WO2014160999A1 - Highly reactive materials for use as desiccants and getters in an enclosed environment and methods for using same - Google Patents

Highly reactive materials for use as desiccants and getters in an enclosed environment and methods for using same Download PDF

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Publication number
WO2014160999A1
WO2014160999A1 PCT/US2014/032389 US2014032389W WO2014160999A1 WO 2014160999 A1 WO2014160999 A1 WO 2014160999A1 US 2014032389 W US2014032389 W US 2014032389W WO 2014160999 A1 WO2014160999 A1 WO 2014160999A1
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WIPO (PCT)
Prior art keywords
insulation panel
thermal insulation
reactive material
vacuum
aluminum
Prior art date
Application number
PCT/US2014/032389
Other languages
French (fr)
Inventor
Timothy WOJCIECHOWSKI
Daniel A. Scherson
Charles Hewitt
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Caralon Global Limited
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Publication date
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Publication of WO2014160999A1 publication Critical patent/WO2014160999A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/28Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer comprising a deformed thin sheet, i.e. the layer having its entire thickness deformed out of the plane, e.g. corrugated, crumpled
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00Thermal insulation in general
    • F16L59/06Arrangements using an air layer or vacuum
    • F16L59/065Arrangements using an air layer or vacuum using vacuum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/304Insulating

Definitions

  • VIP vacuum insulation panel
  • Typical VIPs may include multiple layers of material formed to create an internal cavity that may be in a vacuum state.
  • a VIP may act as an effective insulator due to the low thermal conductivity properties inherent in a space under vacuum.
  • the efficiency of a VIP can be related to the ability of the VIP to enter and maintain an adequate vacuum state.
  • unwanted gases for example, through outgassing of VIP materials
  • moisture may penetrate the evacuated space and cause a rise in internal pressure leading to a loss of vacuum. Accordingly, it would be beneficial to provide a VIP configured to counteract these effects and maintain an effective vacuum pressure for a long duration.
  • a thermal insulation panel may include at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel, and at least one reactive material configured to prevent a loss of the vacuum pressure within the core and arranged within at least one protective material configured to prevent exposure of the at least one reactive material to an environment within the core, wherein the at least one protective material is configured to be transformed to expose the at least one reactive material to the environment.
  • a thermal insulation panel may include at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel, and at least one reactive material arranged within the vacuum insulation panel and configured to prevent a loss of the vacuum pressure therein, the at least one reactive material being configured to be deposited within the vacuum insulation panel in a non-reactive environment and to be reactive under an environment within the core.
  • a method of forming a thermal insulation panel may include providing at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel, arranging at least one reactive material within the thermal insulation panel, the at least one reactive material being configured to prevent a loss of the vacuum pressure within the core, and providing at least one protective material configured to prevent exposure of the at least one reactive material to an environment within the core, wherein the at least one protective material is configured to be transformed to expose the at least one reactive material to the environment.
  • FIG. 1 A depicts an illustrative thermal insulation unit according to a first embodiment.
  • FIG. IB depicts an illustrative thermal insulation unit according to a second embodiment.
  • FIG. 2 depicts an illustrative thermal insulation unit according to a third embodiment.
  • FIGS. 4A and 4B depict an illustrative thermal insulation unit according to a fourth embodiment.
  • FIGS. 5A and 5B depict an illustrative thermal insulation unit according to a fourth embodiment.
  • the thermal insulation units may include one or more layers or walls forming a core within the thermal insulation unit.
  • the core may be evacuated to form a vacuum therein.
  • the core may not have a vacuum formed therein.
  • a layer or wall may have an inner space that is evacuated to form a vacuum therein.
  • desiccants and/or getters may be provided to capture gases coming off the core material of a thermal insulation unit, for instance, through outgassing.
  • the thermal insulation unit may be configured as a vacuum insulation panel (VIP) including multiple layers of core materials.
  • VIP vacuum insulation panel
  • the multiple layers of core materials may be arranged to form a core capable of sustaining a vacuum.
  • the desiccants and/or getters may be applied to one or more of the multiple layers of core materials or on the inside of the core (for example, on, in, or around the barrier material that encloses the core).
  • some embodiments provide desiccants and/or getters that may be applied in standard or substantially standard atmospheric conditions (for example, standard temperature, pressure, humidity, and/or the like) and may be activated as the pressure inside the core of a thermal insulation unit is decreased or gas and/or moisture molecules are removed.
  • the desiccant and/or getter may be arranged within a material that may crack, or become otherwise deformed, in response to a force or reaction such that the desiccant and/or getter disposed therein is exposed to the environment within the core.
  • the material may crack responsive to a mechanical force, a chemical reaction, a temperature change, a pressure change, an electrical force, a magnetic force (for example, a magnetic field), or any combination thereof.
  • the material may be configured as one or more nanoparticles or nanospheres filled with a gas or solid desiccant and/or gettering material.
  • Thermal insulation units may be used to impede energy flow into or out of a system of interest.
  • Thermal insulation units such as VIPs
  • VIPs do not maintain perfect vacuum during their lifetime as moisture and unwanted gases penetrate the core under vacuum. For example, most materials release gases (for instance, through outgassing) when placed in a low pressure environment, such as the core of a VIP under vacuum.
  • One approach to counter these effects is to use desiccants and/or getters.
  • Desiccants are chemicals that absorb moisture, while getters are chemicals that absorb or react with gases. Each of these materials may be used to maintain the vacuum of a VIP and, therefore, increase the effectiveness and extend the life of a VIP by absorbing or reacting with unwanted gases and moisture that promote heat transfer within the core under vacuum.
  • FIG. 1 A depicts an illustrative thermal insulation unit according to a first embodiment.
  • a thermal insulation unit may be configured as a VIP 105 having multiple layers 110, 115, 120.
  • layers 110, 115, 120 may be provided for one or more different purposes.
  • layer 110 may be a protecting layer
  • layer 115 may be a barrier layer
  • layer 120 may be a sealing layer.
