. Nonaqueous slurries can also be used. Such non-aqueous slurries can include one or more organic compounds such as organic solvents, surfactants and diluents. The non-aqueous slurry can include water in an amount of about 0 to about 50% by volume, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, or 49% by volume.

  The slurry viscosity is selected taking into account factors such as the type of batting material utilized, the thickness of the batting, the number of batting layers treated with the slurry, and the technique used to treat the batting with the slurry. Is done. For example, a thicker and / or thicker web may benefit from the use of a low viscosity slurry, while a thicker slurry can be used with a thin and / or open web. In many cases, the slurry is from about 2,000 centipoise (cP) to about 100,000 cP, such as 10,000 cP, 20,000 cP, 30,000 cP, 40,000 cP, 50,000 cP, 60,000 cP, 70,000 cP. , 80,000 cP, or 90,000 cP.

  Batting can be treated with the slurry by various processes. In many embodiments, one or more batting layers are impregnated with the slurry. In some implementations, the selected process provides penetration of at least one batting layer utilized. In other implementations, the process provides penetration of two or more batting layers. In one example, the slurry is applied to a first batting layer, and then the first batting layer is covered by a second batting layer. The slurry is then applied to the second batting layer and the process is continued for the desired number of layers. In further implementations, the selected method is suitable for expansion or industrial processes such as airlaid and / or roll-to-roll manufacturing.

  Specific techniques contemplated for applying the slurry to the batting include immersing or immersing the batting in the slurry, for example with or without bath agitation, pouring the slurry over the batting, Injecting, batting or spraying the slurry to and / or batting and / or other processes such as are known in the art. It has been discovered that soaking batting in the slurry is particularly beneficial for penetrating multiple (two or more) layers of batting. In a specific implementation, soaking was performed in the presence of another suitable form of agitation for the entire period of shaking, stirring, or soaking, or for fewer intervals. Also, intermittent stirring of the immersion bath can be used.

  Applying the slurry to the batting can be performed at ambient conditions, such as room temperature and / or atmospheric pressure, or other suitable conditions. For example, the batting can be processed above room temperature. For example, a pressure differential can be used to improve slurry penetration through the web opening in the batting.

  In many implementations, the airgel-containing particles are distributed throughout the thickness of the single or multiple layers of batting. Insulating structures comprising airgel (or other nanoporous material) distributed throughout the thickness of the entire batting layer (s) utilized can be referred to as “impregnated” structures or materials. In a “partial” impregnated structure, the airgel (or other nanoporous material) is distributed through some but not all of the batting layer utilized. In a “painted” insulating structure, the airgel (or other nanoporous material) is present on one side of the structure, but on the opposite side of the painted layer, eg, inside the outer layer of the batting in a multi-layer arrangement Does not penetrate the surface.

  The treated batting can be dried using air or a special environment such as an inert gas, for example at or above room temperature. Drying can be simply by drying the slurry or by drawing a vacuum through an oven, drying chamber, gas stream directed to the batting containing the slurry, the treated batting, or any such as is known in the art, for example. This can be done by using other suitable drying equipment. In a specific example, the drying step is performed using equipment and / or techniques appropriate for the expansion or industrial manufacturing process.

  The structure can include additional elements. For example, to coat one or both of the outer (outer) surfaces of the structures described herein with another type of outer layer for film, foil, coating or protection to form a multi-layered arrangement Can be provided with a reflective coating, water barrier or water vapor barrier.

  To produce such a structure, one or more cover layers made of, for example, a film, foil, or other suitable material are applied to one or both of the outer surfaces of the structure during or after the manufacturing process. Can be pasted at any appropriate time. For example, a cover can be provided on the outer surface of the outer layer of the batting before applying the mixture (slurry). In other cases, the cover can be attached to the outer surface of the completed structure. The cover layer can be the same or different when both (outer) surfaces of the structure are coated. For example, the coatings can both be made from the same water barrier or water vapor barrier material. In other cases, one cover layer can be designed to provide protection while unrolling, while the other can be a reflective film.

  The cover can be attached by any suitable means. For example, the cover can be laminated, glued, painted, sprayed, secured by mechanical means such as staples and fasteners, or alternatively attached to the outer surface of the batting or the finished structure.

  Additional elements can also be provided in the form of one or more inner layers made from materials other than the batting material. In one approach to making such a structure, one or more non-batting layers are interspersed with the batting layer, and the process is adapted to ensure that one or more batting layers are impregnated with the slurry. Can be done. Dipping techniques, continuous application of slurry to each batting layer, or other suitable methods can be utilized.

  The structure can include at least one inner non-batting layer and at least one cover layer.

