The invention relates to vacuum insulation, possibly vacuum insulation wallpaper for interior insulation, and to a production process for producing vacuum insulation. The invention also relates to polyhedrons such as cubes for vacuum insulation and use of zeolite or Metallic Organic Framework for producing vacuum insulation.

Background of the invention

The building sector differs from the transportation sector and appliances sector in a slow replacement rate of walls, ceiling, floors and other parts of a building. Old houses are only substituted with new houses at a very slow pace of 1-3% a year and the slow population growth in industrialised nations means that only another 1-2% are added. The only two ways to achieve significant energy savings on heating and cooling is to install more efficient heaters/coolers and/or to insulate the existing buildings.

Mounting of conventional insulation includes moving heating installations, moving electric switches and sockets, extending window sills, loosen

approximately 5% of the indoor floor area and reducing ceiling height. The cost is high for installing insulation and plasterboards and for painting, providing a good finish. Mounting of conventional insulation takes much time and renders the house or apartment un-inhabitable in the meantime. Depending on complexity, the costs are 150-250 USD/m ² . In cities, square footage of one m ² may cost around 5.000 USD. Therefore, loosing 5% of the square footage adds another 250 USD to the cost in lost revenue, when selling the house or apartment.

Insulation on the outside of the house or apartment, together with finishing and painting, cost around 200 USD/m ² . If windows also have to be moved during provision of the insulation, the costs are much higher. Until now, both extra internal insulation and extra external insulation have been difficult to sell. However, there is still a very large uncovered need for insulation of existing buildings.

Insulation of existing buildings has to offer something very convenient, fast, inexpensive and easy to do, something that may be done anyway, like painting and/or wallpapering, something that may be done by the handy Do-It-Yourself house owner or apartment owner.

Properties of insulation. Heat is transmitted through a material in three ways: Conduction

Thermal conductivity is a property of a material to conduct heat and evaluated primarily in terms of Fourier's Law for heat conduction. Conduction is roughly proportional to a density of materials. Light materials like aerogel has minimal thermal conduction.

Radiation

Transfer of energy from a movement of charged particles within atoms is converted to electromagnetic radiation. Radiation is infrared light. Radiation can be reduced with low emission materials, that are stopping infrared light like polished metal, titanium dioxide, graphite and similar materials. Radiation can also be reduced by many layers, reducing radiation a little each time radiation is passed from one layer to the next.

Convection

Conduction is transfer of energy between an object and its environment, due to fluid motion. Conduction is proportional to a temperature difference and to a vertical size of the cavities and can be reduced with many small cavities. It can also be reduced with gas having a weight larger than atmospheric air like Krypton, Argon, and CO2.

Knudsen effect

Aerogels and other microporous and mesoporous materials may have a thermal conductivity smaller than the gas the materials contain. This is caused by the Knudsen effect, reducing the thermal conductivity in gases when the size of the cavity encompassing the gas becomes comparable to the mean free path. Effectively, the cavity restricts the movement of the gas particles, decreasing the thermal conductivity, in addition to eliminating convection. For example, thermal conductivity of atmospheric air is about 25 mW/m-K at one atmosphere and in a large container, but decreases to about 5 mW/m- K in a pore of 30 nano-meters in diameter.

Vacuum

Convection and conductance in a gas is also reduced proportional to pressure. The number of molecules per cm ³ in air at ambient atmospheric normal pressure is approximately 2.5xl0 ¹⁹ . By comparison, the normal number is three of molecules per cm ³ in intergalactic space. A manmade vacuum considered to be of high order in a dewar contains approximately 3.3xlO ⁿ molecules per cm ³ . However, it is very difficult to maintain a vacuum at a pressure of 10 ^"8 atmosphere, because even the smallest outgassing from materials will increase the pressure.

Insulation materials like mineral wool and plastic foam has a large outgassing due to a large surface of outgassing material. A dilemma is, that very porous materials are wanted for good insulation, but porous materials, and particularly micro porous materials, have an extremely large surface compared to a solid material. The problem can be overcome by a combination of high temperature, that boils the gas out of the material, evacuation over a longer period of time, and adding a getter. A reduction to 10 ^"3 atmosphere in Knudsen effect materials equals a reduction to 10 ^"8 atmosphere in a larger cavity.

Getter

A getter is a deposit of reactive material that is placed inside a vacuum system, for the purpose of completing and maintaining the vacuum. When gas molecules strike the getter material, the gas molecules combine chemically or by adsorption with the getter. Thereby, the getter removes small amounts of gas from the evacuated space. A getter is activated by heating the getter above a threshold temperature for a duration of hours in vacuum. The getter absorbs outgassing at the surface. A large surface of the getter is more efficient than a small surface of the getter.

