IE20070752A1 - An insulating medium - Google Patents

An insulating medium

Info

Publication number
IE20070752A1
IE20070752A1 IE20070752A IE20070752A IE20070752A1 IE 20070752 A1 IE20070752 A1 IE 20070752A1 IE 20070752 A IE20070752 A IE 20070752A IE 20070752 A IE20070752 A IE 20070752A IE 20070752 A1 IE20070752 A1 IE 20070752A1
Authority
IE
Ireland
Prior art keywords
insulating medium
microbodies
insulating
hollow
foam
Prior art date
Application number
IE20070752A
Inventor
Malcolm Rochefort
Thomas Mccabe
Original Assignee
Kingspan Res & Dev Ltd
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 Kingspan Res & Dev Ltd filed Critical Kingspan Res & Dev Ltd
Priority to IE20070752A priority Critical patent/IE20070752A1/en
Publication of IE20070752A1 publication Critical patent/IE20070752A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/002—Hollow glass particles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C03C17/322—Polyurethanes or polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • F16L59/028—Composition or method of fixing a thermally insulating material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2201/00—Insulation
    • F25D2201/10—Insulation with respect to heat
    • F25D2201/14—Insulation with respect to heat using subatmospheric pressure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Paints Or Removers (AREA)
  • Building Environments (AREA)

Abstract

An insulating medium comprises a plurality of hollow microbodies which are gas impermeable and have a low aspect ratio. The hollow bodies may be microspheres which are formed from a glass material. The microbodies are bonded in a resin such as a phelonic, polyurethane or polyisocyanurate material. The hollow microbodies have an internal void pressure of less than 0.1 bar a. Panels formed from such an insulating medium are described. Such panels have superior insulating properties and can be punctured by a nail or cut to size without adversely affecting its insulating properties.