  • the multiple layers 110, 115, 120 may be formed to provide a core 125 that is under vacuum.
  • the level of vacuum may vary and may depend on the use of the container.
  • the vacuum may be near vacuum pressure at less than 10 ⁇ 2 bar to as low as 10 ⁇ 8 bar.
  • the vacuum pressure may be about 10 ⁇ 2 bar, about 10 ⁇ 3 bar, about 10 "4 bar, about 10 ⁇ 5 bar, about 10 ⁇ 6 bar, 10 ⁇ 7 bar, 10 ⁇ 8 bar, 10 ⁇ 9 bar, from about 10 ⁇ 2 bar to about 10 ⁇ 9 bar, about 10 ⁇ 3 bar to about 10 ⁇ 8 bar, about 10 ⁇ 4 bar to about 10 ⁇ 8 bar, or about 10 ⁇ 5 bar to about 10 ⁇ 8 bar, or any pressure between these ranges (including endpoints).
  • the vacuum pressure may be maintained for various durations.
  • the various durations may include about one day, about one week, about six months, about 1 year, about 2 years, about 3 years, about 4 years, about 5 years, about 6 years, about 7 years, about 8 years, about 9 years, about 10 years, about 1 year to about 5 years, about 5 years to about 10 years, about 2 years to about 5 years, about 2 years to about 10 years, and any duration between these ranges (including endpoints).
  • FIG. IB depicts a second illustrative thermal insulation unit according to some embodiments.
  • a thermal insulation unit may be configured as a VIP 130 including a first box 140 configured to be inserted into a second box 135.
  • the first box 140 and the second box 135 may include multiple layers of insulating material, as depicted in detail 145. Contact between the first box 140 and the second box 135 may be maintained by various methods, for example, by friction or an adhesive layer disposed between the first box 140 and the second box 135, such that a cavity 150 may be formed therebetween. In some embodiments, a vacuum may be established in the cavity 150 to provide thermal insulation properties for the VIP 130.
  • a vacuum may be established between the multiple layers of insulating material of the first box 135. In some embodiments, a vacuum may be established between the multiple layers of insulating material of the second box 140. In this manner, the walls of the first box 135 and/or second box 140 may provide thermal insulation properties for the VIP 130. In such embodiments, a vacuum may not be established within the cavity 150.
  • Embodiments are not limited to the particular form of thermal insulation units (VIPs) depicted in FIG. 1A and FIG. IB, as these are non-restrictive and are for illustrative purposes only.
  • the containers of various embodiments may be of any size or shape.
  • the containers may be a cross-sectional shape that is circular, square, rectangular, triangular, elliptical, oval, lobe-shaped, pentagonal, hexagonal, heptagonal, octagonal, and the like or similar configurations.
  • the containers may be open on both ends, and in other embodiments, one or both ends of the containers may be enclosed by the insulating material or by another material that may or may not include a vacuum cavity.
  • the thermal insulation units may be configured as containers, boxes, cases, cartridges, VIPs and the like, including those with an open end and those with enclosed ends.
  • the thermal insulation units may include any number of additional layers, such as insulation layers, that may be composed of any suitable material and may have spaces or cavities arranged therein that may maintain a vacuum within the layer.
  • the layers may include, without limitation, fiber glass, polystyrene, polyurethane, urea formaldehyde, phenolic or styrene foams, polyisocyanurate, structured polymer or fiber films such as aerogels, fumed silica, polyurethane, or combinations thereof.
  • the thermal insulation unit may include a vacuum cavity.
  • the vacuum cavity may be empty, may have a desiccant and/or getter material disposed therein, may be configured to receive an object or a device, and combinations thereof.
  • the object or device may include any object or device capable of being arranged within the thermal insulation device cavity according to some embodiments.
  • the object or device may include, without limitation, a battery, an electrical power source, an electronic device, a force generating element (for example, an element configured to generate heat, an electrical field, a magnetic field, or physical forces, such as sound waves), or combinations thereof.
  • the desiccants and/or getters are not limited to any particular kind or type of desiccant and/or getter.
  • the desiccants and/or getters may include, but are not limited to, aluminum, silver, indium, nickel, gold, aluminum oxide, aluminum nitride, aluminum oxynitride, silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, indium tin oxide, and/or the like, and combinations thereof.
  • aluminum, silver, indium, nickel, gold aluminum oxide, aluminum nitride, aluminum oxynitride, silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, indium tin oxide, and/or the like, and combinations thereof.
  • the vacuum cavity may include nanoparticles capable of absorbing or reacting with gases and moisture that may enter the cavity.
  • Illustrative nanoparticles may include, but are not limited to, alumina, silica, mica, silver, indium, nickel, gold, aluminum suboxide, aluminum oxynitride, silicon suboxide, silicon carbide, silicon oxynitride, indium zinc oxide, indium tin oxide nanoparticles, iron oxide, and/or the like, and combinations thereof.
  • the nanoparticles may be desiccant nanoparticles prepared from materials including, but not limited to, calcium chloride, calcium sulfate, phosphorus pentoxide, other water-retaining polymers, and/or the like, and combinations thereof.
  • FIG. 2 depicts an illustrative thermal insulation according to a third embodiment.
  • a material 215 may be positioned within a vacuum cavity 225 of a VIP 205.
  • the desiccant and/or getter material 215 may operate to react irreversibly 225 with gas and/or moisture 210 located within the vacuum cavity 225 to form 230 solids or semi-solid compounds 220.
  • the 230 solids or semi-solid compounds 220 may have negligible vapor pressure.
  • the desiccant and/or getter material 215 may comprise various substances, such as highly reactive substances, including, without limitation, metals, metal alloys, oxides, water, oxygen, nitrogen, carbon dioxide, and combinations thereof.
  • the desiccant and/or getter material 215 may comprise aluminum.
  • the material may be used to generate material surfaces having a very high area to increase the ability of the material to absorb or react with gases.