Both outgassing from material and activating the getter is effective at temperatures above 300°C in vacuum. The higher the temperature, the faster the process. When gasses leave micro-porous materials, the gasses diffuse from one cavity to the next. All the pores in molecular sieves like zeolite or Metallic Organic Framework are interconnected, making evacuation of this kind of material much faster and more efficient compared to non-molecular sieves.

An optimal insulation material is achieved from a material with the following properties:

a) Minimal relative density .

b) Radiation-reducing surfaces of the insulation material.

c) Micro porous cavities, where the Knudsen effect is active

d) Vacuum at around 10 ^"3 atmosphere and impermeable containment of the vacuum

e) A getter with a large surface to absorb further outgassing.

A material having these properties may have a heat transmission of 0.004 W/m-K, which is roughly ten times better than prior art mineral wool and plastic foam insulation materials.

Prior art products

Cabot Corporation produces a nanogel, which is an aerogel that is not evacuated and has a thermal performance around 3 times better than mineral wool. The material can be cut, but is not sold as wallpaper. Price is around 100 USD/m ²

Aspen Aerogels, Inc., produces an aerogel called Spaceloft®, which is a kind of wallpaper. The material is sold without a finished surface. The U-value is around 2,5 times better than mineral wool and the price is around 60 USD/m ² Morgan Porextherm produces Vacupor® panels, which have a core insulation around 8 times higher than mineral wool, but in real life the value is

significantly reduced at the edges. The price of Vacupor® is around 150 USD/m ² . However, Vacupor® is not very practical for building insulation, because Vacupor® cannot be cut to measure. Vacupor® will also be destroyed first time somebody drills a hole through the panels or hammer a nail trough the panels.

Saarpor Klaus Eckhardt GmbH produces a 4 mm Saarpor Graphite Insulating Lining wallpaper, which has insulation property of 20% better than mineral wool. However, the insulation is insignificant from an energy point of view.

Hy-Tech Thermal Solutions, Inc., claim having invented a vacuum microsphere filler material as part of a CVM (ceramic vacuum matrix) technology.

US20120231161A1 describes a process for production of vacuum

microspheres, utilizing a spray dryer having a top mounted atomizer rotary wheel and a side or bottom mounted dual fluid nozzle, forming microspheres by spraying solution from the top mounted atomizer rotary wheel and simultaneously coating the microspheres by spraying solution from the side or bottom mounted dual fluid nozzle, transferring the microspheres to a secondary heating unit, and drying the microspheres, all under vacuum of between 100 N/m ² to 500 N/m ² .

US20120231161A1 does not disclose a getter. The problem with vacuum in each microsphere is that one cannot expand a balloon with a vacuum.

KR2009000249 discloses a warmth-keeping wallpaper using vacuum glass beads to reduce the fuel cost and to improve a warm convenience of a construction. The warmth-keeping wallpaper using the vacuum glass beads comprises an original paper layer; a resin layer, which is formed on the original paper layer; and a printed layer, which is formed on the resin layer, where the resin layer comprises a first resin layer and a second forming resin layer, and where the first resin layer and the second forming resin layer contain the vacuum glass beads. KR20090002459 does not disclose the warmth-keeping wallpaper having properties or features ensuring covering an entire wall with vacuum glass beads.

US 4 303 732 A discloses hollow glass microspheres made from a low heat conductivity glass composition containing a high vacuum and a thin metal coating deposited on the inner wall surface of the microspheres are described. The hollow glass microspheres can also be made to contain a thin transparent or reflective metal coating deposited on the inner wall surface of the microspheres by adding to the blowing gas small dispersed metal particles and/or gases of organometaliic compounds and decomposing the organometallic compounds. The hollow glass microspheres can be made from low heat conductivity glass compositions.

DE 195 19 984 Al discloses a thermal insulation layer or wall, of the required dimensions, is filled to the max. with evacuated hollow balls which can be loose. The shells for the hollow balls are of wood, glass, PVC and the like, with the maximum quotients of bail diameter to shell thickness. The insulating layer can be covered with heat reflection and shroudings against electro-magnetic rays, and a watertight and sealed plastics covering.

Ail above prior art discloses beads being hollow spheres because only spheres can withstand atmospheric pressure when evacuated and hollow.

DE 10 2005 054 805 Al discloses a vacuum insulation panel having a stable, plate-like carrier and a method for manufacturing the vacuum insulation panel. The panel is divided into several small, evacuated chambers, which are individually closed in a steam and gas-tight manner, and cavities of the chambers are empty or are filled with prefabricated vacuum insulating elements or with an open-cell carrier material.