  The resulting structure (article) can be in the form of a blanket, mat, sheet, flexible board, and the like. The structure is at least partially flexible and often wraps around the object, wraps or unwraps the structure, folds, folds, and into an airgel-containing blanket or flexible composition There is enough flexibility to allow other actuations as desired. A photograph of a flexible insulating material according to an embodiment described herein is shown in FIG.

  In many cases, the flexible insulating structure described herein is about 50 milliwatts divided by meters per degree Kelvin (mW / (m · K) or less, such as about 30 or less, such as about 25 or less, and many In this case, it has a thermal conductivity (at 23 ° C. and 1 atm) of about 23 mW / (m · K) or less.

  The structure can have specific light transmission characteristics, for example, other properties such as soundproofing characteristics, eg sound absorption and / or acoustic reflection characteristics, that allow at least some visible light to pass through. The flexible insulating structure described herein can also have electrical insulating properties.

  It can also provide properties related to fire protection equipment, such as total heat content, flame propagation index, surface combustion characteristics, flammability and the like.

  In many implementations, the structure is at least 150 ° C., often at least 300 ° C., for example, in the range of about 100 ° C. to about 800 ° C., for example, in the range of about 200 ° C. to about 600 ° C. without significant degradation. Can withstand.

  In many cases, the structure has hydrophobic properties.

  The structure can perform well under compressive load, for example with load bearing properties.

  Use flexible insulation structures, for example, in insulation pipes, containers or other industrial equipment in pipe-in-pipe arrangements, in buildings, automobiles, ships, aircraft and other applications, in clothing, footwear, and sporting goods it can. In many implementations, the structure is used in high temperature applications, such as in the range of about 150 ° C to about 800 ° C. In one example, a method for insulating an object includes incorporating the flexible insulating structure of claim 1 in an article including the object, and exposing the article to a temperature of at least 150 ° C.

Example 1
300 g of deionized water, 0.33 g of a 50% solution of Pluronic P84 (BASF), 16.7 g of calcium sulfate hemihydrate (Sigma Aldrich) and 33 g of TLD 302 grade Nanogel® airgel in Connecticut, USA The mixture (or slurry) was formed using a Waring Commercial 7010G Blender mixer from Waring Products, mixing for 3 minutes at the Low setting.

  The mixture was poured (with the back removed) into two types of ultrafine synthetic fiber insulation, namely Thinsulent ™ 100 (made by 3M) and PrimaLoft® 1.8 oz. After 45 minutes, inspection of the sample revealed that only water penetrated through the PrimaLoft® insulator, and none penetrated through the Thinsulate ™ material. It is believed that batting within the Thinsulate ™ insulator prevented airgel particle penetration.

Example 2
Waring Commercial 7010G with 500 g deionized water, 0.33 g 50% solution Pluronic P84 (BASF), 16.7 g calcium sulfate hemihydrate (Sigma Aldrich) and 33 g TLD302 grade Nanogel® airgel. Blended using Blender for 3 minutes at “Low” setting.

  The mixture was poured into a PrimaLoft® sample with the support removed. The PrimaLoft® material was composed of four layers of fibers. Several groups of samples were studied. Each layer in the sample corresponds to a quarter of PrimaLoft® fiber. The first group of samples has one layer, the second group of samples is in the form of a single layer sandwich, the third group of samples has two layers, the fourth group of samples has a two layer sandwich configuration Had.

  In the “sandwich” configuration, one or two layers were placed below, the mixture was poured over the top surface of the bottom layer (s), and one or two layers were placed on the top.

  For illustration, for example, the bottom fiber layer 12 is shown in FIG. 2A. Mixture 14 contained airgel and binder and was added to the top surface of layer 12 as shown in FIG. 2B. Layer 16 was then placed on top of mixture 14 resulting in a sandwich structure comprising two layers (12 and 16) as shown in FIG. 2C.

  Sandwich structures having more than two layers can be prepared as shown in FIGS. Two stacked bottom fiber layers, specifically fiber layers 22 and 24, are shown in FIG. 3A. Mixture 14 (including aerogel and binder) is added (cast) to the top surface of the fiber layer 24 as shown in FIG. 3B. The structure is completed by coating the top of the mixture 14 comprising layers 26 and 28, resulting in a sandwich structure comprising 3 or more layers (in this case a total of 4 layers) as shown in FIG. 3C.

  After 24 hours, for each one layer sample (Group 1), the mixture penetrated through the layer to the bottom. Upon decomposition, one layer of the sandwiched sample (second group) had the same amount of dry mixture on both sides. For the two layer sample (Group 3), the mixture did not penetrate the bottom. Upon decomposition, the two-layer sandwich type sample (Group 4) presented a clean top layer with no dry mixture.