Description

The invention relates to an insulating medium and in particular to an insulating board or panel incorporating such an insulating medium.
Insulating boards manufactured from, for example, an open cell foam, mineral fibre, or particle panel, vacuum packed in an outer layer of metal foil are known. High thermal insulation values are achievable with this method of panel manufacture, with thermal conductivity (λ or k-values) of 0.006 W/m.K or better being achieved. Such boards have been used commercially, for example, to improve refrigerator and freezer thermal insulation efficiency thereby enabling thinner wall sections. One of the problems with such boards, however, is that the foil is easily punctured which breaks the vacuum and consequently the insulation performance deteriorates to λ-values of 0.030 W/m.K or worse. This makes the boards unsuitable for practical use in the building construction industry and other applications where puncturing caused by penetrative fixing methods or rough handling is likely to occur.
There is therefore a need for an improved high efficiency thermal insulation medium which is robust. Such a medium would facilitate the formation of an insulating board for use in the construction sector and other areas employing penetrative fixing methods or where rough handling is likely.
Statements of invention According to the invention there is provided an insulating medium having a plurality of hollow microbodies bonded in a suitable resin, the hollow microbodies having an internal void pressure of less than 0.1 bar a.
In one embodiment of the invention the microbodies are filled with a porous material, such as open cell organic foam or porous inorganic material. Filling with open cell or I ®70752 -2microporous material will reduce pore size to be comparable to mean free path which means reduction in pressure enables a proportional reduction in gas thermal conductivity. If the pore size significantly exceeds mean free path, the increase in mean free path with reduction of pressure cancels the pressure reduction effect on thermal conductivity.
In a preferred embodiment the microbodies have a low aspect ratio. The microbodies may be of generally spherical shape. Typically the microbodies are microspheres.
The microbodies may have a particle size up to 1cm across. The typical microbody, especially microsphere particle size range is 5 to lOOOpm, preferably 10 to 200 pm.
In one embodiment of the invention the internal void pressure of the microbodies is less than 0.01 bar a, preferably less than 0.001 bar a and ideally less than 0.0001 bar a.
Preferably the resin is of a foam or non foaming material such as a phenolic, polyurethane or polyisocyanurate material.
Alternatively the resin is of a foam or non foaming material such as a polyester, an epoxy, acrylic, silicone, urea formaldehyde resin or vinyl ester.
In one embodiment of the invention the hollow microbodies are of substantially the same size.
Alternatively the hollow microbodies are of different sizes.
The hollow microbodies may have a bi-modal size distribution. Alternatively the hollow microbodies have a tri-modal size distribution.
The microbodies may be of an inorganic material. 070 7 52 -3The microbodies are preferably of glass material. The microbodies may be of alumino silicate material or of calcined clay material.
In another embodiment the microbodies are of organic material. In this case the microbodies are of a phenolic material or of a thermoplastic material.
In one embodiment of the invention the hollow microbodies are coated with gas permeability reducing material. The coating material is preferably a metallic material, especially of aluminium flake material.
The internal surface(s) of the microbodies are coated with the coating material.
The invention also provides an insulating board having an insulating medium as claimed in any preceding claim. The insulating board may include a facing on one or both faces thereof.
Alternatively the insulating board is free of facings.
Detailed Description The invention provides an insulating medium comprising a plurality of hollow microbodies such as microspheres bonded in any suitable resin or matrix. The resin used to bond the microspheres may be unfoamed, or a foam type resin such as phenolic, polyurethane or polyisocyanurate, which may contain a blowing agent or blowing agent mixtures to enhance the thermal resistivity of the matrix. Other thermoset organic or inorganic resins such as, but not exclusively, a polyester, an epoxy, acrylic, silicone or urea formaldehyde or vinyl ester material, may be used to bind the microspheres.
The microbodies may be filled with a porous material, such as open cell organic foam or porous inorganic material. 070752 -4The hollow microspheres may be all of the same size or may be of different sizes to provide a more packed matrix. In particular, the hollow microspheres may possess a bimodal or trimodal particle size distribution which provides the ability to maximise packing density.
The hollow microspheres may be formed from any suitable stable gas impermeable material such as glass. To provide the required insulation properties the hollow microspheres have a substantially reduced internal pressure close to vacuum, that is of less than 0.1 bar a, preferably less thanO.Ol bar a, most preferably less than 0.001 bar a, and ideally less than 0.0001 bar a [1 bar a = 100 kPa = -750 mm Hg], These hollow microspheres may or may not incorporate an internal metallic reflective layer as described in US patent 4,303,732 (L B Torobin), the contents of which are incorporated herein by reference.
The invention also provides an insulation board including the insulation medium. Such a board may have facing(s) or may be without facings. The faceless board may have one or more faces coated with a suitable coating such as a metallised paint. This technology is described in our WO 00/05051, the contents of which are incorporated herein by reference.
The strength of the foamed resin matrix is sufficient to maintain integrity of the insulation panel with or without facings. For economic production of the panel it is desirable to keep the foam matrix density to less than 40 kg/m3, preferably less than 30 kg/m3, and ideally less than 25 kg/nf.
To manufacture an insulating board or panel, a first facing is led from a supply reel to a foam lay down area and liquid foam reactants are deposited from a dispensing head and spread across the facing. Hollow microspheres are introduced either before, with or just after the liquid foam reactants. A second facing from a second facing supply reel is laid down over the liquid foam reactants and hollow microspheres forming a sandwich. The sandwich may be passed through a nipping means to evenly spread and to set the -5070752 thickness ofthe foam. The sandwich is then passed through an oven in which the foam expands under a free or controlled rise technique. The output from the oven is a continuous length of panel comprising outer and inner facings with an insulating core therebetween. The panel is then cut to a desired length and, generally, palletised and stacked ready for delivery to a customer. One such process is described in GB 2340432A, the entire contents of which are incorporated by reference.
In one variation of the invention, at least one of the facings may be removed from the panel and preferably re-wound onto a reel for re-use, prior to cutting the panel to the desired length. Both of the facings may be separately removed from the core and rewound onto separate reels for re-use. One such process is described in WO 00/05051 A, the entire contents of which are incorporated by reference.
A coating may be applied either in-line or off-line to one or both faces of the foam after removal of the facing(s). The coating is typically a paint, containing non-gas permeable flake-like particles or platelets such as metal or glass flakes. The paint may be an aluminium flaking or non-flaking paint or a nano-composite. Such paint coatings provide a hairier to provide low gas permeability. Thus, the panels are resistant to gas permeating from within the cells of the foam and from air permeating in. The net effect of the painting of the foam faces is to substantially maintain the thermal conductance or λ-value of the foam over prolonged periods of use. Thus, such paints provide a gas barrier to reduce gas transfer between the cells of the foam when exposed to atmospheric conditions. Hence improved aged thermal conductivity properties are provided. This is especially important for polyurethane, polyisocyanurate foams and phenolic foams.