DE 10 2005 054 805 Al discloses a common subdivided containment.

CH 699 099 A2 discloses a panel having a closed vacuum chamber provided with closed vacuum cells, The vacuum chamber is arranged between two plates. The vacuum cells are formed in a spherical shape and a honeycomb shape. The vacuum chamber is made of foamed material e.g. foam plastic such as polyurethane or foam glass. Closing plates are arranged on both sides of a honeycomb-like ceil wail structure and connected with the honeycomb-like cell wall structure in an airtight manner. The vacuum cells exhibit larger dimension in range of 0.01 mm to 10 mm.

CH 699 099 A2 actually discloses two different inventions. One like the first group of hollow sphere prior art above and one similar to a honeycomb structure.

WO 91/19867 Al discloses an insulation panel with two adjacent metal sheets spaced close together with a plurality of spherical, or other glass or ceramic beads positioned between the sheets to provide support and maintain the spacing (15) between the metal sheets when the gases are evacuated to form a vacuum. The two metal sheets are textured with ribs or convex bulges in conjunction with the glass beads to maximize the structural integrity of the panels while increasing the spacing between beads, thereby reducing the number of beads and the number of thermal conduction paths.

US 5,107,649 A discloses an ultra-thin compact vacuum insulation panel. The panel is comprised of two hard, but bendabie metal wall sheets spaced apart from each other and welded around the edges to enclose a vacuum chamber. Glass or ceramic spacers hold the wall sheets apart. The spacers can be discrete spherical beads or monolithic sheets of glass or ceramic webs with nodules protruding therefrom to form point or line contacts with the metal wall sheets. Corrugations accommodate bending and expansion, tubular insulated pipes and conduits.

WO 91/19867 Al and US 5,107,649 A disclose spheres , which are spacers keeping the containment apart. The vacuum is outside the spheres rather than inside

GB 2464369 A discloses a panel comprising an aerogel fibre composite between fibre- reinforced layers. The composite is preferably hydrophobic. The fibre-reinforced layers may be bonded to the core with fire resistant glue. The reinforced layers comprise woven or knitted glass or mineral fibre tissue, paper, or fibre reinforced polymer (FRP) . The panels can be bonded to a building's wall or ceiling by means of an acrylic adhesive. Disclosed polyester fibre reinforced aerogels include silica, alumina, similar metal oxides, carbon, resocinol formaldehyde resin, meiamine formaldehyde resin, polyimide, polyurethane and polyisocyanurate.

The panel is not evacuated to vacuum and therefore has a poor insulation performance

Functionality requirement of insulation

Optimal properties of a Do-It- Yourself material for insulation of existing constructions, especially houses and apartments, would be:

a) Thin material, but still highly efficient insulation material

b) Easy to cut material to measure a wall, ceiling, floor etc.

c) Easy mounting with no need for special handyman skills

d) Not destroyed by nails and drills driven through the material

e) Finished surfaces with no need finishing after mounting.

f) Long lifetime, especially for use in houses and apartments

The prior art materials fall short of one or more of these properties.

Thus, there is a need for a product, which has at least some of the optimal properties, and which reduces or even eliminates the above-mentioned disadvantages of the prior art insulation.

Summary of the invention

The objects is obtained by the invention of a vacuum insulation comprising vacuum evacuated beads composed from a core material with cavities so small that the Knudsen effect significantly reduces Brownian movements, and with getter functionality and contained within a vacuum impermeable containment, and where said vacuum evacuated beads are attached to each other and to a vacuum insulation composite. Vacuum insulation according to the invention may be selected from one or more of the following vacuum insulations: wallpaper, wall panels, flooring insulation, window frames, flooring tiles, wall tiles, ceiling tiles, plaster board cladding. In the following, reference will mostly be made to wallpaper.

Reference to wallpaper must not be viewed as limiting the invention in general, which is to vacuum insulation in general.

For filling the gaps between the beads and preventing thermal bridges along the containment surface of the beads and making the composite stick together said beads are attached to each other.

The vacuum insulation according to the invention has a minimal weight due to thousands of micro porous cavities surrounded by walls of a few atoms thickness. Micro-porous cavities are provided at a scale of 3- 30 nano-meter, where the Knudsen effect is active. Vacuum at around 10 ^"3 atmosphere is provided inside the cavities. An impermeable containment of this vacuum is provided. A getter is provided with a large surface to absorb further

outgassing. Radition thus passes approximately a million layers in one cm, reducing radiation to almost zero.

