WO2002081833A1 - Shapeable vacuum insulation panel containing a single core component - Google Patents

Shapeable vacuum insulation panel containing a single core component Download PDF

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Publication number
WO2002081833A1
WO2002081833A1 PCT/US2002/008608 US0208608W WO02081833A1 WO 2002081833 A1 WO2002081833 A1 WO 2002081833A1 US 0208608 W US0208608 W US 0208608W WO 02081833 A1 WO02081833 A1 WO 02081833A1
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WO
WIPO (PCT)
Prior art keywords
core component
insulation panel
vacuum insulation
vip
single core
Prior art date
Application number
PCT/US2002/008608
Other languages
French (fr)
Inventor
Robert G. Henson
Bruce A. Malone
Original Assignee
Dow Global Technologies Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Publication of WO2002081833A1 publication Critical patent/WO2002081833A1/en

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Classifications

    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04BGENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/78Heat insulating elements
    • E04B1/80Heat insulating elements slab-shaped
    • E04B1/803Heat insulating elements slab-shaped with vacuum spaces included in the slab
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2201/00Insulation
    • F25D2201/10Insulation with respect to heat
    • F25D2201/14Insulation with respect to heat using subatmospheric pressure
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00Adapting or protecting infrastructure or their operation
    • Y02A30/24Structural elements or technologies for improving thermal insulation
    • Y02A30/242Slab shaped vacuum insulation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B80/00Architectural or constructional elements improving the thermal performance of buildings
    • Y02B80/10Insulation, e.g. vacuum or aerogel insulation