  • aluminum may be electroplated at room temperature from an ionic liquid, such as an ionic liquid containing trichloroaluminum and an organic chloride salt.
  • a highly reactive metal such aluminum or a compound including aluminum, either by itself or co-deposited with at least one other reactive material or a non-reactive material, for instance, that may be heated from the outside of the enclosure without the need to open the enclosure.
  • the at least one other reactive material may be from an ionic liquid, for example, as a constituent or dispersed within the reactive material.
  • the at least one other reactive material may include lithium or a compound including lithium.
  • the electrodeposition may operate to produce single phase microporous films or layered formations involving one or more materials described herein, such as aluminum, a compound including aluminum, lithium, a compound containing lithium, magnesium, a compound containing magnesium, or a compound containing aluminum and/or lithium and/or magnesium.
  • the single phase microporous films or layered formations may be generated on a variety of substrates configured to operate as desiccants and/or getters for such gases including, without limitation, water, oxygen, carbon dioxide, dinitrogen, and a combination thereof.
  • a desiccant and/or getter material may be introduced into a thermal insulation unit through co-deposition of a desiccant and/or getter metal and or alloy from an ionic liquid containing nanoparticles and/or microparticles of a second material dispersed in the media that may be entrapped within the structure of the deposit.
  • the second material may include a desiccant and/or getter material.
  • the nanoparticles and/or microparticles may have a
  • FIGS. 3A and 3B depict an illustrative thermal insulation unit according to a fourth embodiment.
  • a VIP 305 may include a first material 310 disposed within a cavity 320.
  • the cavity 320 may be under vacuum.
  • the first material 310 may include a second material 315 arranged therein.
  • the second material 315 may be wholly or partially sealed within the first material 310 such that the second material does not interface with the cavity 320
  • the first material 310 may be configured as a protective material or protective layer for the second material 315.
  • the first material 310 may include lithium or some form of lithium and the second material 315 may comprise aluminum or some form of aluminum.
  • the first material 310 may be configured as a coating, film, paste, gel, solid, semi-solid, or some combination thereof that is deposited on one or more layers of the VIP 305.
  • the first material 310 - second material 315 co-deposit may be configured as a coating that is a deep and capable of capturing significant amounts of gases and/or moisture in one, two, or three dimensions. In this manner, the first material 310 - second material 315 co-deposit may operate to prevent, among other things, the ingress of gases from the atmosphere through the barrier materials that form the VIP 305 and the vacuum cavity 320.
  • the first material 310 may crack, deform, open, dissolve, break apart, crumble, or otherwise transform such that the second material 315 may be exposed to the environment of the cavity 320.
  • the first material 310 may transform responsive to various forces and/or reactions including, without limitation, a mechanical force, a chemical reaction, a pressure change, a magnetic force (for instance, a magnetic field), an electrical force, and/or a temperature change.
  • the forces and/or reactions may be internal to the VIP 305.
  • the forces and/or reactions may be external to the VIP 305.
  • the first material 310 and the second material 315 may have different temperature expansion coefficients so that heating and/or cooling of the cavity 320 environment may induce transformation of the first material and not the second material or vice versa.
  • a desiccant and/or getter material (for example, in the form of the first material 310 - second material 315 formation) may be introduced within the VIP 305, but the reactive material may not be exposed or may have limited exposure until a force or reaction is generated sufficient to transform the first material 310 and expose all or part of the second material 315.
  • FIGS. 4 A and 4B depict an illustrative thermal insulation unit according to a fifth embodiment.
  • a VIP 405 may include a plurality of nanospheres 425 including a first material 410 disposed within a cavity 420.
  • the cavity 420 may be under vacuum.
  • the first material 410 may enclose a second material 415 arranged therein.
  • the second material 415 may be wholly or partially sealed within the first material 410 such that the second material does not interface with the cavity 420 environment.
  • the first material 410 may be configured as a protective material or protective layer for the second material 415.
  • the first material 410 may crack, deform, open, dissolve, break apart, crumble, or otherwise transform such that the second material 415 may be exposed to the environment of the cavity 420.
  • the first material 410 may transform responsive to various forces or reactions such as a mechanical force (for example, shaking the VIP 405), a chemical reaction (for example, exposure of the nanospheres 425 to a chemical or gas), a temperature change (for example, a temperature change that causes thermal expansion of a layer, such as the first layer 410), and/or a change in pressure within the cavity 420.
  • the nanospheres 425 may be filled with a gas and/or solid desiccant or gettering material, such as calcium oxide (CaO), which, upon expansion, may transform (for example, crack) and expose the encapsulated second material 415 to the vacuum cavity 420 environment.
  • a gas and/or solid desiccant or gettering material such as calcium oxide (CaO)
  • CaO calcium oxide
  • FIGS. 5A and 5B depict an illustrative thermal insulation panel according to a sixth.
  • a VIP 505 may include a vacuum cavity 520 and a nanoparticle layer 530 having a plurality of nanoparticles 525 arranged therein.
  • the outer surfaces of the nanoparticle layer 530 may be configured as a protective material or protective layer for the nanoparticles 525.
  • a reaction element 535 may be configured to generate energy, a force, or the like that will react with or otherwise modify the nanoparticle layer 530.
  • the reaction element 535 may be configured to generate a magnetic field.
  • the nanoparticle layer 530 may be formed from a material that will react with the energy, force, or the like generated by the reaction element 535.
  • the nanoparticle layer 530 may be formed at least partially from a highly reactive metal, such as lithium, magnesium, aluminum, or the like, or combinations thereof.
  • the reaction element 535 may be external to the VIP 505 or the core 520. In another embodiment, the reaction element 535 may be internal to the VIP 505 or the core 520.
  • the reaction element 535 may generate a reaction 540, such as the generation of energy, a force, or the like that may penetrate at least a portion of the VIP 505 and crack, deform, open, dissolve, break apart, crumble, or otherwise transform at least a portion of the VIP to cause a breach in the nanoparticle layer 530.