For minimizing conductance and convection, said materials with cavities are so small that the Knudsen effect significantly reduces Brownian movements- The materials are preferable molecular sieves like zeolites or Metallic Organic Frameworks

For sustaining vacuum, said containment material is preferably ceramics or metal in a thickness of preferably 100 nano-meter, preferable sprayed or sputtered on the beads in vacuum.

For sustaining a good vacuum in the evacuated beads for a long period of time, comparable with a lifetime of a building, said getter material is preferably selected from zeolite or Metallic Organic Framework.

Micro porous materials like zeolite and Metallic Organic Framework has an extremely large surface to volume ratio. Zeolite and Metallic Organic Framework has a very special ordered structure providing minimal thermal conduction through pillars of only one molecule thickness.

Said vacuum is preferably within an order of magnitude around 0,001 atmosphere.

The vacuum insulation composite is preferably made with a finished surface from a durable, cleanable, flexible material preferably from paper, plastic, polycarbonate, glass fibre, woven or non woven fibres, metal foil.

The backside is preferably covered with a self-adhesive material with protective removable cover for easy mounting onto a surface.

Key benefits of the invention, compared to known Vacuum Insulation Panels, are:

a) The vacuum insulation can be cut to measure, unlike any other vacuum insulation.

b) The insulation is not at risk of puncturing or degrading as is the case with known Vacuum Insulation Panels.

c) Nails and drills will only harm a few vacuum evacuated beads, without destroying the entire vacuum insulation.

d) The vacuum is sustainable during the lifetime, or at least most of the

lifetime, of use of the vacuum insulation.

Compared to conventional insulation,

e) 10 mm of the vacuum insulation of the invention insulates like 10 cm

conventional insulation.

f) Wallpaper produced from vacuum insulation according to the invention is much easier and much faster to mount and a price is less of the wallpaper of the invention.

According to a possible embodiment of the invention, the vacuum evacuated beads of the vacuum insulation are polyhedrons, preferably cubes, fitted in abutment with each other, where said polyhedrons such as cubes preferably are made from extruded zeolite or Metallic Organic Framework being coated with an impermeable coating,

Polyhedrons and especially cubes are supported by molecular sieve material. The benefit of cubes is that cubes fit closely to each other, improving insulation.

Alternatively, the embodiment of the invention can be made with another material than zeolite or Metallic Organic Framework having the properties needed such as molecular sieves, mesa-porous silica, nano-porous materials, or aluminum phosphate.

According to another embodiment of the invention, said cubes has a size of 10 mm x 10 mm x 10 mm. The advantage is that the vacuum insulation can be cut to measure close enough for most uses.

According to another embodiment of the invention, said impermeable coating is made from silicium carbide, SiC. The advantage is, that silicium carbine, SiC, used for the impermeable coating may provide a coating being resistant to wear and/or being non-porous. One such coating material is silicium carbide, SiC. Coating with SiC is typically around 80 micrometers, which will cover the pores, which are a thousand times smaller. Research report "SiC Coatings for Carbon/Carbon Composites Fabricated by Vacuum Plasma Spraying

Technology" by Cui Hu, Yaran Niu, Hong Li, Musu Ren, Xuebin Zheng, Jinliang Sun document, that SiC technology can be used in vacuum plasma spraying technology.

According to another embodiment of the invention, said impermeable coating is made from graphene oxide. The advantage is, that graphene oxide used for the impermeable coating may provide a coating being optically transparent and/or being resistant to corrosion. Coating with graphene oxide is typically around 20 nano-meters and and may also be very thin as documented in "Impermeable barrier films and protective coatings based on reduced graphene oxide" by Y. Sul, V.G. Kravetsl, S.L. Wong l, J. Waters2, A.K. Geiml & R.R. Nair

According to another embodiment of the invention, said impermeable coating is made from plasma deposited metal. The advantage is, that plasma deposited used for the impermeable coating may reduce process temperatures during coating of the cubes and may provide a coating with physical properties selected among a range of physical properties.

According to another embodiment of the invention, said vacuum insulation has a tile format, and a size of the tile format is preferably from 30 x 30 to 100 x 100 cm. The advantage is, that the vacuum insulation may be used as individual tiles at selected positions on a wall or ceiling.

A preferred embodiment constitutes a vacuum insulation vacuum insulation, which is covered by cubes fitting tight to each other and are made from extruded zeolite matrix or Metallic Organic Framework, where said cubes are baked for sintering and outgassing and baked in vacuum for activation of getter, and where said cubes are coated with multiple layers of impermeable coating while in vacuum.