Definitions

  • the present invention relates to shapeable vacuum insulation panels, each containing a single core component, and insulating containers containing at least one such shapeable panel .
  • Vacuum insulation panels comprise a gas- impermeable barrier enclosing an evacuated airtight volume.
  • the airtight volume typically contains at least one core component within the airtight volume.
  • Evacuating the airtight volume reduces the thermal conductivity through the volume, making VIPs particularly effective thermal insulating materials .
  • Constructing insulating containers using VIPs is challenging and time consuming.
  • VIPs are often planar while containers are not. Insulating rectilinear containers having two or more surfaces typically requires piecing together two or more VIPs, one for each surface.
  • Insulating cylindrical containers with VIPs requires either customized VIPs or at least one flexible vacuum insulation panel that can conform to the cylindrical configuration.
  • Custom VIPs are complex to manufacture and limited in their use to the custom application. Flexible VIPs are versatile, but flexible VIP technology is limited. United States Patents (USP)
  • USP 4,726,974 discloses a VIP comprising a shaped and compressed fiberglass substrate in an enclosure that is under vacuum.
  • the fiberglass substrate is an article having a specific shape for conforming to a specific container, for example a curved article for insulating a cylindrical container.
  • Fiberglass is challenging to implement in a VIP. Binders are necessary to inhibit individual fiberglass fibers from piercing the enclosure or protruding into or through the enclosure while manufacturing the VIP.
  • USP 5,107,649 and USP 5,175,975 both disclose a VIP comprising two hard but bendable metal sheets welded together around the edges and spaced apart with glass or ceramic spacers .
  • the bendable VIPs contain multiple discrete spacers.
  • USP 5,273,801 discloses a VIP comprising a thermoformed vacuum insulation container having a receptacle area for icroporous insulation material .
  • the container may have multiple receptacle areas and may fold at least 90° along a line between adjacent receptacle areas. Each receptacle area receives microporous insulation material in loose form or in a pre- filled package.
  • USP 6,010,762 discloses an insulation panel comprising an air- impermeable container having disposed therein a gas and an adsorbent material. The combination of a flexible container and a flexible adsorbent material ensures that the insulation panel will be flexible at ambient temperature. The panel loses flexibility, however, upon evacuation.
  • PCT 96/32605 discloses a non-planar evacuated insulation panel containing an insulating filler material and a method for preparing such an insulation panel by providing grooves in the filler material prior to forming the evacuated insulation panel. The panel can bend along the groove in the filler material.
  • the flexible VIPs of the cited USPs and PCT publication are less than optimal, suffering from one or more of the following handicaps: fiberglass in the cores that can breach a gas -impermeable barrier, multiple discrete core components requiring specific placement within the VIP, limited flexibility, and a requirement that the VIP contain an insulating material containing a groove.
  • a flexible VIP that can conform to a variety of container shapes after formation is desirable, particularly if its core is not made of fiberglass.
  • Such a shapeable VIP containing a single core component rather than discrete core components is even more desirable.
  • the present invention is a vacuum insulation panel comprising a single core component enclosed within a gas-impermeable barrier; wherein said vacuum insulation panel can bend or fold at least 90 degrees ( s ) relative to an initial configuration without breaking said single core component into two or more discrete pieces when said single core component is free of grooves; and wherein said single core component contains less than 50 weight - percent (wt%) of fiberglass fibers, based on single core component weight.
  • the single core component contains at least one core component section comprising a polymeric foam that is 90 percent or more open-celled according to American Society for Testing and Materials (ASTM) method D2856-A.
  • the present invention is an insulated container comprising at last one vacuum insulation panel of the first aspect.
  • the present invention is a method of insulating a container shell comprising: (a) bending the vacuum insulation panel of the first aspect into a desired configuration; then (b) disposing the vacuum insulation panel into or around said container shell.
  • the present invention advances the art with a vacuum insulation panel that is shapeable after formation and that contains a single core component.
  • FIG. la shows a cut-away view of a VIP of the present invention containing a single core component comprising two indirectly interconnected core component sections in a first configuration.
  • FIG lb shows another cut-away view of the VIP of FIG la after bending 90 9 into a second configuration.
  • FIG 2a shows an indirectly interconnected single core component comprising six core component sections.
  • FIG 2b shows the single core component of FIG 2a after bending into a container configuration.
  • FIG 3a shows a core component section with beveled edges .
  • FIG 3b shows a core component containing five interconnecting core component sections similar to that in FIG 3a.
  • FIG 3c shows the core component of FIG 3b bent into a wall configuration.
  • FIG 4 shows an insulated container with a shapeable VIP of the present invention within a container shell.
  • Shapeable VIPs of the present invention contain a single core component hermetically sealed within a gas -impermeable barrier.
  • the single core component resides in a vacuum within the gas impermeable barrier material.
  • the shapeable VIP is capable of bending 90 s or more, preferably 180 s or more without breaking the single core component into two or more discrete pieces.
  • FIG la shows VIP 5 in an initial configuration
  • FIG lb shows VIP 5 bent 90 s relative to the initial configuration in FIG la.
  • VIPs of the present invention are shapeable even when the core component of the VIP is free of grooves. Grooves extend from one end to another end in a chosen direction.
  • WO 96/32605 describes VIPs with core components. A method for preparing grooves in a core component and a definition of a "groove" is on page 10, lines 7-17 of WO 96/32605. While grooves are not necessary, core components of the present invention can contain grooves or be free of grooves.
  • the vacuum within the gas-impermeable barrier is preferably 10 torr (1,330 pascal (Pa)) or less, more preferably 1 torr (133 Pa) or less, most preferably 0.1 torr (13.3 Pa) or less. Lower pressures are preferable to achieve lower thermal conductivity through the VIP. A VIP that has a pressure greater than 10 torr (1,330 Pa) tends to have an undesirably high thermal conductivity.
  • a gas -impermeable barrier in the present invention preferably has a gas permeation rate of 1.5 cubic centimeter per day per square meter (cc/day/m 2 ) or less, more preferably 0.15 cc/day/m 2 or less, most preferably 0.015 cc/day/m 2 or less. Measure gas permeation rate according to ASTM method D- 3985.
  • a VIP having a gas -impermeable barrier having a gas permeation rate of greater than 1.5 cc/day/m 2 tends to lose vacuum and insulating properties more quickly than is desirable.
  • Suitable materials for use as gas -impermeable barriers include metal sheet, metal foil, polymeric film, and combinations thereof. Some materials, such as metal sheet, tend to be rigid and preferably contain corrugation to enhance flexibility, allowing a VIP to be shapeable. Corrugation may be uniform along the rigid material or only occur in sections of the material where bending or folding occurs.
  • USP 5,175,975 (column 9 lines 3-16 and lines 29-36 and FIGs 16, 17, and 19) describes examples of corrugated metal sheets as VIP gas barrier materials.
  • USP 5,175,975 describes planar VIPs in which corrugations are in a direction parallel to an X-axis when the VIP is in a plane containing X and Y axes. The corrugations allow the VIP to move in the +Z and -Z axis while remaining rigid in the X- axis .
  • the gas - impermeable barrier is a polymeric film.
  • Polymeric films offer a desirable combination of flexibility and durability. Suitable polymeric films can contain any common polymer or combination of polymers provided the films have a gas permeation rate of 1.5 cc/day/m 2 or less, according to ASTM method D-3985.
  • Polymeric films may contain, for example, polyesters, copolyesters, tetrafluoroethylene, polyi ide, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol (PVOH) , polystyrene (PS) polymers and copolymers, polyethylene (PE) polymers and copolymers, and polypropylene (PP) polymers and copolymers.
  • Polymeric films may include a coating disposed on at least one surface to reduce gas permeability of the film.
  • Suitable coatings include those selected from the group consisting of inorganic materials, such as a metal, ceramic, or glass, as well as organic materials such as polyvinylidene chloride (PVDC) .
  • Suitable metals include gold, aluminum and silver.
  • Suitable means for coating a film include any method known in the art such as plasma coating, sputter coating, spray coating, and electromagnetic bonding.
  • the gas-impermeable barrier is a multilayer film, desirably having an exposed layer that is heat sealable.
  • One particularly preferred multilayer film comprises an outer layer, a middle layer and an inner layer.
  • the outer layer desirably comprises a scratch resistant material such as a polyester or copolyester.
  • the middle layer desirably consists of a barrier material such as aluminum, PVDC, PVOH, or a polymeric film having a coating of aluminum.
  • the inner layer desirably contains a heat sealable material such as PE, ethylene/acrylic acid copolymer, PE- vinylacetate copolymer, high density PE, and PP blends.
  • Lamination, extrusion coating, and coextrusion are all suitable means for preparing gas -impermeable multilayer films.
  • Commercially available multilayer films suitable as barrier materials for the present invention are also available and include films NA-1, NA-2, NA-3, and NA-4 from Toyo Aluminum .K.; aluminum foil containing films SA-1, SA- 2, SA-3, SA-4, SA-5, and SA-6, also from Toyo Aluminum K.K.; and MYLARTM (trademark of E. I. du Pont de Nemours and Company) 200 RSBL, MYLAR 250 RSBL 300, and MYLAR 350 RSBL 300 polyester films.
  • a skilled artisan can determine any of a number of ways to hermetically seal a suitable barrier material. For example, one can weld metal sheets together and heat-seal or melt polymeric films together. If necessary, one may use an additional adhesive or glue to hermetically seal together sheets or plies of the barrier material.
  • the shapeable VIP contains a singe core component that may or may not be shapeable apart from the VIP.
  • some PS foams may not be shapeable until they are under vacuum within a VIP and supported by a gas-impermeable barrier.
  • single core component refers to a core component comprising a single structure.
  • a single core component enables fast and simple manufacture of a VIP.
  • manufacturing a VIP with a single core component can involve inserting the core component into a gas- impermeable barrier receptacle (such as a bag) ; evacuating the receptacle; and hermetically sealing the receptacle.
  • manufacturing VIPs that contain two or more discrete core components requires specific placement of each core component.
  • Discrete core components may disadvantageously move or re-orient relative to one another during manufacture.
  • a VIP of the present invention requires placement of only a single core component and minimizes the risk of discrete core components moving during manufacture.
  • a single core component may comprise a single core component section or two or more interconnected core component sections.
  • a "core component section” is a portion of a single core component that extends from one face to an opposing face of the single core component.
  • a shapeable VIP of the present invention that has a core component consisting of a single core component section is characterizable by a "D/T" ratio.
  • T is the thickness of the VIP and "D” is the smallest diameter of a mandrel about which the VIP will bend 90 2 without breaking the core component into discrete pieces. Measure “T” and “D” using the same units. Dividing T into D achieves the D/T ratio, a unitless value.
  • the D/T ratio for a shapeable VIP having a core component comprising a single core component section is greater than zero, generally one or more.
  • the D/T ratio is preferably 48 or less, more preferably 24 or less, still more preferably 12 or less, most preferably 8 or less.
  • VIPs having a D/T ratio of greater than 48 lack sufficient flexibility for most uses requiring a flexible VIP.
  • a single core component may contain two or more interconnected core component sections .
  • Interconnecting core component sections may be the same or different.
  • interconnecting core component sections may have different compositions, densities, structures, and sizes.
  • Core component sections may be directly interconnected, indirectly interconnected, or a combination of both.
  • Directly interconnected core component sections attach directly to each other without the use of a connector.
  • melt-welding polymeric foam boards together directly interconnects the boards.
  • VIPs that have a single core component consisting of only directly interconnected core component sections are preferably characterizable by a D/T ratio and the D/T ratio values previously specified.
  • Indirectly interconnected core component sections utilize at least one connector to join the core component sections together.
  • Two indirectly interconnected core component sections may or may not be touching each other and include a connector with one portion of the' connector attached to one core component section and another portion of the connector attached to the other core component section.
  • Connectors may be flexible or rigid. Flexible connectors are preferable because they tend to contribute to a VIP's flexibility. A connector that can bend at least 90 s without fracturing is a "flexible" connector. A connector that fractures upon bending 90 s is a “rigid” connector. Flexible connectors may become rigid connectors under certain conditions, and vice versa. For example, a polymeric film may be a flexible connector at or near its glass transition temperature (Tg) yet be rigid connector 100 S C below its Tg. Therefore, whether a connector is a rigid connector or a flexible connector is dependent upon what the connector is made of and at what temperature it is at. Herein, connectors are considered to be at 23 S C unless otherwise indicated.
  • Tg glass transition temperature