Example 3
500 g deionized water, 0.33 g 50% solution Pluronic P84 (BASF), 16.7 g calcium sulfate hemihydrate (Sigma Aldrich) and 33 g TLD302 grade Nanogel® airgel (particle size is (Range 1.2-3.2 mm) using a Waring Commercial 7010G Blender mixer from Waring Products, Connecticut, USA for 3 minutes at the Low setting.

  A portion of the mixture was placed in the top container of a plastic screw as follows. The first container contains the mixture with 2 layers of 1 layer of PrimeLoft®, and the second container contains the mixture with 1 layer of PrimeLoft® 45 pieces of 2 cm × 2 cm. It was. Both containers were shaken for 1 hour. The sample was removed and laid flat in the mold and allowed to dry overnight. Both approaches resulted in a sample of PrimaLoft® that was fully impregnated with the Nanogel® airgel mixture.

Example 4
Except for the use of grade TLD201 (gel size 1-30 microns, d50 of 8-10 microns) Nanogel® type airgel (not the TLD302 grade of Example 3) in the mixture, The same contents and amounts used were included. Mixing was done manually and the mixture was shaken with one large piece and one 2 cm x 2 cm piece and dried overnight. The sample was found to be fully impregnated with the airgel-containing mixture.

  TLD201 grade Nanogel® aerogels have a particle size of 8-10 microns, 8-10 micron particle size using TLD302 grade Nanogel® type airgel and mechanical mixing It is believed that it was approximately the same as the sheared particle size obtained. This result indicated that both approaches were sufficient to impregnate the sample.

Example 5
500 g of deionized water, 0.33 g of a 50% solution of Pluronic P84 (BASF), 16.7 g of calcium sulfate hemihydrate (Sigma Aldrich) and 33 g of TLD 302 grade Nanogel® airgel, Connecticut, USA 3 minutes using a Waring Commercial 7010G Blender mixer from Waring Products.

  The mixture was placed in a 1 gallon plastic container. Fully laminated (a total of 4 layers of PrimaLoft®) material was cut into 6 inches x 6 inches (sample A) (with the back removed). Another piece of fully laminated PrimaLoft® material was cut into a sample, ie 4 cm x 2 cm (Sample B). All these samples were immersed in the mixture for 5 minutes, after which these samples were placed on a wire mesh funnel. Excess liquid was removed by applying a vacuum. Another sample (Sample C) consists of 2 pieces of 6 inch x 6 inch PrimaLoft (R) fully stacked, dipped in the two pieces, then placed on top of each other (total 8 layers) and dried I was able to. All samples were subsequently dried in an 80 ° C. oven for 16 hours.

  Thermal conductivity measurements were performed according to the ASTM C518 method on a Lasercomp Model FOX200 manufactured by Lasercomp, Massachusetts, USA.

  Sample A had a thermal conductivity of 25.57 mW / m · K, and Sample C had a thermal conductivity of 23.46 mW / m · K. A sample (Sample B) made from multiple smaller pieces was not flat enough to allow thermal conductivity measurements.

  Both Samples A and C were foldable and severable. Sample B was more rigid.

Other Considerations Drawing a vacuum has been found useful for the drying process, but it seemed ineffective to pull the slurry through an insulating material such as PrimaLoft®.

  Both agitation and vibration appeared to be advantageous for impregnating the PrimeLoft® material and were particularly effective when processing fully laminated PrimeaLoft®.