  • a reaction 540 such as the generation of energy, a force, or the like that may penetrate at least a portion of the VIP 505 and crack, deform, open, dissolve, break apart, crumble, or otherwise transform at least a portion of the VIP to cause a breach in the nanoparticle layer 530.
  • the reaction element 535 may be configured to generate a reaction 540 in the form of a magnetic field.
  • reactions 540 may include electrical fields, magnetic fields, temperature changes, pressure changes, sound waves, or combinations thereof.
  • the breach in the nanoparticle layer 530 may expose the nanoparticles 525 to the environment of the inside of the cavity 520.
  • the nanoparticles 525 may include gas and/or solid desiccant or gettering material according to some embodiments. Although nanoparticles 525 were used in the depiction of a VIP in FIGS. 5 A and 5B, embodiments are not so limited, as the gas and/or solid desiccant or gettering material may be have any form capable of operating according to some embodiments described herein, such as a solid, liquid, gel, and/or paste material.

Abstract

Thermal insulation panels and methods for making same are described. A vacuum insulation panel may include at least one layer configured to form a central core under vacuum pressure. One or more reactive materials may be arranged within the vacuum insulation panel, such as within the core or the at least one layer. The one or more reactive materials may be configured to absorb and/or react with moisture or gas within the vacuum insulation panel to maintain a vacuum pressure therein. In some embodiments, the reactive materials may be arranged within a protective material configured to prevent exposure of the one or more reactive materials. The protective material may be configured to be transformed (for example, crack, crumble, break apart, or the like) responsive to certain events and/or conditions to expose the one or more reactive materials within the thermal insulation panel.

Description

HIGHLY REACTIVE MATERIALS FOR USE AS DESICCANTS AND GETTERS IN AN
ENCLOSED ENVIRONMENT AND METHODS FOR USING SAME
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 61/806572 filed on March 29, 2013, the contents of which are incorporated by reference in their entirety as if fully set forth herein.
BACKGROUND
[0002] There are numerous technological applications requiring the removal and/or regulation of gases within an enclosed environment. One application includes thermal insulation products employed to impede energy flow into or out of a system. An illustrative thermal insulation product is a vacuum insulation panel (VIP). Typical VIPs may include multiple layers of material formed to create an internal cavity that may be in a vacuum state. A VIP may act as an effective insulator due to the low thermal conductivity properties inherent in a space under vacuum.
[0003] The efficiency of a VIP, or other similar thermal insulation product, can be related to the ability of the VIP to enter and maintain an adequate vacuum state. However, unwanted gases (for example, through outgassing of VIP materials) and moisture may penetrate the evacuated space and cause a rise in internal pressure leading to a loss of vacuum. Accordingly, it would be beneficial to provide a VIP configured to counteract these effects and maintain an effective vacuum pressure for a long duration.
SUMMARY
[0004] This disclosure is not limited to the particular systems, devices and methods described, as these may vary. The terminology used in the description is for the purpose of describing the particular versions or embodiments only, and is not intended to limit the scope.
[0005] As used in this document, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. Nothing in this disclosure is to be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. As used in this document, the term "comprising" means "including, but not limited to."
[0006] In an embodiment, a thermal insulation panel may include at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel, and at least one reactive material configured to prevent a loss of the vacuum pressure within the core and arranged within at least one protective material configured to prevent exposure of the at least one reactive material to an environment within the core, wherein the at least one protective material is configured to be transformed to expose the at least one reactive material to the environment.
[0007] In an embodiment, a thermal insulation panel may include at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel, and at least one reactive material arranged within the vacuum insulation panel and configured to prevent a loss of the vacuum pressure therein, the at least one reactive material being configured to be deposited within the vacuum insulation panel in a non-reactive environment and to be reactive under an environment within the core.
[0008] In an embodiment, a method of forming a thermal insulation panel may include providing at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel, arranging at least one reactive material within the thermal insulation panel, the at least one reactive material being configured to prevent a loss of the vacuum pressure within the core, and providing at least one protective material configured to prevent exposure of the at least one reactive material to an environment within the core, wherein the at least one protective material is configured to be transformed to expose the at least one reactive material to the environment.
BRIEF DESCRIPTION OF DRAWINGS
[0009] FIG. 1 A depicts an illustrative thermal insulation unit according to a first embodiment.
[0010] FIG. IB depicts an illustrative thermal insulation unit according to a second embodiment.
[0011] FIG. 2 depicts an illustrative thermal insulation unit according to a third embodiment. [0012] FIGS. 3A and 3B depict an illustrative thermal insulation unit according to a fourth embodiment.
[0013] FIGS. 4A and 4B depict an illustrative thermal insulation unit according to a fourth embodiment.
[0014] FIGS. 5A and 5B depict an illustrative thermal insulation unit according to a fourth embodiment.
DETAILED DESCRIPTION
[0015] The described technology generally relates to thermal insulation units. In some embodiments, the thermal insulation units may include one or more layers or walls forming a core within the thermal insulation unit. In some embodiments, the core may be evacuated to form a vacuum therein. In some embodiments, the core may not have a vacuum formed therein. In some embodiments, a layer or wall may have an inner space that is evacuated to form a vacuum therein. In some embodiments, desiccants and/or getters may be provided to capture gases coming off the core material of a thermal insulation unit, for instance, through outgassing. In an embodiment, the thermal insulation unit may be configured as a vacuum insulation panel (VIP) including multiple layers of core materials. The multiple layers of core materials may be arranged to form a core capable of sustaining a vacuum. The desiccants and/or getters may be applied to one or more of the multiple layers of core materials or on the inside of the core (for example, on, in, or around the barrier material that encloses the core).