  • Suitable connectors include those selected from the group consisting of polymeric films and foams, adhesive films, corrugated metal, adhesive tape, paper, metal foil, string, and wire. Flexible glues and adhesives, such as silicone rubber are also suitable flexible connectors. Polymeric films and adhesive tapes, such as SCOTCHTM brand adhesive tape (SCOTCH is a trademark of 3M) are desirable connectors. Polymeric films comprising at least one polymer selected from the group consisting of polyesters, PE, PS, and copolymers thereof are more desirable. Polymeric films may comprise more than one layer to achieve desired properties. For example, a polymeric film having opposing surfaces may include an adhesive layer on one surface and a durable film layer on an opposing surface.
  • a shapeable VIP containing only core component sections directly interconnected by rigid connectors typically bend within at least one core component section.
  • the VIP preferably has a D/T ratio in the previously specified ranges.
  • the VIP is only shapeable under conditions that transform any rigid connector (or connectors) between any two core component sections into a flexible connector (or connectors) , thereby allowing the VIP to bend along the connector (s) .
  • Core component sections beneficially comprise highly open- celled foam.
  • "Highly open- celled" foams are 90% or more open-celled, preferably 95% or more open-celled, more preferably 98% or more open-celled, most preferably 99% or more open-celled according to ASTM method D2856-A. Foams that are less than 90% open-celled are difficult to evacuate when manufacturing a VIP.
  • Highly open-celled foams may be inorganic, such as ceramic or glass, or organic, such as cellulose or organic polymer-based. More preferably, core component sections are highly open- celled polymeric foam comprising at least one polymer.
  • Preferred polymers include those selected from the group consisting of alkenyl aromatic homo- and copolymers including PS homo- and copolymers, PP homo- and copolymers, PE homo- and copolymers, polycarbonate homo- and copolymers, polyurethane (PU) polymers, polyisocyanurate polymers, and blends ⁇ thereof .
  • alkenyl aromatic homo- and copolymers including PS homo- and copolymers, PP homo- and copolymers, PE homo- and copolymers, polycarbonate homo- and copolymers, polyurethane (PU) polymers, polyisocyanurate polymers, and blends ⁇ thereof .
  • Suitable polymer blends include blends of an alkenyl aromatic polymer and an ethylene copolymer such as an ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene- methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethylacrylate copolymer, ionomer, or an ethylene copolymer made with either constrained geometry or metallocene catalyst technology.
  • a core component section comprises a highly open- celled PS foam.
  • a core component section may comprise particulate or fibrous materials, provided the materials interconnect or are within a container.
  • NANOGELTM advanced thermal insulation is an example of particulate material inside of a bag that is suitable as a core component section within the scope of this invention.
  • Suitable particulate materials include open- celled porous materials such as silica gel, titania gel, alumina gel; and polymeric gels such as resocinol- formaldehyde gels, and melamine formaldehyde gels.
  • Fibrous materials include fiberglass, glasswool, and mineral wool.
  • a single core component of the present invention contains less than 50 wt%, preferably less than 25 wt%, more preferably less than 10 wt% of fiberglass fibers relative to core component weight.
  • Core component sections are preferably essentially free of fibrous material such as fiberglass, glass wool, and mineral wool.
  • a core component section is essentially free of fibrous material when it contains 10 wt% or less, preferably 5 wt% or less, more preferably 1 wt% or less of fibrous material by weight of the core component section.
  • a core component that is essentially free of fibrous materials, particularly fiberglass, minimizes the chance that fibers may puncture the barrier material or breach the hermetic seal by traversing the seal during manufacture.
  • Particulate or fibrous materials may interconnect mechanically, adhesively, or chemically.
  • inter- weaving fibers mechanically binds them together.
  • Glue or non-reactive binders can adhesively bind particles or fibers together.
  • Reactive binders such as those that chemically crosslink fibrous or particulate materials together, can chemically bind fibers and particles.
  • Interconnected non- porous particles and fibers preferably have void spaces between particles or fibers to reduce the VIP density and facilitate evacuation of the VIP.
  • FIGs la, lb, 2a, 2b, 3b, and 3c There are many suitable configurations for interconnecting core component sections with at least one connector, some of which are evident in FIGs la, lb, 2a, 2b, 3b, and 3c. Like numbers in different figures refer to the same feature.
  • FIG la shows a cut-away view of VIP 5 in an initial configuration.
  • VIP 5 contains core component 10 within gas- impermeable barrier 8.
  • Core component 10 contains two indirectly interconnected core component sections 12 and 14.
  • Core component section 12 has edge 17 (shown only in FIG la) that is proximate to core component section 14.
  • Flexible connector 16 adheres to a surface portion of both core component sections 12 and 14, thereby interconnecting them.
  • Core component section 14 has a thickness T (shown only in FIG la) , while core component section 12 has thickness T' (shown only in FIG la) . Thickness T and thickness T' may be the same or different. Core component sections 12 and 14 are spaced a distance S (shown only in FIG la) apart. The magnitude of distance S is preferably the same as that of thickness T.
  • FIG lb shows VIP 5 in a configuration bent 90 s by way of flexible connector 16, relative to the initial configuration shown in FIG la.
  • edge 17 of core component 12 contacts face 18 (not shown) of core component 14, forming a fully insulated right angle corner, as shown in FIG lb.
  • Variations in thickness T and spacing S can allow VIP 5 to bend to angles other than 90 s . For instance, increasing spacing S while maintaining thickness T, or decreasing thickness T while maintaining spacing S can allow VIP 5 to bend more than 90 s .
  • FIG 2a shows single core component 20 containing core component connectors 30 and 32 simultaneously interconnecting core component sections 22, 24, 26, and 28.
  • Connectors 30 and 32 can be, for example, adhesive tape extending across and attaching to surface portions of core component sections 22, 24, 26, and 28.
  • Core component 20 further includes connectors 38 and 40 interconnecting core component sections 34 and 36, respectively, to core component section 24.
  • FIG 2b shows core component 20 in a configuration wherein core component sections 22, 24, 26, and 28 (not shown) form the sides of a box while core component sections 34 and 36 form a top and bottom for the box.
  • a VIP containing single core component 20 can form an insulating box when the core component is in the configuration of FIG 2b.
  • FIG 3a shows core component section 50 that has opposing faces 60 and 62 (not shown) , and opposing edges 64 and 66
  • opposing edges can have different bevel angles, although bevel angle 68 is preferably the same as bevel angle 69 in core component 50.
  • face 60 identify face 60 as an inside face and face 62 as an outside face. Outside face 62 has a larger surface area than inside face 60.
  • FIG 3b shows core component 80 comprising core component sections 51, 52, 53, 54, and 55, each similar to core component section 50 in that each of such sections have two bevel angles, each of which is 36 s .
  • Core component sections 51, 52, 53, 54, and 55 each have opposing bevel edges (shown only in FIG 3b) 90 and 91, 92 and 93, 94 and 95, 96 and 97, and 98 and 99, respectively.
  • the core component sections are touching along lines 82, 83, 84, and 85, thereby creating continuous outside face 86 along the core component.
  • Connectors 70 and 72 attach to a portion of outside face 86 of core component 80, interconnecting core component sections 51, 52, 53, 54, and 55.
  • FIG 3c shows core component 80 bent such that beveled edges 90 and 99 (shown in FIG 3b) meet. Adjacent beveled edges 91 and 92, 93 and 94, 95 and 96, and 97 and 98 (shown only in FIG 3b) also meet.
  • core component 80 forms a wall for a five- sided container having a continuous outside face 86 and a continuous inside face 87 (shown only in FIG 3c) .
  • a VIP containing core component 80 can form the walls of a five- sided insulated container by folding the core component, and thereby the VIP, into the configuration shown in FIG 3c.
  • VIP 80 can also be provided with a top, a bottom, or both in a manner similar to that illustrated in FIGs 2a and 2b.
  • VIPs having core component sections similar to core component section 50 are useful for forming containers having three or more sides wherein edges of adjacent sides contact each other.
  • a VIP has a core component that includes one core component section for each side of the container and each core component section has bevel angle equal to 180° divided by the number of sections in the core component, or 180 2 divided by the number of sides to the container.
  • Shapeable VIPs of the present invention preferably have a thermal conductivity, according to ASTM method C- 518 -98, of 0.083 British Thermal Unit- inch per hour- square foot-degree Fahrenheit (BTU*in/hr*ft 2 *°F) (12 milliwatt per meter-Kelvin (mW/m*K) ) or less, more preferably 0.056 BTU*in/hr*ft 2 *°F (8.1 mW/m*K) or less, and still more preferably 0.042 BTU*in/hr*ft 2 *°F (6.0 mW/m*K) or less.
  • BTU*in/hr*ft 2 *°F 12 milliwatt per meter-Kelvin
  • Shapeable VIPs may further comprise additives, such as water-absorbent materials or getters within the VIP.
  • Water- absorbent materials are useful to capture any moisture that is trapped within a VIP.
  • getters are useful to capture gases such as oxygen, nitrogen, carbon dioxide, helium and hydrogen that are trapped within a VIP. Both water absorbers and getters help maintain a vacuum within a VIP.
  • Suitable water-absorbent materials include anhydrous calcium oxide, anhydrous barium oxide, anhydrous silica gel, anhydrous silica powder, and anhydrous molecular sieves.
  • Suitable getters include alloys of barium, lithium, and cobalt oxide.
  • COMBGETTERTM One commercially available getter is available under the trademark COMBGETTERTM from SAES getters.
  • Additives may or may not be bound to one or both of a single core component or a gas -impermeable barrier of the present invention.
  • the present invention also relates to an insulating container containing at least one shapeable VIP having a single core component.
  • a shapeable VIP may form the container itself, or act as an insulating component within or around a container shell such as a box or a tube.
  • a container comprises a wall structure having opposing top and bottom ends. The wall structure encloses a volume, which is the inside the container. The wall structure can be any conceivable shape, for example, cylindrical or rectilinear.
  • a container typically includes a base attached to the bottom of the container and a lid for covering the top of the container. Preferably, the base and lid also contain a VIP. More preferably, a container includes a gasket between its lid and the wall structure. A gasket may also exist between a base and the wall structure.
  • FIG 2b shows a core component in the form of a container.
  • a VIP containing the core component of FIG 2a may assume the configuration of FIG 2b to create an insulating container of the present invention.
  • FIG 3c shows a core component in the form of a pentagonal wall structure.
  • a VIP containing the core component of FIG 3b can assume the configuration in FIG 3c, thereby creating an insulated wall structure for a container.
  • Two or more shapeable VIPs may work cooperatively to form an insulating container of the present invention. For example, two VIPs in an orthogonal "C" orientation can combine to form a six-sided insulating container.
  • a VIP containing a single core component section may also form a wall structure for a container.
  • FIG 4 shows insulating container 100 consisting of container shell 102 and VIP 104.
  • VIP 104 contains a single core component section (not shown), opposing ends 106 and 108, and opposing faces 110 and 112. Ends 106 and 108 meet and VIP 104 forms a continuous VIP wall structure. Taping ends 106 and 108 together helps maintain the continuous wall structure. Alternatively, end 106 or end 108 may meet face 110 to form a similar VIP wall structure, not shown.
  • Other shapes of container shells, such as cylindrical or polyhedral, would work equally well as container shell 102.
  • VIP 104 may assume a cylindrical shape with a circular cross section as in FIG 4, or it may assume a teardrop or oval cross section.
  • a protective film or other material may cover one or more surfaces of the VIPs to enhance durability.
  • a protective film is particularly useful for protecting VIPs in the absence of any container other than the VIPs.
  • Example (Ex) 1. Shapeable VIP Containing a Single Core
  • a bag from two sheets of polymeric film (such as MYLAR 250 RSBL 300 film) that are each 37 inches (in.) (94 centimeter (cm)) long and 13.5 in. (34 cm) wide. Overlay one sheet on the other sheet and heat seal three edges together using a heat seal bar at 120- 150 S C to form a bag with an open end. Cut a single core component from a polymeric foam that is greater than 95% open celled (for example, INSTILLTM-UC foam, INSTILL is a trademark of The Dow Chemical Company) . The single core component is 10 in. (25 cm) wide, 35 in. (89 cm) long, and 1 in. (2.5 cm) thick. Insert the foam core component into the bag.
  • polymeric film such as MYLAR 250 RSBL 300 film
  • Ex 1 illustrates a shapeable VIP having a single core component comprising a single core component section that is free of grooves and the use of such a VIP in forming an insulating container.
  • a Shapeable VIP Having an Indirectly Interconnected Core Component Create a core component consisting of four indirectly interconnected core component sections .
  • Each core component section is a polymeric foam similar to that of Ex 1. Cut four pieces of foam into rectangular core component sections that are 1 in. (2.5 cm) thick and have opposing 10 in. (25 cm) long edges and opposing 11 in. (28 cm) wide ends.
  • each core component section Position the four core component sections in a row such that the 11 in. (28 cm) wide ends of each core component section are collinear with the 11 in. (28 cm) wide ends of each other core component section. Adjacent 10 in. (25 cm) long edges are parallel and spaced 1 in. (2.5 cm) away from any adjacent core component section edge. Interconnect the core component sections by adhering two strips of 0.5 in. (1.3 cm) wide adhesive tape (such as SCOTCH brand adhesive tape) across portions of the core component sections, similar to the way connectors 30 and 32 interconnect core component sections 22, 24, 26, and 28 in FIG 2a.
  • SCOTCH brand adhesive tape such as SCOTCH brand adhesive tape
  • Prepare an insulating container by inserting the wall structure into a container shell.
  • apply tape as necessary to secure the wall structure from unfolding and add a lid and base to create an insulated container.
  • the lid and base may be VIPs.
  • Ex 2 illustrates a VIP having an indirectly interconnected single core component that is free of grooves and the use of such a VIP to form an insulating container.