Although the invention has been particularly shown and described with reference to preferred embodiments thereof, various changes in form and detail may be made therein without departing from the scope of the invention as encompassed by the appended claims. Those skilled in the art will understand that this can be done.
The present invention includes the following aspects.
(1) (a) batting,
(B) a mixture of airgel-containing particles and a binder, wherein the airgel-containing particles impregnate at least one layer of the batting;
A flexible insulating structure comprising:
(2) The flexible insulating structure according to (1), wherein the thermal conductivity of the structure is about 23 mW / m · K or less at 23 ° C. and 1 atm.
(3) The flexible insulating structure according to (1), wherein the entire batting is impregnated with the airgel-containing particles.
(4) The flexible insulating structure according to (1), wherein the binder is an inorganic binder.
(5) The flexible insulating structure according to (1), wherein the binder is gypsum.
(6) The flexible insulating structure according to (1), wherein the mixture further includes a surfactant.
(7) The flexibility according to (1), wherein the batting is a woven fabric or a non-woven fabric, and is selected from the group consisting of polymer fiber batting, glass fiber batting, mineral cotton fiber batting, carbon fiber, and any combination thereof. Insulating structure.
(8) The flexible insulating structure according to (1), wherein the batting is a polyester fiber batting.
(9) The flexible insulating structure according to (1), wherein the structure has one or more of flame retardancy, soundproofing properties, electrical insulation properties, hydrophobicity, light transmission properties, or fire resistance.
(10) The flexible insulating structure according to (1), wherein the structure has load bearing characteristics.
(11) The flexible insulating structure according to (1), further comprising at least one cover layer that provides protection, a reflective coating, a water barrier, or a water vapor barrier.
(12) The flexible insulating structure according to (1), further comprising one or more non-batting inner layers.
(13) A method for preparing a flexible insulating structure comprising:
Applying a mixture comprising airgel-containing particles and a binder to a batting having one or more batting layers;
The binder can be dried or dried, thereby forming the flexible insulating structure;
Including a method.
(14) The method according to (13), wherein the mixture further comprises a surfactant.
(15) The method according to (13), wherein the mixture is a slurry.
(16) The method according to (15), wherein the batting is immersed or immersed in the slurry.
(17) The method according to (16), wherein the immersion or immersion is performed in the presence of stirring.
(18) The method according to (17), wherein the stirring is performed by stirring or vibrating.
(19) The method according to (17), wherein the stirring is performed at time intervals equal to or less than a time used for performing the immersion or immersion.
(20) The method of (13), wherein the mixture is applied by pouring, spraying, painting, dipping or any combination thereof into the batting.
(21) The method according to (13), wherein the entire flexible insulating structure is impregnated with airgel-containing particles.
(22) The method according to (13), wherein the flexible insulating structure is partially impregnated or coated with airgel-containing particles.
(23) The method according to (13), further comprising applying a cover layer to the outer surface of the batting.
(24) The method according to (13), further comprising applying a cover layer to an outer surface of the flexible insulating structure.
(25) The method according to (13), wherein the flexible insulating structure further includes at least one non-batting inner layer.
(26) An article comprising the flexible insulating structure according to (1).
(27) An article comprising a flexible insulating structure adjusted by the method of (13).
(28) A method for insulating an object,
In an article comprising said object (incorporating one flexible insulating structure;
Exposing the article to a temperature of at least 150 ° C;
Including a method.
(29) The method according to (28), wherein the flexible insulating structure covers a surface of the object.
(30) The method according to (28), wherein the article is selected from the group consisting of clothes, footwear, pipe-in-pipe arrangements, insulating containers, buildings, automobiles, ships, aircraft and exercise equipment.

Claims (17)

A method for preparing a flexible insulating blanket comprising:
And applying a mixture comprising a prefabricated airgel-containing particles and a binder on one or more have a batting layer Luba potting,
The binder can be dried or dried, thereby forming the flexible thermal blanket ;
Wherein the said the thickness of the batting is 4Mm～50mm, a weight of ^{50g / m 2 ~250g / m 2} , method.   The method of claim 1, wherein the mixture further comprises a surfactant.   The method of claim 1, wherein the mixture is a slurry.   The method according to claim 3, wherein the batting is immersed or immersed in the slurry.   The method according to claim 4, wherein the immersion or immersion is performed in the presence of stirring.   The method of claim 5, wherein the agitation is by stirring or shaking.   The method according to claim 5, wherein the stirring is performed at a time interval equal to or less than a time used for performing the immersion or immersion.   The method of claim 1, wherein the mixture is applied by pouring, spraying, painting, dipping or any combination thereof on the batting. The method of claim 1, wherein the entire flexible insulating blanket is impregnated with airgel-containing particles. The method of claim 1, wherein the flexible thermal blanket is partially impregnated or painted with airgel-containing particles.   The method of claim 1, further comprising applying a cover layer to an outer surface of the batting. The method of claim 1, further comprising applying a cover layer to an outer surface of the flexible thermal blanket . The method of claim 1, wherein the flexible thermal blanket further comprises at least one non-batting inner layer. It said flexible insulation blanket solves the and / or the winding wrapping the blanket, the blanket has sufficient flexibility to cause it possible to wrap the circumference of the article, according to claim 1 Method. The airgel-containing particles have the following characteristics:
(1) Bulk density of 0.15 g / cm ³ or less,
(2) 300-1,000 m ² / g surface area,
(3) a porosity of 90% or more,
The method of claim 1, comprising a combination of (4) a pore volume of 3 mL / g or more, and (5) a nanoporous structure having pores less than 1 micron.   The method according to claim 1, wherein the batting has a thermal conductivity of 80 mW / m · K or less at 23 ° C.   The method of claim 1, wherein the binder is gypsum, cement, lime, mixed magnesium salt, silicate, or plaster binder.