The paint may be formulated to have specific properties. For example the paint may be fire resistant. The paint is preferably applied in-line just after facing removal. The are/weight is at least 0.5g/m2 and is preferably 10 to 50g/m2. The upper limit will be determined by the type of application and the economics of the process. 07 52 -6The paint may be applied by passing the panel between coating calendering rollers to apply paint to both faces. Alternatively the foam panel may be passed through a curtain of paint, for application. The paint may also be spayed onto one or both faces by spray heads.
Electrostatic techniques may also be used to apply the paint. For example, the frame along which the foam passes may be charged to repel paint which is consequently preferentially attracted to the faces of the foam.
After coating, the paint is cured. For example, a localised heat or radiation source may be applied in the form of a directed hot air source, an IR source, a UV source, a microwave source or the like. The foam may also be cured in an oven. To provide additional curing time, in-line, the panel may be passed through an accumulator.
To assist coating and/or curing the panel may be turned on edge.
Ideally, if required the facings can be removed when the panel exits the oven and in advance of cutting. Alternatively, it may be possible to remove the facings from the panel as the panel passes through the oven. The removal within the oven would be at a stage where the foam has sufficiently cured but before final cooling. Then one or both facings may be more easily removed at this particular stage. Indeed, both facings may not have to be removed at the same stage.
The re-wound removed facings are coiled and the coils may then be re-used at the infeed either as a first or second facing. If desired, the facing may be reversed for re-use and/or a cleaning means may be provided for the collected facing before re-use.
To facilitate removal, one or both facings may be treated with a release agent on the foam-engaging face of the facing. For example, PTFE silicone or wax may be applied.
In order to improve the facing removal, preferably the outer foam layers are not corona treated. 070752 -7The foam preferably has a significant cellular structure for use in thermal and/or acoustic insulation applications. The foam is preferably based on polyurethane, polyisocyanurate, or phenolic resins.
Example 1 Insulation panel with facings.
A typical foam formulation which may be used in the process of the invention is as follows: A B C (parts by weight) Polyester polyol 70 Polyether polyol 30 Silicone surfactant 1 1 Dimethylcyclohexylamine 0.6 Potassium acetate in monoethyleneglycol 3.0 Water 1.3 141b Blowing agent (Solvay) 25 20 Fire Retardant (tris -2-chloroisopropyl phosphate) 10 Crude methylene diphenyl isocyanate (MDI) 100 120 (e.g. 44V20L as supplied by Bayer) Hollow microspheres 100 The hollow microspberes are introduced into mix C prior to dispersion in a closed tank using a low shear mixing device. When fully mixed, mix C is introduced as a low pressure (<10 bar g) third stream into the impingement mixing chamber of the two high pressure (>100 bar g) streams from mixes A and B. An impingement mixing device is described in our EP1311596, the entire contents of which are incorporated herein by reference. 070752 -8The mix is laid down onto a moving tri-laminate foil/kraft/foil facing and a second facing introduced above it before both are passed into a heated laminator set at a fixed gap where the foam is fully expanded. After exiting the heated laminator as a solid laminate the panels are cut to size and the edges trimmed square to produce insulation panels in the normal way.
The thermal conductivity of this panel is enhanced o ver the normal thermal conductivity (λ-value 0.015 vs. 0.019 W/m.K) of a polyurethane panel without hollow near vacuum microspheres in the mix, and this is not seriously affected by puncturing the panel, unlike a monolithic vacuum panel.
Example 2 In this case the process of example 1 is repeated, but the first and/or second removable facings are typically selected from: polyolefin films (such as polypropylene, high or medium density polyethylene, low or linear low density, polyethylene), poly halogenated polyolefins (such as polytetrafluoro ethylene), waxed paper and waxed plastic films, other suitably treated paper, plastic, metal foil or glass films and facings grp films, fabrics and combinations thereof such that the facing can be continuously removed from the foam without significant damage to either lacing or foam during or just following the production process.
Example 3 In this example the hollow near-vacuum microspheres are low-shear mixed with a aqueous-borne polyurethane adhesive formulation in a closed tank to form a mix of high viscosity (>8000 mPa.s). This mix is then heated and poured via a fanned chute continuously across the width onto a facing carrier of glass matting. The second glass mat facing is introduced above this and it is passed into a heated laminator set at a fixed gap. The sides of the laminator are constrained by steel plates so that the volume of mix is matched exactly to the volume of the final product. The panel is cut to size before 070752 -9stacking and left to cure fully either for several days in a well ventilated covered area at ambient temperatures, or accelerated curing by placing the stacks in drying ovens at elevated temperatures (typically 50°C).
By this example insulation panels with λ-values of < 0.010 W/m.K are prepared.
Example 4 In this example, the procedure of Example 1 is followed, but the blowing agent 141b is replaced with cyclo-pentane at 15 parts in mix A and 12 parts in mix C.
Hollow Microbodies The hollow microbodies are substantially gas impermeable and preferably have a low aspect ratio and may be generally spherical in shape. Preferably the microbodies are microspheres. The hollow microspheres may be formed as described in the US patent 4,303,732 or other methods to provide a low internal void pressure of less than 0.1 bar a, preferably less than 0.01 bar a, most preferably less than 0.001 bar a, and ideally less than 0.0001 bar a.
The preferred material is sodium borosilicate glass, but other non-gas permeable waterresistant inorganic materials may be used such as alumino silicate or calcined clay. The microspheres may also be of an organic material such as phenolic microballoons or thermoplastic microspheres. The material should be capable of forming into microbodies, especially microspheres and is ideally capable of forming a film.
The hollow microbodies may be coated with a gas permeability reducing agent such as a metallic material, for example aluminium flake. Either the inner and/or outer surface of the hollow microbodies may be coated.
The microbodies may have a particle size up to 1cm across 070752 -ΙΟThe typical microbody, especially microsphere particle size range is 5 to ΙΟΟΟμηι, preferably 10 to 200 μιη.
The panel may be used as an underfloor, roof or wall insulation panel. Alternatively the panel may be an insulation liner panel, for example for use in refrigeration applications such as for a refrigerated transport vehicle.
The panel thus formed has superior insulation properties and will typically achieve a λvalue of <0.015 W/m.K , and preferably <0.010 W/m.K. The panel also has the very considerable advantage of being more durable and less prone to damage, especially in exposed environments. The panel can be punctured by a nail or cut to size without significantly adversely affecting the insulating properties. Thus, the boards to be cut and shaped on site without significant loss of thermal insulation efficiency.
The invention is not limited to the embodiments hereinbefore described which may be varied in detail.