Abstract

A shapeable vacuum insulation panel containing a single core component is particularly useful for preparing thermally insulating containers.

Description

SHAPEABLE VACUUM INSULATION PANEL CONTAINING A SINGLE CORE
COMPONENT The present invention relates to shapeable vacuum insulation panels, each containing a single core component, and insulating containers containing at least one such shapeable panel .
Vacuum insulation panels (VIPs) comprise a gas- impermeable barrier enclosing an evacuated airtight volume. Typically, the airtight volume. contains at least one core component within the airtight volume. Evacuating the airtight volume reduces the thermal conductivity through the volume, making VIPs particularly effective thermal insulating materials . Constructing insulating containers using VIPs is challenging and time consuming. VIPs are often planar while containers are not. Insulating rectilinear containers having two or more surfaces typically requires piecing together two or more VIPs, one for each surface. Insulating cylindrical containers with VIPs requires either customized VIPs or at least one flexible vacuum insulation panel that can conform to the cylindrical configuration. Custom VIPs are complex to manufacture and limited in their use to the custom application. Flexible VIPs are versatile, but flexible VIP technology is limited. United States Patents (USP)
4,726,974; 5,107,649; 5,175,975; 5,273,801; and 6,010,762 as well as Patent Cooperation Treaty (PCT) publication WO 96/32605 disclose examples of flexible VIPs.
USP 4,726,974 discloses a VIP comprising a shaped and compressed fiberglass substrate in an enclosure that is under vacuum. The fiberglass substrate is an article having a specific shape for conforming to a specific container, for example a curved article for insulating a cylindrical container. Fiberglass, however, is challenging to implement in a VIP. Binders are necessary to inhibit individual fiberglass fibers from piercing the enclosure or protruding into or through the enclosure while manufacturing the VIP.
USP 5,107,649 and USP 5,175,975 both disclose a VIP comprising two hard but bendable metal sheets welded together around the edges and spaced apart with glass or ceramic spacers . The bendable VIPs contain multiple discrete spacers.
USP 5,273,801 discloses a VIP comprising a thermoformed vacuum insulation container having a receptacle area for icroporous insulation material . The container may have multiple receptacle areas and may fold at least 90° along a line between adjacent receptacle areas. Each receptacle area receives microporous insulation material in loose form or in a pre- filled package. USP 6,010,762 discloses an insulation panel comprising an air- impermeable container having disposed therein a gas and an adsorbent material. The combination of a flexible container and a flexible adsorbent material ensures that the insulation panel will be flexible at ambient temperature. The panel loses flexibility, however, upon evacuation.
PCT 96/32605 discloses a non-planar evacuated insulation panel containing an insulating filler material and a method for preparing such an insulation panel by providing grooves in the filler material prior to forming the evacuated insulation panel. The panel can bend along the groove in the filler material.
The flexible VIPs of the cited USPs and PCT publication are less than optimal, suffering from one or more of the following handicaps: fiberglass in the cores that can breach a gas -impermeable barrier, multiple discrete core components requiring specific placement within the VIP, limited flexibility, and a requirement that the VIP contain an insulating material containing a groove. A flexible VIP that can conform to a variety of container shapes after formation is desirable, particularly if its core is not made of fiberglass. Such a shapeable VIP containing a single core component rather than discrete core components is even more desirable.
In a first aspect, the present invention is a vacuum insulation panel comprising a single core component enclosed within a gas-impermeable barrier; wherein said vacuum insulation panel can bend or fold at least 90 degrees (s) relative to an initial configuration without breaking said single core component into two or more discrete pieces when said single core component is free of grooves; and wherein said single core component contains less than 50 weight - percent (wt%) of fiberglass fibers, based on single core component weight. In one preferred variation of the first aspect, the single core component contains at least one core component section comprising a polymeric foam that is 90 percent or more open-celled according to American Society for Testing and Materials (ASTM) method D2856-A.
In a second aspect, the present invention is an insulated container comprising at last one vacuum insulation panel of the first aspect.
In a third aspect, the present invention is a method of insulating a container shell comprising: (a) bending the vacuum insulation panel of the first aspect into a desired configuration; then (b) disposing the vacuum insulation panel into or around said container shell.
The present invention advances the art with a vacuum insulation panel that is shapeable after formation and that contains a single core component.
BRIEF DESCRIPTION OF DRAWINGS , Figure (FIG) la shows a cut-away view of a VIP of the present invention containing a single core component comprising two indirectly interconnected core component sections in a first configuration.
FIG lb shows another cut-away view of the VIP of FIG la after bending 909 into a second configuration. FIG 2a shows an indirectly interconnected single core component comprising six core component sections.
FIG 2b shows the single core component of FIG 2a after bending into a container configuration. FIG 3a shows a core component section with beveled edges .
FIG 3b shows a core component containing five interconnecting core component sections similar to that in FIG 3a. FIG 3c shows the core component of FIG 3b bent into a wall configuration.
FIG 4 shows an insulated container with a shapeable VIP of the present invention within a container shell.
Herein, -"shapeable" describes an object that is capable of bending 90s or more without breaking. Herein, "bending" and "folding" are interchangeable. An object bends a certain number of degrees by displacing one of two opposing ends of the object that certain number of degrees relative to the other end without breaking the object. Shapeable VIPs of the present invention contain a single core component hermetically sealed within a gas -impermeable barrier. The single core component resides in a vacuum within the gas impermeable barrier material. The shapeable VIP is capable of bending 90s or more, preferably 180s or more without breaking the single core component into two or more discrete pieces. For example, FIG la shows VIP 5 in an initial configuration and FIG lb shows VIP 5 bent 90s relative to the initial configuration in FIG la.
VIPs of the present invention are shapeable even when the core component of the VIP is free of grooves. Grooves extend from one end to another end in a chosen direction. WO 96/32605 describes VIPs with core components. A method for preparing grooves in a core component and a definition of a "groove" is on page 10, lines 7-17 of WO 96/32605. While grooves are not necessary, core components of the present invention can contain grooves or be free of grooves. The vacuum within the gas-impermeable barrier is preferably 10 torr (1,330 pascal (Pa)) or less, more preferably 1 torr (133 Pa) or less, most preferably 0.1 torr (13.3 Pa) or less. Lower pressures are preferable to achieve lower thermal conductivity through the VIP. A VIP that has a pressure greater than 10 torr (1,330 Pa) tends to have an undesirably high thermal conductivity.
A gas -impermeable barrier in the present invention preferably has a gas permeation rate of 1.5 cubic centimeter per day per square meter (cc/day/m2) or less, more preferably 0.15 cc/day/m2 or less, most preferably 0.015 cc/day/m2 or less. Measure gas permeation rate according to ASTM method D- 3985. A VIP having a gas -impermeable barrier having a gas permeation rate of greater than 1.5 cc/day/m2 tends to lose vacuum and insulating properties more quickly than is desirable.
Suitable materials for use as gas -impermeable barriers include metal sheet, metal foil, polymeric film, and combinations thereof. Some materials, such as metal sheet, tend to be rigid and preferably contain corrugation to enhance flexibility, allowing a VIP to be shapeable. Corrugation may be uniform along the rigid material or only occur in sections of the material where bending or folding occurs. USP 5,175,975 (column 9 lines 3-16 and lines 29-36 and FIGs 16, 17, and 19) describes examples of corrugated metal sheets as VIP gas barrier materials. USP 5,175,975 describes planar VIPs in which corrugations are in a direction parallel to an X-axis when the VIP is in a plane containing X and Y axes. The corrugations allow the VIP to move in the +Z and -Z axis while remaining rigid in the X- axis .
Preferably, the gas - impermeable barrier is a polymeric film. Polymeric films offer a desirable combination of flexibility and durability. Suitable polymeric films can contain any common polymer or combination of polymers provided the films have a gas permeation rate of 1.5 cc/day/m2 or less, according to ASTM method D-3985. Polymeric films may contain, for example, polyesters, copolyesters, tetrafluoroethylene, polyi ide, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol (PVOH) , polystyrene (PS) polymers and copolymers, polyethylene (PE) polymers and copolymers, and polypropylene (PP) polymers and copolymers.
Polymeric films may include a coating disposed on at least one surface to reduce gas permeability of the film. Suitable coatings include those selected from the group consisting of inorganic materials, such as a metal, ceramic, or glass, as well as organic materials such as polyvinylidene chloride (PVDC) . Suitable metals include gold, aluminum and silver. Suitable means for coating a film include any method known in the art such as plasma coating, sputter coating, spray coating, and electromagnetic bonding.
More preferably, the gas-impermeable barrier is a multilayer film, desirably having an exposed layer that is heat sealable. One particularly preferred multilayer film comprises an outer layer, a middle layer and an inner layer. The outer layer desirably comprises a scratch resistant material such as a polyester or copolyester. The middle layer desirably consists of a barrier material such as aluminum, PVDC, PVOH, or a polymeric film having a coating of aluminum. The inner layer desirably contains a heat sealable material such as PE, ethylene/acrylic acid copolymer, PE- vinylacetate copolymer, high density PE, and PP blends. Lamination, extrusion coating, and coextrusion are all suitable means for preparing gas -impermeable multilayer films. Commercially available multilayer films suitable as barrier materials for the present invention are also available and include films NA-1, NA-2, NA-3, and NA-4 from Toyo Aluminum .K.; aluminum foil containing films SA-1, SA- 2, SA-3, SA-4, SA-5, and SA-6, also from Toyo Aluminum K.K.; and MYLAR™ (trademark of E. I. du Pont de Nemours and Company) 200 RSBL, MYLAR 250 RSBL 300, and MYLAR 350 RSBL 300 polyester films.