[0016] In another aspect, some embodiments provide desiccants and/or getters that may be applied in standard or substantially standard atmospheric conditions (for example, standard temperature, pressure, humidity, and/or the like) and may be activated as the pressure inside the core of a thermal insulation unit is decreased or gas and/or moisture molecules are removed. In an embodiment, the desiccant and/or getter may be arranged within a material that may crack, or become otherwise deformed, in response to a force or reaction such that the desiccant and/or getter disposed therein is exposed to the environment within the core. For instance, the material may crack responsive to a mechanical force, a chemical reaction, a temperature change, a pressure change, an electrical force, a magnetic force (for example, a magnetic field), or any combination thereof. In some embodiments, the material may be configured as one or more nanoparticles or nanospheres filled with a gas or solid desiccant and/or gettering material.
[0017] Thermal insulation units may be used to impede energy flow into or out of a system of interest. Thermal insulation units, such as VIPs, may generally include a core in a vacuum state formed from one or more layers of material. VIPs do not maintain perfect vacuum during their lifetime as moisture and unwanted gases penetrate the core under vacuum. For example, most materials release gases (for instance, through outgassing) when placed in a low pressure environment, such as the core of a VIP under vacuum. One approach to counter these effects is to use desiccants and/or getters.
[0018] Desiccants are chemicals that absorb moisture, while getters are chemicals that absorb or react with gases. Each of these materials may be used to maintain the vacuum of a VIP and, therefore, increase the effectiveness and extend the life of a VIP by absorbing or reacting with unwanted gases and moisture that promote heat transfer within the core under vacuum.
[0019] FIG. 1 A depicts an illustrative thermal insulation unit according to a first embodiment. As shown in FIG. 1A, A thermal insulation unit may be configured as a VIP 105 having multiple layers 110, 115, 120. In some embodiments, layers 110, 115, 120 may be provided for one or more different purposes. For example, layer 110 may be a protecting layer, layer 115 may be a barrier layer, and layer 120 may be a sealing layer. The multiple layers 110, 115, 120 may be formed to provide a core 125 that is under vacuum. In embodiments in which a vacuum is applied within the cavity, the level of vacuum may vary and may depend on the use of the container. In some embodiments, the vacuum may be near vacuum pressure at less than 10~2 bar to as low as 10~8 bar. For example, the vacuum pressure may be about 10~2 bar, about 10~3 bar, about 10"4 bar, about 10~5 bar, about 10~6 bar, 10~7 bar, 10~8 bar, 10~9 bar, from about 10~2 bar to about 10~9 bar, about 10~3 bar to about 10~8 bar, about 10~4 bar to about 10~8 bar, or about 10~5 bar to about 10~8 bar, or any pressure between these ranges (including endpoints). The vacuum pressure may be maintained for various durations. In some embodiments, the various durations may include about one day, about one week, about six months, about 1 year, about 2 years, about 3 years, about 4 years, about 5 years, about 6 years, about 7 years, about 8 years, about 9 years, about 10 years, about 1 year to about 5 years, about 5 years to about 10 years, about 2 years to about 5 years, about 2 years to about 10 years, and any duration between these ranges (including endpoints). [0020] FIG. IB depicts a second illustrative thermal insulation unit according to some embodiments. As shown in FIG. IB, a thermal insulation unit may be configured as a VIP 130 including a first box 140 configured to be inserted into a second box 135. The first box 140 and the second box 135 may include multiple layers of insulating material, as depicted in detail 145. Contact between the first box 140 and the second box 135 may be maintained by various methods, for example, by friction or an adhesive layer disposed between the first box 140 and the second box 135, such that a cavity 150 may be formed therebetween. In some embodiments, a vacuum may be established in the cavity 150 to provide thermal insulation properties for the VIP 130.
[0021] In some embodiments, a vacuum may be established between the multiple layers of insulating material of the first box 135. In some embodiments, a vacuum may be established between the multiple layers of insulating material of the second box 140. In this manner, the walls of the first box 135 and/or second box 140 may provide thermal insulation properties for the VIP 130. In such embodiments, a vacuum may not be established within the cavity 150.
[0022] Embodiments are not limited to the particular form of thermal insulation units (VIPs) depicted in FIG. 1A and FIG. IB, as these are non-restrictive and are for illustrative purposes only. The containers of various embodiments may be of any size or shape. For example, the containers may be a cross-sectional shape that is circular, square, rectangular, triangular, elliptical, oval, lobe-shaped, pentagonal, hexagonal, heptagonal, octagonal, and the like or similar configurations. In some embodiments, the containers may be open on both ends, and in other embodiments, one or both ends of the containers may be enclosed by the insulating material or by another material that may or may not include a vacuum cavity.
[0023] According to embodiments, the thermal insulation units may be configured as containers, boxes, cases, cartridges, VIPs and the like, including those with an open end and those with enclosed ends. The thermal insulation units may include any number of additional layers, such as insulation layers, that may be composed of any suitable material and may have spaces or cavities arranged therein that may maintain a vacuum within the layer. For example, in some embodiments, the layers may include, without limitation, fiber glass, polystyrene, polyurethane, urea formaldehyde, phenolic or styrene foams, polyisocyanurate, structured polymer or fiber films such as aerogels, fumed silica, polyurethane, or combinations thereof.
[0024] As described herein, the thermal insulation unit may include a vacuum cavity. In an embodiment, the vacuum cavity may be empty, may have a desiccant and/or getter material disposed therein, may be configured to receive an object or a device, and combinations thereof. The object or device may include any object or device capable of being arranged within the thermal insulation device cavity according to some embodiments. For instance, the object or device may include, without limitation, a battery, an electrical power source, an electronic device, a force generating element (for example, an element configured to generate heat, an electrical field, a magnetic field, or physical forces, such as sound waves), or combinations thereof. The desiccants and/or getters are not limited to any particular kind or type of desiccant and/or getter. For example, the desiccants and/or getters may include, but are not limited to, aluminum, silver, indium, nickel, gold, aluminum oxide, aluminum nitride, aluminum oxynitride, silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, indium tin oxide, and/or the like, and combinations thereof. In some
embodiments, the vacuum cavity may include nanoparticles capable of absorbing or reacting with gases and moisture that may enter the cavity. Illustrative nanoparticles may include, but are not limited to, alumina, silica, mica, silver, indium, nickel, gold, aluminum suboxide, aluminum oxynitride, silicon suboxide, silicon carbide, silicon oxynitride, indium zinc oxide, indium tin oxide nanoparticles, iron oxide, and/or the like, and combinations thereof. In some embodiments, the nanoparticles may be desiccant nanoparticles prepared from materials including, but not limited to, calcium chloride, calcium sulfate, phosphorus pentoxide, other water-retaining polymers, and/or the like, and combinations thereof.