Claims (32)

1. An insulating medium having a plurality of hollow microbodies bonded in a suitable resin, the hollow microbodies having an internal void pressure of less than 0.1 bar a.
2. An insulating medium as claimed in claim 1 wherein the microbodies have a low aspect ratio.
3. An insulating medium as claimed in claim 1 wherein the microbodies are filled with an open celled organic foam or porous inorganic material
4. An insulating medium as claimed in claim 1 or 2 wherein the microbodies are of generally spherical shape.
5. An insulating medium as claimed in any of claims 1 to 4 wherein the microbodies have a particle size up to 1cm across.
6. An insulating medium as claimed in any of claims 1 to 5 wherein the microbody size range is from 5 to 1000pm.
7. An insulating medium as claimed in any of claims 1 to 6 wherein the microbody size range is from 10 to 200 pm.
8. An insulating medium as claimed in any preceding claim wherein the microbodies are microspheres.
9. An insulating medium as claimed in any receding claim wherein the internal void pressure of the microbodies is less than 0.01 bar a.
10. An insulating medium as claimed in any preceding claim wherein the internal void pressure of the microbodies is less than 0.001 bar a. -120/0752
11. An insulating medium as claimed in any preceding claim wherein the internal void pressure of the microbodies is less than 0.0001 bar a.
12. An insulating medium as claimed in any preceding claim wherein the resin is of a foam or non foaming material such as a phenolic, polyurethane or polyisocyanurate material.
13. An insulating medium as claimed in any of claims 1 to 11 wherein the resin is of a foam or non foaming material such as a polyester, an epoxy, acrylic, silicone, urea formaldehyde resin or vinyl ester.
14. An insulating medium as claimed in any preceding claim wherein the hollow microbodies are of substantially the same size.
15. An insulating medium as claimed in any of claims 1 to 13 wherein the hollow microbodies are of different sizes.
16. An insulating medium as claimed in claim 15 wherein the hollow microbodies have a bi-modal size distribution.
17. An insulating medium as claimed in claim 15 wherein the hollow microbodies have a tri-modal size distribution.
18. An insulating medium as claimed in any preceding claim wherein the microbodies are of an inorganic material.
19. An insulating medium as claimed in any preceding claim wherein the microbodies are of glass material.
20. An insulating medium as claimed in of claims 1 to 18 wherein the microbodies are of alumino silicate material. -13070752
21. An insulating medium as claimed in any of claims 1 to 18 wherein the microbodies are of calcined clay material. 5
22. An insulating medium as claimed in any of claims 1 to 17 wherein the microbodies are of organic material.
23. An insulating medium as claimed in claim 22 wherein the microbodies are of a phenolic material.
24. An insulating medium as claimed in claim 22 wherein the microbodies are of a thermoplastic material.
25. An insulating medium as claimed in any preceding claim wherein the hollow 15 microbodies are coated with gas permeability reducing material.
26. An insulating medium as claimed in claim 25 wherein the coating material is a metallic material. 20
27. An insulating medium as claimed in claim 25 or 26 wherein the coating is of aluminium flake material.
28. An insulating medium as claimed in any of claims 25 to 27 wherein the internal surface of the microbodies are coated with the coating material.
29. An insulating medium as claimed in any of claims 25 to 28 wherein the external surface of the microbodies are coated with the coating material.
30. An insulating medium substantially as hereinbefore described.
31. An insulating board having an insulating medium as claimed in any preceding claim. -1432. An insulating board as claimed in claim 31 including a facing on one or both faces thereof. 5 33. An insulating board as claimed in claim 31 which is free of facings.
32. 34. An insulating panel having an insulating medium as claimed in any of claims 1 to 30.
IE20070752A 2006-10-17 2007-10-17 An insulating medium IE20070752A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
IE20070752A IE20070752A1 (en) 2006-10-17 2007-10-17 An insulating medium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IE20060764 2006-10-17
IE20070752A IE20070752A1 (en) 2006-10-17 2007-10-17 An insulating medium