A skilled artisan can determine any of a number of ways to hermetically seal a suitable barrier material. For example, one can weld metal sheets together and heat-seal or melt polymeric films together. If necessary, one may use an additional adhesive or glue to hermetically seal together sheets or plies of the barrier material.
The shapeable VIP contains a singe core component that may or may not be shapeable apart from the VIP. For example, some PS foams may not be shapeable until they are under vacuum within a VIP and supported by a gas-impermeable barrier.
Herein, "single core component" refers to a core component comprising a single structure. A single core component enables fast and simple manufacture of a VIP. For example, manufacturing a VIP with a single core component can involve inserting the core component into a gas- impermeable barrier receptacle (such as a bag) ; evacuating the receptacle; and hermetically sealing the receptacle. In contrast, manufacturing VIPs that contain two or more discrete core components requires specific placement of each core component. Discrete core components may disadvantageously move or re-orient relative to one another during manufacture. A VIP of the present invention requires placement of only a single core component and minimizes the risk of discrete core components moving during manufacture.
A single core component may comprise a single core component section or two or more interconnected core component sections. A "core component section" is a portion of a single core component that extends from one face to an opposing face of the single core component.
A shapeable VIP of the present invention that has a core component consisting of a single core component section is characterizable by a "D/T" ratio. "T" is the thickness of the VIP and "D" is the smallest diameter of a mandrel about which the VIP will bend 902 without breaking the core component into discrete pieces. Measure "T" and "D" using the same units. Dividing T into D achieves the D/T ratio, a unitless value. The D/T ratio for a shapeable VIP having a core component comprising a single core component section is greater than zero, generally one or more. The D/T ratio is preferably 48 or less, more preferably 24 or less, still more preferably 12 or less, most preferably 8 or less. VIPs having a D/T ratio of greater than 48 lack sufficient flexibility for most uses requiring a flexible VIP.
Alternatively, a single core component may contain two or more interconnected core component sections . Interconnecting core component sections may be the same or different. For example, interconnecting core component sections may have different compositions, densities, structures, and sizes. Core component sections may be directly interconnected, indirectly interconnected, or a combination of both.
Directly interconnected core component sections attach directly to each other without the use of a connector. For example, melt-welding polymeric foam boards together directly interconnects the boards. VIPs that have a single core component consisting of only directly interconnected core component sections are preferably characterizable by a D/T ratio and the D/T ratio values previously specified.
Indirectly interconnected core component sections utilize at least one connector to join the core component sections together. Two indirectly interconnected core component sections may or may not be touching each other and include a connector with one portion of the' connector attached to one core component section and another portion of the connector attached to the other core component section.
Connectors may be flexible or rigid. Flexible connectors are preferable because they tend to contribute to a VIP's flexibility. A connector that can bend at least 90s without fracturing is a "flexible" connector. A connector that fractures upon bending 90s is a "rigid" connector. Flexible connectors may become rigid connectors under certain conditions, and vice versa. For example, a polymeric film may be a flexible connector at or near its glass transition temperature (Tg) yet be rigid connector 100 SC below its Tg. Therefore, whether a connector is a rigid connector or a flexible connector is dependent upon what the connector is made of and at what temperature it is at. Herein, connectors are considered to be at 23 SC unless otherwise indicated. Suitable connectors include those selected from the group consisting of polymeric films and foams, adhesive films, corrugated metal, adhesive tape, paper, metal foil, string, and wire. Flexible glues and adhesives, such as silicone rubber are also suitable flexible connectors. Polymeric films and adhesive tapes, such as SCOTCH™ brand adhesive tape (SCOTCH is a trademark of 3M) are desirable connectors. Polymeric films comprising at least one polymer selected from the group consisting of polyesters, PE, PS, and copolymers thereof are more desirable. Polymeric films may comprise more than one layer to achieve desired properties. For example, a polymeric film having opposing surfaces may include an adhesive layer on one surface and a durable film layer on an opposing surface.
A shapeable VIP containing only core component sections directly interconnected by rigid connectors typically bend within at least one core component section. As such, the VIP preferably has a D/T ratio in the previously specified ranges. Alternatively, the VIP is only shapeable under conditions that transform any rigid connector (or connectors) between any two core component sections into a flexible connector (or connectors) , thereby allowing the VIP to bend along the connector (s) .
Core component sections beneficially comprise highly open- celled foam. "Highly open- celled" foams are 90% or more open-celled, preferably 95% or more open-celled, more preferably 98% or more open-celled, most preferably 99% or more open-celled according to ASTM method D2856-A. Foams that are less than 90% open-celled are difficult to evacuate when manufacturing a VIP. Highly open-celled foams may be inorganic, such as ceramic or glass, or organic, such as cellulose or organic polymer-based. More preferably, core component sections are highly open- celled polymeric foam comprising at least one polymer. Preferred polymers include those selected from the group consisting of alkenyl aromatic homo- and copolymers including PS homo- and copolymers, PP homo- and copolymers, PE homo- and copolymers, polycarbonate homo- and copolymers, polyurethane (PU) polymers, polyisocyanurate polymers, and blends thereof . Examples of suitable polymer blends include blends of an alkenyl aromatic polymer and an ethylene copolymer such as an ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene- methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethylacrylate copolymer, ionomer, or an ethylene copolymer made with either constrained geometry or metallocene catalyst technology. Most preferably, a core component section comprises a highly open- celled PS foam. A core component section may comprise particulate or fibrous materials, provided the materials interconnect or are within a container. For instance, NANOGEL™ advanced thermal insulation (NANOGEL is a trademark of Cabot Corporation) is an example of particulate material inside of a bag that is suitable as a core component section within the scope of this invention. Suitable particulate materials include open- celled porous materials such as silica gel, titania gel, alumina gel; and polymeric gels such as resocinol- formaldehyde gels, and melamine formaldehyde gels. Fibrous materials include fiberglass, glasswool, and mineral wool. However, a single core component of the present invention contains less than 50 wt%, preferably less than 25 wt%, more preferably less than 10 wt% of fiberglass fibers relative to core component weight.
Core component sections are preferably essentially free of fibrous material such as fiberglass, glass wool, and mineral wool. A core component section is essentially free of fibrous material when it contains 10 wt% or less, preferably 5 wt% or less, more preferably 1 wt% or less of fibrous material by weight of the core component section. A core component that is essentially free of fibrous materials, particularly fiberglass, minimizes the chance that fibers may puncture the barrier material or breach the hermetic seal by traversing the seal during manufacture.
Particulate or fibrous materials may interconnect mechanically, adhesively, or chemically. For example, inter- weaving fibers mechanically binds them together. Glue or non-reactive binders can adhesively bind particles or fibers together. Reactive binders, such as those that chemically crosslink fibrous or particulate materials together, can chemically bind fibers and particles. Interconnected non- porous particles and fibers preferably have void spaces between particles or fibers to reduce the VIP density and facilitate evacuation of the VIP.
There are many suitable configurations for interconnecting core component sections with at least one connector, some of which are evident in FIGs la, lb, 2a, 2b, 3b, and 3c. Like numbers in different figures refer to the same feature.
FIG la shows a cut-away view of VIP 5 in an initial configuration. VIP 5 contains core component 10 within gas- impermeable barrier 8. Core component 10 contains two indirectly interconnected core component sections 12 and 14. Core component section 12 has edge 17 (shown only in FIG la) that is proximate to core component section 14. Flexible connector 16 adheres to a surface portion of both core component sections 12 and 14, thereby interconnecting them.
Core component section 14 has a thickness T (shown only in FIG la) , while core component section 12 has thickness T' (shown only in FIG la) . Thickness T and thickness T' may be the same or different. Core component sections 12 and 14 are spaced a distance S (shown only in FIG la) apart. The magnitude of distance S is preferably the same as that of thickness T.
FIG lb shows VIP 5 in a configuration bent 90s by way of flexible connector 16, relative to the initial configuration shown in FIG la. When thickness T and spacing S are the same, edge 17 of core component 12 contacts face 18 (not shown) of core component 14, forming a fully insulated right angle corner, as shown in FIG lb. Variations in thickness T and spacing S can allow VIP 5 to bend to angles other than 90s. For instance, increasing spacing S while maintaining thickness T, or decreasing thickness T while maintaining spacing S can allow VIP 5 to bend more than 90s.