[0025] FIG. 2 depicts an illustrative thermal insulation according to a third embodiment. As shown in FIG. 2, a material 215 may be positioned within a vacuum cavity 225 of a VIP 205. The desiccant and/or getter material 215 may operate to react irreversibly 225 with gas and/or moisture 210 located within the vacuum cavity 225 to form 230 solids or semi-solid compounds 220. In some embodiments, the 230 solids or semi-solid compounds 220 may have negligible vapor pressure. According to some embodiments, the desiccant and/or getter material 215 may comprise various substances, such as highly reactive substances, including, without limitation, metals, metal alloys, oxides, water, oxygen, nitrogen, carbon dioxide, and combinations thereof. [0026] In an embodiment, the desiccant and/or getter material 215 may comprise aluminum. According to some embodiments, the material may be used to generate material surfaces having a very high area to increase the ability of the material to absorb or react with gases. For example, aluminum may be electroplated at room temperature from an ionic liquid, such as an ionic liquid containing trichloroaluminum and an organic chloride salt. Accordingly, some embodiments provide for employing room temperature electrodeposition of a highly reactive metal, such aluminum or a compound including aluminum, either by itself or co-deposited with at least one other reactive material or a non-reactive material, for instance, that may be heated from the outside of the enclosure without the need to open the enclosure. Some embodiments provide that the at least one other reactive material may be from an ionic liquid, for example, as a constituent or dispersed within the reactive material. In some embodiments, the at least one other reactive material may include lithium or a compound including lithium. In some embodiments, the electrodeposition may operate to produce single phase microporous films or layered formations involving one or more materials described herein, such as aluminum, a compound including aluminum, lithium, a compound containing lithium, magnesium, a compound containing magnesium, or a compound containing aluminum and/or lithium and/or magnesium. The single phase microporous films or layered formations may be generated on a variety of substrates configured to operate as desiccants and/or getters for such gases including, without limitation, water, oxygen, carbon dioxide, dinitrogen, and a combination thereof.
[0027] According to some embodiments, a desiccant and/or getter material may be introduced into a thermal insulation unit through co-deposition of a desiccant and/or getter metal and or alloy from an ionic liquid containing nanoparticles and/or microparticles of a second material dispersed in the media that may be entrapped within the structure of the deposit. In an embodiment, the second material may include a desiccant and/or getter material. In an embodiment, the nanoparticles and/or microparticles may have a
circumference of about 1 nanometer, about 10 nanometers, about 50 nanometers, about 100 nanometers, about 200 nanometers, about 500 nanometers, about 1 millimeter, and ranges between any two of these values (including endpoints). The desiccant and/or getter material and/or any protective materials associated therewith may be deposited within a thermal insulation panel, such as VIP 205, using any technique capable of providing a thermal insulation panel according to some embodiments, including electrodeposition, vacuum deposition, and/or spray and/or layering technologies. [0028] FIGS. 3A and 3B depict an illustrative thermal insulation unit according to a fourth embodiment. As shown in FIG. 3A, a VIP 305 may include a first material 310 disposed within a cavity 320. In some embodiments, the cavity 320 may be under vacuum. The first material 310 may include a second material 315 arranged therein. According to some embodiments, the second material 315 may be wholly or partially sealed within the first material 310 such that the second material does not interface with the cavity 320
environment. In this manner, the first material 310 may be configured as a protective material or protective layer for the second material 315. In an embodiment, the first material 310 may include lithium or some form of lithium and the second material 315 may comprise aluminum or some form of aluminum.
[0029] According to some embodiments, the first material 310 may be configured as a coating, film, paste, gel, solid, semi-solid, or some combination thereof that is deposited on one or more layers of the VIP 305. In an embodiment, the first material 310 - second material 315 co-deposit may be configured as a coating that is a deep and capable of capturing significant amounts of gases and/or moisture in one, two, or three dimensions. In this manner, the first material 310 - second material 315 co-deposit may operate to prevent, among other things, the ingress of gases from the atmosphere through the barrier materials that form the VIP 305 and the vacuum cavity 320.
[0030] As shown in FIG. 3B, responsive to a force and/or reaction, the first material 310 may crack, deform, open, dissolve, break apart, crumble, or otherwise transform such that the second material 315 may be exposed to the environment of the cavity 320. For example, the first material 310 may transform responsive to various forces and/or reactions including, without limitation, a mechanical force, a chemical reaction, a pressure change, a magnetic force (for instance, a magnetic field), an electrical force, and/or a temperature change. In an embodiment, the forces and/or reactions may be internal to the VIP 305. In an embodiment, the forces and/or reactions may be external to the VIP 305. In an embodiment, the first material 310 and the second material 315 may have different temperature expansion coefficients so that heating and/or cooling of the cavity 320 environment may induce transformation of the first material and not the second material or vice versa.
[0031] In this manner, a desiccant and/or getter material (for example, in the form of the first material 310 - second material 315 formation) may be introduced within the VIP 305, but the reactive material may not be exposed or may have limited exposure until a force or reaction is generated sufficient to transform the first material 310 and expose all or part of the second material 315.