Publications (1)

Publication Number Publication Date
IE20070752A1 true IE20070752A1 (en) 2008-06-11

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Family Applications (1)

Application Number Title Priority Date Filing Date
IE20070752A IE20070752A1 (en) 2006-10-17 2007-10-17 An insulating medium

Country Status (2)

Country Link
IE (1) IE20070752A1 (en)
WO (1) WO2008047334A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007034298A1 (en) 2007-07-24 2009-01-29 BSH Bosch und Siemens Hausgeräte GmbH Refrigeration unit with vacuum insulation
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
US11518917B2 (en) 2020-05-07 2022-12-06 Alliance For Sustainable Energy, Llc Conductive polymers with reduced radiative transport and emissivity for insulating materials

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US948541A (en) * 1908-03-23 1910-02-08 Clyde J Coleman Heat-insulating wall.
US3978269A (en) * 1973-11-26 1976-08-31 Coors Porcelain Company Hollow pellets and method of making same
US4079162A (en) * 1974-03-20 1978-03-14 Aim Associates, Inc. Soundproof structure
US4349456A (en) * 1976-04-22 1982-09-14 Minnesota Mining And Manufacturing Company Non-vitreous ceramic metal oxide microcapsules and process for making same
US4303732A (en) 1979-07-20 1981-12-01 Torobin Leonard B Hollow microspheres
US5077241A (en) * 1988-11-17 1991-12-31 Minnesota Mining And Manufacturing Company Sol gel-derived ceramic bubbles
US6103003A (en) * 1998-03-28 2000-08-15 Ledbetter; C. Burgess Textured coating and method of applying same
AU4643399A (en) 1998-07-21 2000-02-14 Kingspan Research And Developments Limited A method for manufacturing a foam panel
ATE330988T1 (en) 2000-07-21 2006-07-15 Kingspan Res & Dev Ltd METHOD AND APPARATUS FOR PRODUCING PHENOLIC FOAM BY MIXING THE COMPONENTS IN AN IMPACT FLOW
AU2003250614B2 (en) * 2002-08-23 2010-07-15 James Hardie Technology Limited Synthetic hollow microspheres

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