A single connector may simultaneously connect two or more core component sections, as FIGs 2a and 2b show. FIG 2a shows single core component 20 containing core component connectors 30 and 32 simultaneously interconnecting core component sections 22, 24, 26, and 28. Connectors 30 and 32 can be, for example, adhesive tape extending across and attaching to surface portions of core component sections 22, 24, 26, and 28. Core component 20 further includes connectors 38 and 40 interconnecting core component sections 34 and 36, respectively, to core component section 24. FIG 2b shows core component 20 in a configuration wherein core component sections 22, 24, 26, and 28 (not shown) form the sides of a box while core component sections 34 and 36 form a top and bottom for the box. A VIP containing single core component 20 can form an insulating box when the core component is in the configuration of FIG 2b.
FIG 3a shows core component section 50 that has opposing faces 60 and 62 (not shown) , and opposing edges 64 and 66
(not shown) which are each beveled to bevel "angles 69 and 68, respectively. In general, opposing edges can have different bevel angles, although bevel angle 68 is preferably the same as bevel angle 69 in core component 50. For convenience, identify face 60 as an inside face and face 62 as an outside face. Outside face 62 has a larger surface area than inside face 60.
FIG 3b shows core component 80 comprising core component sections 51, 52, 53, 54, and 55, each similar to core component section 50 in that each of such sections have two bevel angles, each of which is 36s. Core component sections 51, 52, 53, 54, and 55 each have opposing bevel edges (shown only in FIG 3b) 90 and 91, 92 and 93, 94 and 95, 96 and 97, and 98 and 99, respectively. The core component sections are touching along lines 82, 83, 84, and 85, thereby creating continuous outside face 86 along the core component.
Connectors 70 and 72 attach to a portion of outside face 86 of core component 80, interconnecting core component sections 51, 52, 53, 54, and 55.
FIG 3c shows core component 80 bent such that beveled edges 90 and 99 (shown in FIG 3b) meet. Adjacent beveled edges 91 and 92, 93 and 94, 95 and 96, and 97 and 98 (shown only in FIG 3b) also meet. In the configuration of FIG 3c, core component 80 forms a wall for a five- sided container having a continuous outside face 86 and a continuous inside face 87 (shown only in FIG 3c) . A VIP containing core component 80 can form the walls of a five- sided insulated container by folding the core component, and thereby the VIP, into the configuration shown in FIG 3c. VIP 80 can also be provided with a top, a bottom, or both in a manner similar to that illustrated in FIGs 2a and 2b.
VIPs having core component sections similar to core component section 50 are useful for forming containers having three or more sides wherein edges of adjacent sides contact each other. Preferably, such a VIP has a core component that includes one core component section for each side of the container and each core component section has bevel angle equal to 180° divided by the number of sections in the core component, or 1802 divided by the number of sides to the container.
Shapeable VIPs of the present invention preferably have a thermal conductivity, according to ASTM method C- 518 -98, of 0.083 British Thermal Unit- inch per hour- square foot-degree Fahrenheit (BTU*in/hr*ft2*°F) (12 milliwatt per meter-Kelvin (mW/m*K) ) or less, more preferably 0.056 BTU*in/hr*ft2*°F (8.1 mW/m*K) or less, and still more preferably 0.042 BTU*in/hr*ft2*°F (6.0 mW/m*K) or less.
Shapeable VIPs may further comprise additives, such as water-absorbent materials or getters within the VIP. Water- absorbent materials are useful to capture any moisture that is trapped within a VIP. Similarly, getters are useful to capture gases such as oxygen, nitrogen, carbon dioxide, helium and hydrogen that are trapped within a VIP. Both water absorbers and getters help maintain a vacuum within a VIP. Suitable water-absorbent materials include anhydrous calcium oxide, anhydrous barium oxide, anhydrous silica gel, anhydrous silica powder, and anhydrous molecular sieves. Suitable getters include alloys of barium, lithium, and cobalt oxide. One commercially available getter is available under the trademark COMBGETTER™ from SAES getters. Additives may or may not be bound to one or both of a single core component or a gas -impermeable barrier of the present invention.
The present invention also relates to an insulating container containing at least one shapeable VIP having a single core component. A shapeable VIP may form the container itself, or act as an insulating component within or around a container shell such as a box or a tube. A container comprises a wall structure having opposing top and bottom ends. The wall structure encloses a volume, which is the inside the container. The wall structure can be any conceivable shape, for example, cylindrical or rectilinear. A container typically includes a base attached to the bottom of the container and a lid for covering the top of the container. Preferably, the base and lid also contain a VIP. More preferably, a container includes a gasket between its lid and the wall structure. A gasket may also exist between a base and the wall structure.
FIG 2b shows a core component in the form of a container. A VIP containing the core component of FIG 2a may assume the configuration of FIG 2b to create an insulating container of the present invention.
Similarly, FIG 3c shows a core component in the form of a pentagonal wall structure. A VIP containing the core component of FIG 3b can assume the configuration in FIG 3c, thereby creating an insulated wall structure for a container. Two or more shapeable VIPs may work cooperatively to form an insulating container of the present invention. For example, two VIPs in an orthogonal "C" orientation can combine to form a six-sided insulating container.
A VIP containing a single core component section may also form a wall structure for a container. For example, FIG 4 shows insulating container 100 consisting of container shell 102 and VIP 104. VIP 104 contains a single core component section (not shown), opposing ends 106 and 108, and opposing faces 110 and 112. Ends 106 and 108 meet and VIP 104 forms a continuous VIP wall structure. Taping ends 106 and 108 together helps maintain the continuous wall structure. Alternatively, end 106 or end 108 may meet face 110 to form a similar VIP wall structure, not shown. ' Other shapes of container shells, such as cylindrical or polyhedral, would work equally well as container shell 102. VIP 104 may assume a cylindrical shape with a circular cross section as in FIG 4, or it may assume a teardrop or oval cross section.
A protective film or other material may cover one or more surfaces of the VIPs to enhance durability. A protective film is particularly useful for protecting VIPs in the absence of any container other than the VIPs.
. A skilled artisan can conceive of many ways to use a shapeable VIP to form a thermally insulating container. The following examples further illustrate but do not limit the scope of the present invention.
Example (Ex) 1. Shapeable VIP Containing a Single Core
Component Section
Prepare a bag from two sheets of polymeric film (such as MYLAR 250 RSBL 300 film) that are each 37 inches (in.) (94 centimeter (cm)) long and 13.5 in. (34 cm) wide. Overlay one sheet on the other sheet and heat seal three edges together using a heat seal bar at 120- 150 SC to form a bag with an open end. Cut a single core component from a polymeric foam that is greater than 95% open celled (for example, INSTILL™-UC foam, INSTILL is a trademark of The Dow Chemical Company) . The single core component is 10 in. (25 cm) wide, 35 in. (89 cm) long, and 1 in. (2.5 cm) thick. Insert the foam core component into the bag. Place the bag containing the foam core component inside of a vacuum chamber and position a heat seal bar at the open end of the bag. Evacuate the chamber to a pressure of 0.1 torr or less and then clamp the heat seal bar (at 120- 150 SC) onto the open end of the bag, thereby sealing the bag and creating a VIP (Ex 1) . Relieve the vacuum and remove Ex 1.
Bend Ex 1 into a teardrop configuration such that opposing ends of Ex 1 contact each other. Tape the ends together using adhesive tape. Insert Ex 1 into a 12 in. (30.5 cm) by 12 in. (30.5 cm) by 12 in. (30.5 cm) corrugated box, thereby fabricating an insulated container similar to that in FIG 4.
Ex 1 illustrates a shapeable VIP having a single core component comprising a single core component section that is free of grooves and the use of such a VIP in forming an insulating container.
Ex 2. A Shapeable VIP Having an Indirectly Interconnected Core Component Create a core component consisting of four indirectly interconnected core component sections . Each core component section is a polymeric foam similar to that of Ex 1. Cut four pieces of foam into rectangular core component sections that are 1 in. (2.5 cm) thick and have opposing 10 in. (25 cm) long edges and opposing 11 in. (28 cm) wide ends.
Position the four core component sections in a row such that the 11 in. (28 cm) wide ends of each core component section are collinear with the 11 in. (28 cm) wide ends of each other core component section. Adjacent 10 in. (25 cm) long edges are parallel and spaced 1 in. (2.5 cm) away from any adjacent core component section edge. Interconnect the core component sections by adhering two strips of 0.5 in. (1.3 cm) wide adhesive tape (such as SCOTCH brand adhesive tape) across portions of the core component sections, similar to the way connectors 30 and 32 interconnect core component sections 22, 24, 26, and 28 in FIG 2a.
Create a bag with an open end using two 13.5 in. (34 cm) by 47 in. (119 cm) sheets of polymeric film, as described for Ex 1. Insert the core component into the bag. The adhesive tape interconnecting core component sections allows sliding of the core component into the bag as a single unit. The four core component sections may slide together during insertion into the bag, but pulling on the sections until the tape is taut restores a 1 in. (2.54 cm) spacing between sections. Evacuate the bag and seal it as described for Ex 1 to create Ex 2.
Fold Ex 2 along the connectors to form a four- sided wall structure with each core component section within Ex 2 corresponding to a side. Prepare an insulating container by inserting the wall structure into a container shell. Alternatively, apply tape as necessary to secure the wall structure from unfolding and add a lid and base to create an insulated container. The lid and base may be VIPs.
Ex 2 illustrates a VIP having an indirectly interconnected single core component that is free of grooves and the use of such a VIP to form an insulating container.