[0032] FIGS. 4 A and 4B depict an illustrative thermal insulation unit according to a fifth embodiment. As shown in FIG. 4A, a VIP 405 may include a plurality of nanospheres 425 including a first material 410 disposed within a cavity 420. In some embodiments, the cavity 420 may be under vacuum. The first material 410 may enclose a second material 415 arranged therein. According to some embodiments, the second material 415 may be wholly or partially sealed within the first material 410 such that the second material does not interface with the cavity 420 environment. In this manner, the first material 410 may be configured as a protective material or protective layer for the second material 415.
[0033] As shown in FIG. 4B, responsive to a force or reaction according to some embodiments, the first material 410 may crack, deform, open, dissolve, break apart, crumble, or otherwise transform such that the second material 415 may be exposed to the environment of the cavity 420. For example, the first material 410 may transform responsive to various forces or reactions such as a mechanical force (for example, shaking the VIP 405), a chemical reaction (for example, exposure of the nanospheres 425 to a chemical or gas), a temperature change (for example, a temperature change that causes thermal expansion of a layer, such as the first layer 410), and/or a change in pressure within the cavity 420. In an embodiment, the nanospheres 425 may be filled with a gas and/or solid desiccant or gettering material, such as calcium oxide (CaO), which, upon expansion, may transform (for example, crack) and expose the encapsulated second material 415 to the vacuum cavity 420 environment.
[0034] FIGS. 5A and 5B depict an illustrative thermal insulation panel according to a sixth. As shown in FIG. 5A, a VIP 505 may include a vacuum cavity 520 and a nanoparticle layer 530 having a plurality of nanoparticles 525 arranged therein. The outer surfaces of the nanoparticle layer 530 may be configured as a protective material or protective layer for the nanoparticles 525. A reaction element 535 may be configured to generate energy, a force, or the like that will react with or otherwise modify the nanoparticle layer 530. In an embodiment, the reaction element 535 may be configured to generate a magnetic field. In an embodiment, the nanoparticle layer 530 may be formed from a material that will react with the energy, force, or the like generated by the reaction element 535. For example, the nanoparticle layer 530 may be formed at least partially from a highly reactive metal, such as lithium, magnesium, aluminum, or the like, or combinations thereof. In an embodiment, the reaction element 535 may be external to the VIP 505 or the core 520. In another embodiment, the reaction element 535 may be internal to the VIP 505 or the core 520.
[0035] As shown in FIG. 5B, the reaction element 535 may generate a reaction 540, such as the generation of energy, a force, or the like that may penetrate at least a portion of the VIP 505 and crack, deform, open, dissolve, break apart, crumble, or otherwise transform at least a portion of the VIP to cause a breach in the nanoparticle layer 530. In an
embodiment, the reaction element 535 may be configured to generate a reaction 540 in the form of a magnetic field. Other non-limiting examples of reactions 540 may include electrical fields, magnetic fields, temperature changes, pressure changes, sound waves, or combinations thereof. The breach in the nanoparticle layer 530 may expose the nanoparticles 525 to the environment of the inside of the cavity 520. The nanoparticles 525 may include gas and/or solid desiccant or gettering material according to some embodiments. Although nanoparticles 525 were used in the depiction of a VIP in FIGS. 5 A and 5B, embodiments are not so limited, as the gas and/or solid desiccant or gettering material may be have any form capable of operating according to some embodiments described herein, such as a solid, liquid, gel, and/or paste material.
[0036] Various of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art each of which is also intended to be encompassed by the disclosed embodiments.

Claims

What is claimed is:
1. A thermal insulation panel comprising: at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel; and at least one reactive material configured to prevent a loss of the vacuum pressure within the core and arranged within at least one protective material configured to prevent exposure of the at least one reactive material to an environment within the core, wherein the at least one protective material is configured to be transformed to expose the at least one reactive material to the environment.
2. The thermal insulation panel of claim 1, wherein the at least one reactive material comprises at least one of a desiccant material and a getter material.
3. The thermal insulation panel of claim 1, wherein the at least one reactive material comprises at least one of aluminum, silver, indium, nickel, gold, aluminum oxide, aluminum nitride, aluminum oxynitride, silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, and indium tin oxide.
4. The thermal insulation panel of claim 1, wherein the at least one protective material allows the at least one reactive material to be handled in standard atmospheric conditions.
5. The thermal insulation panel of claim 1, wherein the at least one reactive material is arranged within the core.
6. The thermal insulation panel of claim 1, wherein the at least one layer comprises a plurality of layers and the at least one reactive material is arranged within at least one of the plurality of layers.
7. The thermal insulation panel of claim 1, wherein the vacuum pressure is about 10~3 bar to about 10~6 bar.
8. The thermal insulation panel of claim 1, wherein the thermal insulation panel is configured to maintain the vacuum pressure within the core for a duration of about 10 years.
9. The thermal insulation panel of claim 1, wherein the at least one reactive material comprises nanoparticles.
10. The thermal insulation panel of claim 9, wherein the nanoparticles comprise at least one of alumina, silica, mica, silver, indium, nickel, gold, aluminum suboxide, aluminum oxynitride, silicon suboxide, silicon carbide, silicon oxynitride, indium zinc oxide, indium tin oxide nanoparticles, and iron oxide.
11. The thermal insulation panel of claim 9, wherein the nanoparticles comprise at least one of calcium chloride, calcium sulfate, phosphorus pentoxide, and water-retaining polymers.
12. The thermal insulation layer of claim 1, wherein the at least one protective material is configured as a plurality of nanoparticles.
13. The thermal insulation layer of claim 1, wherein the at least one protective material is configured to be transformed by at least one of cracking, deforming, opening, dissolving, breaking apart, and crumbling.
14. The thermal insulation panel of claim 1, wherein the at least one protective material is configured to be transformed responsive to one of a force or a reaction.
15. The thermal insulation panel of claim 14, wherein the one of a force or a reaction comprises at least one of a mechanical force, a chemical reaction, a temperature change, a pressure change, an electrical force, a magnetic force, or combinations thereof.
16. The thermal insulation panel of claim 1 , wherein the thermal insulation panel is configured as a vacuum insulation panel.