Claims

CLAIMS :
1. A vacuum insulation panel comprising a single core component enclosed within a gas -impermeable barrier; wherein said vacuum insulation panel can bend or fold at least 90 degrees relative to an initial configuration without breaking said single core component into two or more discrete pieces when said single core component is free of grooves; and wherein said single core component contains less than 50 weight -percent of fiberglass fibers, based on single core component weight.
2. The vacuum insulation panel of Claim 1, wherein said single core component contains at least one core component section comprising a polymeric foam that is 90 percent or more open- celled according to American Society for Testing and Materials method D2856-A.
3. The vacuum insulation panel of Claim 2, wherein the polymeric foam comprises polystyrene.
4. The vacuum insulation panel of Claim 1, wherein said single core component comprises two or more interconnected core component sections.
5. The vacuum insulation panel of Claim 4, wherein said core component sections are interconnected by at least one material selected from the group consisting of polymeric films and foams, adhesive films, corrugated metal, adhesive tape, paper, metal foil, string, wire, and glue.
6. The vacuum insulation panel of Claim 1, wherein said core component contains at least one core component section that has loose particulate material inside of a container.
7. The vacuum insulation panel of Claim 1, wherein said gas- impermeable barrier comprises a polymeric film.
8. The vacuum insulation panel of Claim 7, wherein said polymeric film is a multilayered polymeric film.
9. The vacuum insulation panel of Claim 8, wherein said multilayered polymeric film has an exposed layer that is heat sealable.
10. The vacuum insulation panel of Claim 8, wherein said multilayered polymeric film includes a coating disposed on at least one surface and said coating is selected from the group consisting of metal, ceramic, glass, and organic materials.
11. The vacuum insulation panel of Claim 1, wherein said vacuum insulation panel has a D/T ratio of less than 48.
12. The vacuum insulation panel of any of Claim 1- 12, wherein said core component is essentially free of fiberglass, glass wool, and mineral wool.
13. An insulated container comprising at least one vacuum insulation panel of Claim 1.
14. The insulated container of Claim 13, further comprising a container shell, wherein said vacuum insulation panel fits around or within said container shell.
15. A method of insulating a container shell comprising:
(a) bending the vacuum insulation panel of Claim 1 into a desired configuration; then (b) disposing the vacuum insulation panel into or around said container shell.
PCT/US2002/008608 2001-04-06 2002-03-18 Shapeable vacuum insulation panel containing a single core component WO2002081833A1 (en)

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Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7422143B2 (en) * 2002-10-23 2008-09-09 Minnesota Thermal Science, Llc Container having passive controlled temperature interior
WO2004071885A2 (en) 2003-02-13 2004-08-26 Martin Marietta Materials, Inc. Insulated cargo containers
US7997044B2 (en) * 2004-04-19 2011-08-16 Marhaygue, Llc Enclosure and method for making an enclosure
TW200632245A (en) * 2005-01-28 2006-09-16 Matsushita Electric Ind Co Ltd A thermal insulator
US7721566B1 (en) 2006-08-14 2010-05-25 Minnesota Thermal Science, Llc Collapsible interconnected panels of phase change material
JP2008105748A (en) * 2006-09-28 2008-05-08 Nichias Corp Heat insulating container and its manufacturing method
US7516600B1 (en) * 2006-11-17 2009-04-14 Minnesota Thermal Science, Llc Method of packaging thermally labile goods employing color-coded panels of phase change material
JP4920468B2 (en) * 2007-03-26 2012-04-18 ニチアス株式会社 Insulated container and manufacturing method thereof
DE102007023368A1 (en) * 2007-05-18 2008-11-27 Deutsche Rockwool Mineralwoll Gmbh + Co Ohg Method for producing an insulating element and insulating element
US7950246B1 (en) * 2008-02-13 2011-05-31 Minnesota Thermal Science, Llc Assembly of abutting vacuum insulated panels arranged to form a retention chamber with a slip surface interposed between the panels
US8733033B2 (en) * 2008-06-27 2014-05-27 Millport Associates, SA Sandwich panel ground anchor and ground preparation for sandwich panel structures
US8782991B2 (en) * 2008-07-10 2014-07-22 Millport Associates S.A. Building roof structure having a round corner
US20100050553A1 (en) * 2008-08-29 2010-03-04 Innovida Factories, Ltd. sandwich panel joint and method of joining sandwich panels
US8333279B2 (en) * 2008-09-11 2012-12-18 Simple Container Solutions, Inc. Expandable insulated packaging
US9751682B2 (en) 2009-02-20 2017-09-05 Pelican Biothermal Llc Modular cuboidal passive temperature controlled shipping container
US8424335B2 (en) * 2009-12-17 2013-04-23 Minnesota Thermal Science, Llc Cascading series of thermally insulated passive temperature controlled containers
AT511420A1 (en) 2011-04-21 2012-11-15 Ros Nico PACKAGING WITH ENCLOSING HEAT BARRIER
CN102330475B (en) * 2011-07-13 2013-07-31 苏州维艾普新材料有限公司 Vacuum insulation panel core material with high performance and low cost and manufacturing method thereof
US9221210B2 (en) 2012-04-11 2015-12-29 Whirlpool Corporation Method to create vacuum insulated cabinets for refrigerators
US8986483B2 (en) 2012-04-02 2015-03-24 Whirlpool Corporation Method of making a folded vacuum insulated structure
US8875475B2 (en) 2013-03-14 2014-11-04 Millport Associates S.A. Multiple panel beams and methods
WO2015071544A1 (en) * 2013-11-15 2015-05-21 Wimacor Oy Method for manufacturing cargo container, and panel element for a cargo container
US10052819B2 (en) 2014-02-24 2018-08-21 Whirlpool Corporation Vacuum packaged 3D vacuum insulated door structure and method therefor using a tooling fixture
US9599392B2 (en) * 2014-02-24 2017-03-21 Whirlpool Corporation Folding approach to create a 3D vacuum insulated door from 2D flat vacuum insulation panels
USD759185S1 (en) * 2014-12-31 2016-06-14 Magpul Industries Corporation Slot cover for a firearm
US9476633B2 (en) 2015-03-02 2016-10-25 Whirlpool Corporation 3D vacuum panel and a folding approach to create the 3D vacuum panel from a 2D vacuum panel of non-uniform thickness
US10161669B2 (en) 2015-03-05 2018-12-25 Whirlpool Corporation Attachment arrangement for vacuum insulated door
US9897370B2 (en) 2015-03-11 2018-02-20 Whirlpool Corporation Self-contained pantry box system for insertion into an appliance
US9441779B1 (en) 2015-07-01 2016-09-13 Whirlpool Corporation Split hybrid insulation structure for an appliance
US20170088337A1 (en) * 2015-09-28 2017-03-30 Package Depot, Inc. Method and Apparatus for Providing an Insulated Shipping Container
CN112722591A (en) 2015-11-25 2021-04-30 野醍冷却器有限责任公司 Insulated container with vacuum insulated panel and method
US10041724B2 (en) 2015-12-08 2018-08-07 Whirlpool Corporation Methods for dispensing and compacting insulation materials into a vacuum sealed structure
US10429125B2 (en) 2015-12-08 2019-10-01 Whirlpool Corporation Insulation structure for an appliance having a uniformly mixed multi-component insulation material, and a method for even distribution of material combinations therein
US10422573B2 (en) 2015-12-08 2019-09-24 Whirlpool Corporation Insulation structure for an appliance having a uniformly mixed multi-component insulation material, and a method for even distribution of material combinations therein
US11052579B2 (en) 2015-12-08 2021-07-06 Whirlpool Corporation Method for preparing a densified insulation material for use in appliance insulated structure
US10222116B2 (en) 2015-12-08 2019-03-05 Whirlpool Corporation Method and apparatus for forming a vacuum insulated structure for an appliance having a pressing mechanism incorporated within an insulation delivery system
US10808987B2 (en) 2015-12-09 2020-10-20 Whirlpool Corporation Vacuum insulation structures with multiple insulators
US10422569B2 (en) 2015-12-21 2019-09-24 Whirlpool Corporation Vacuum insulated door construction
US10610985B2 (en) 2015-12-28 2020-04-07 Whirlpool Corporation Multilayer barrier materials with PVD or plasma coating for vacuum insulated structure
US10018406B2 (en) 2015-12-28 2018-07-10 Whirlpool Corporation Multi-layer gas barrier materials for vacuum insulated structure
US10807298B2 (en) 2015-12-29 2020-10-20 Whirlpool Corporation Molded gas barrier parts for vacuum insulated structure
US11247369B2 (en) 2015-12-30 2022-02-15 Whirlpool Corporation Method of fabricating 3D vacuum insulated refrigerator structure having core material
WO2017180145A1 (en) 2016-04-15 2017-10-19 Whirlpool Corporation Vacuum insulated refrigerator structure with three dimensional characteristics
US10712080B2 (en) 2016-04-15 2020-07-14 Whirlpool Corporation Vacuum insulated refrigerator cabinet
JP6695736B2 (en) * 2016-05-13 2020-05-20 黒崎播磨株式会社 Insulation and its construction method
EP3491308B1 (en) 2016-07-26 2021-03-10 Whirlpool Corporation Vacuum insulated structure trim breaker
WO2018034665A1 (en) 2016-08-18 2018-02-22 Whirlpool Corporation Machine compartment for a vacuum insulated structure
EP3548813B1 (en) 2016-12-02 2023-05-31 Whirlpool Corporation Hinge support assembly
US10352613B2 (en) 2016-12-05 2019-07-16 Whirlpool Corporation Pigmented monolayer liner for appliances and methods of making the same
US10683158B2 (en) 2017-01-26 2020-06-16 Pelican Biothermal, Llc Protectively framed and covered thermal insulation panel
US11511928B2 (en) 2017-05-09 2022-11-29 Cold Chain Technologies, Llc Shipping system for storing and/or transporting temperature-sensitive materials
EP3634879B1 (en) 2017-05-09 2023-11-01 Cold Chain Technologies, LLC Shipping system for storing and/or transporting temperature-sensitive materials
USD821824S1 (en) 2017-05-16 2018-07-03 Yeti Coolers, Llc Insulating device
USD820647S1 (en) 2017-05-16 2018-06-19 Yeti Coolers, Llc Insulating device
USD821156S1 (en) 2017-05-16 2018-06-26 Yeti Coolers, Llc Insulating device
USD820648S1 (en) 2017-05-16 2018-06-19 Yeti Coolers, Llc Insulating device
USD821157S1 (en) 2017-05-16 2018-06-26 Yeti Coolers, Llc Insulating device
USD821155S1 (en) 2017-05-16 2018-06-26 Yeti Coolers, Llc Insulating device
US11130622B2 (en) 2018-04-25 2021-09-28 Pelican Biothermal, Llc Thermally insulated shipping container with layered articulating vacuum insulated panels
US10907888B2 (en) 2018-06-25 2021-02-02 Whirlpool Corporation Hybrid pigmented hot stitched color liner system
US10907891B2 (en) 2019-02-18 2021-02-02 Whirlpool Corporation Trim breaker for a structural cabinet that incorporates a structural glass contact surface
US11402141B1 (en) * 2020-12-01 2022-08-02 Tracy Polk Refrigerator and freezer conversion system
CN114321570B (en) * 2021-12-29 2023-08-08 安徽吉曜玻璃微纤有限公司 Vacuum insulation panel and production method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4726974A (en) 1986-10-08 1988-02-23 Union Carbide Corporation Vacuum insulation panel
US5107649A (en) 1988-04-15 1992-04-28 Midwest Research Institute Compact vacuum insulation embodiments
US5175975A (en) 1988-04-15 1993-01-05 Midwest Research Institute Compact vacuum insulation
US5273801A (en) 1991-12-31 1993-12-28 Whirlpool Corporation Thermoformed vacuum insulation container
WO1996032605A1 (en) 1995-04-13 1996-10-17 Imperial Chemical Industries Plc Non-planar evacuated insulation panels and a method for making same
US5566849A (en) * 1994-06-20 1996-10-22 Goehner Industries, Inc. Hinge structure for a box
US5857307A (en) * 1994-06-29 1999-01-12 Sanyo Electric Co., Ltd. Heat insulating structure and production process thereof
US6010762A (en) 1998-01-15 2000-01-04 Cabot Corporation Self-evacuating vacuum insulation panels

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4726974A (en) 1986-10-08 1988-02-23 Union Carbide Corporation Vacuum insulation panel
US5107649A (en) 1988-04-15 1992-04-28 Midwest Research Institute Compact vacuum insulation embodiments
US5175975A (en) 1988-04-15 1993-01-05 Midwest Research Institute Compact vacuum insulation
US5273801A (en) 1991-12-31 1993-12-28 Whirlpool Corporation Thermoformed vacuum insulation container
US5566849A (en) * 1994-06-20 1996-10-22 Goehner Industries, Inc. Hinge structure for a box
US5857307A (en) * 1994-06-29 1999-01-12 Sanyo Electric Co., Ltd. Heat insulating structure and production process thereof
WO1996032605A1 (en) 1995-04-13 1996-10-17 Imperial Chemical Industries Plc Non-planar evacuated insulation panels and a method for making same
US6010762A (en) 1998-01-15 2000-01-04 Cabot Corporation Self-evacuating vacuum insulation panels

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