17. The thermal insulation panel of claim 1, wherein the at least one reactive material and the at least one protective material are co-deposited within the thermal insulation panel.
18. The thermal insulation panel of claim 1, wherein the at least one reactive material is deposited within the thermal insulation panel through at least one of electrodeposition and vacuum deposition.
19. The thermal insulation panel of claim 1, wherein the at least one reactive material comprises at least one of a gas, a solid, a liquid, a gel, and a paste.
20. The thermal insulation panel of claim 1 , wherein the at least one reactive material is configured to prevent a loss of the vacuum pressure via reacting with moisture or gas within the vacuum insulation panel.
21. A thermal insulation panel comprising: at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel; and at least one reactive material arranged within the vacuum insulation panel and configured to prevent a loss of the vacuum pressure therein, the at least one reactive material being configured to be deposited within the vacuum insulation panel in a non-reactive environment and to be reactive under an environment within the core.
22. The vacuum insulation panel of claim 21, wherein the at least one reactive material is deposited within the vacuum insulation panel at a first pressure that is greater than the vacuum pressure and is configured to be reactive at the vacuum pressure.
23. The vacuum insulation panel of claim 21, wherein the at least one reactive material is arranged within at least one protective material.
24. The thermal insulation panel of claim 21, wherein the at least one reactive material comprises at least one of a desiccant material and a getter material.
25. The thermal insulation panel of claim 21, wherein the at least one reactive material comprises at least one of aluminum, silver, indium, nickel, gold, aluminum oxide, aluminum nitride, aluminum oxynitride, silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, and indium tin oxide.
26. The thermal insulation panel of claim 21, wherein the at least one reactive material is arranged within the core.
27. The thermal insulation panel of claim 21, wherein the at least one layer comprises a plurality of layers and the at least one reactive material is arranged within at least one of the plurality of layers.
28. The thermal insulation panel of claim 21, wherein the vacuum pressure is about 10" bar to about 10"6 bar.
29. The thermal insulation panel of claim 21, wherein the thermal insulation panel is configured to maintain the vacuum pressure within the core for a duration of about 10 years.
30. The thermal insulation panel of claim 21, wherein the at least one reactive material comprises nanoparticles.
31. The thermal insulation panel of claim 30, wherein the nanoparticles comprise at least one of alumina, silica, mica, silver, indium, nickel, gold, aluminum suboxide, aluminum oxynitride, silicon suboxide, silicon carbide, silicon oxynitride, indium zinc oxide, indium tin oxide nanoparticles, and iron oxide.
32. The thermal insulation panel of claim 30, wherein the nanoparticles comprise at least one of calcium chloride, calcium sulfate, phosphorus pentoxide, and water-retaining polymers.
33. The thermal insulation panel of claim 21, wherein the thermal insulation panel is configured as a vacuum insulation panel.
34. The thermal insulation panel of claim 21, wherein the at least one reactive material is deposited within the thermal insulation panel through at least one of electrodeposition and vacuum deposition.
35. The thermal insulation panel of claim 21, wherein the at least one reactive material is configured to prevent a loss of the vacuum pressure via reacting with moisture or gas within the vacuum insulation panel.
36. A method of forming a thermal insulation panel, the method comprising: providing at least one layer configured to form a core under a vacuum pressure within the thermal insulation panel; arranging at least one reactive material within the thermal insulation panel, the at least one reactive material being configured to prevent a loss of the vacuum pressure within the core; and providing at least one protective material configured to prevent exposure of the at least one reactive material to an environment within the core, wherein the at least one protective material is configured to be transformed to expose the at least one reactive material to the environment.
37. The method of claim 36, wherein the at least one reactive material comprises at least one of a desiccant material and a getter material.
38. The method of claim 36, wherein the at least one reactive material comprises at least one of aluminum, silver, indium, nickel, gold, aluminum oxide, aluminum nitride, aluminum oxynitride, silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, and indium tin oxide.
39. The method of claim 36, wherein the at least one reactive material is arranged within the core.
40. The method of claim 36, wherein the at least one layer comprises a plurality of layers and the at least one reactive material is arranged within at least one of the plurality of layers.
41. The method of claim 36, wherein the vacuum pressure is about 10~3 bar to about 10~6 bar.
42. The method of claim 36, wherein the at least one reactive material comprises nanoparticles.
43. The method of claim 42, wherein the nanoparticles comprise at least one of alumina, silica, mica, silver, indium, nickel, gold, aluminum suboxide, aluminum oxynitride, silicon suboxide, silicon carbide, silicon oxynitride, indium zinc oxide, indium tin oxide
nanoparticles, and iron oxide.
44. The method of claim 42, wherein the nanoparticles comprise at least one of calcium chloride, calcium sulfate, phosphorus pentoxide, and water-retaining polymers.
45. The method of claim 36, wherein the at least one protective material is configured as a plurality of nanoparticles.
46. The method of claim 36, wherein the at least one protective material is configured to be transformed by at least one of cracking, deforming, opening, dissolving, breaking apart, and crumbling.
47. The method of claim 36, wherein the at least one protective material is configured to be transformed responsive to one of a force or a reaction.
48. The method of claim 47, wherein the one of a force or a reaction comprises at least one of a mechanical force, a chemical reaction, a temperature change, a pressure change, an electrical force, a magnetic force, or combinations thereof.
49. The method of claim 36, wherein the thermal insulation panel is configured as a vacuum insulation panel.
50. The method of claim 36, wherein the at least one reactive material and the at least one protective material are co-deposited within the thermal insulation panel.
51. The method of claim 36, wherein the at least one reactive material is deposited within the thermal insulation panel through at least one of electrodeposition and vacuum deposition.
52. The method of claim 36, wherein the at least one reactive material comprises at least one of a gas, a solid, a liquid, a gel, and a paste.
PCT/US2014/032389 2013-03-29 2014-03-31 Highly reactive materials for use as desiccants and getters in an enclosed environment and methods for using same WO2014160999A1 (en)

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