A preferred embodiment of vacuum insulation vacuum insulation is made from : a) Cubes made from extruded zeolite or Metallic Organic Framework b) Said cubes baked for sintering and outgassing

c) Said cubes exposed to high temperature and vacuum for activation of getter inside the cubes

d) Said cubes coated with multiple layers of impermeable coating, while in vacuum

e) Said vacuum insulation with said cubes attached to tape with adhesives on one or both sides

f) Said cubes preferably having a size of 10 mm x 10 mm x 10 mm or similar g) Said coated cubes used for any insulation material for any insulation

purpose Zeolite or Metallic Organic Framework are preferred materials for the vacuum evacuated beads, because of the following properties of zeolite or Metallic Organic Framework: has a low thermal conductivity, has a crystal structure creating cavities of the preferred Knudsen effect size, has open connection between these pores making evacuation feasible, has a small pore size that can be covered with a thin coating, has an extremely large internal surface functioning as getter, has good strength because the pores are made from the crystal structure rather than from bubbles, is made from inexhaustible resources without any environmental side effects.

A size of 10 mm x 10 mm x 10 mm may be chosen because 10 mm thick insulation is appropriate for most purposes. A grid of 1 cm cubes can be cut to measure close enough for most use. Smaller strips of 5 mm square cubes for filling gaps is possible. Larger 20 mm square cubes are possible providing for larger surfaces, where the vacuum insulation need not be cut.

Cubes chosen because the interface between cubes creates minimal thermal bridges and therefore maximum insulation performance as long as the coating of the cubes is thin.

A cube having a size of 10 mm x 10 mm x 10 mm with pores of 100 nanometers has roughly 60 billion pores on the surface to be covered.

The cubes are covered with one thick layer or multiple thin layers of coating to avoid pin holes. It is believed that layer(s) at least as thick as the pore diameter is needed to cover the pores.

A coating should meet one or more of the following properties: Minimum 100 nano-meter thick, completely impermeable coating, chemically stable, durable, mechanically scratch resistant

Production process

An industrial production process for producing a vacuum insulation with cubes may be: - Mixing zeolite or Metallic Organic Framework with clay

- Extruding the mixed material in a 1 x 1 cm rod

- Sintering the rod

- Cutting the sintered rod every 1 cm for 1 x 1 x 1 cm cubes

- Evacuating the cubes in a vacuum oven

- Activating a getter effect of the zeolite or Metallic Organic Framework by heating the cubes

- Coating the cubes in vacuum with multiple layers of coating one after the other and turning the cubes during the process of coating

- Letting the cubes leave the vacuum chamber

- Putting the cubes next to each other by a sloping vibration plate and aligning the cubes with some rulers,

- Sandwiching the cubes between polymer foil.

Description of the Figures

The invention will become more fully understood from the detailed description given herein below. The accompanying figures are given by way of illustration only, and thus, they are not limitative of the invention. In the accompanying figures:

Fig. 1 is a drawing showing a possible molecular structure of zeolite

Fig. 2 is a sketch showing spherical vacuum evacuated beads for a wallpaper,

Fig. 3 is a sketch showing a cubical vacuum evacuated bead for a wallpaper,

Fig. 4 is a sketch showing a cubical version of beads for a wallpaper composite,

Fig. 4 is a cross-section showing cubes of the wallpaper, and attached to each other.

Detailed description of embodiments of the invention

Reference is now made in detail to the figures for the purpose of illustrating preferred embodiments of the invention. In the following, reference is made to wallpaper as a preferred embodiment of the invention. But, vacuum insulation according to the invention may be selected from one or more of the following vacuum insulations: wallpaper, wall panels, flooring insulation, window frames, flooring tiles, wall tiles, ceiling tiles, plaster board cladding. Therefore, reference to wallpaper must not be viewed as limiting the invention in general, which is to vacuum insulation in general.

Fig. 1 shows the molecular structure of zeolite. The structure is reproduced complete accurate throughout the material because it is a molecular structure, not a man-made structure. The entire figure is in the magnitude of 50-500 nano meter (depending of the chemical formula), so this figure is around 2 million times enlarged.

The figure illustrates that:

• All the cavities in the material are interconnected enabling evacuation of the cavities.

• The very large surface area of the material enabling getter functionality binding the gas molecules to the surface.

• That the thermal conduction through the solid material is trough

columns the width of a single atom

• That the cavities are sufficiently miniature to achieve Knudsen effect slowing the speed of the molecules

Fig. 2 is a cross-sectional view through the vacuum evacuated beads 4. The filler material is very small compared to the beads, so each bead is composed from millions of filler particles (not shown) contained inside a gastight surface 10 of the beads 4. The beads 4 are preferably zeolite grains sintered together with clay or aluminium material, and where the grains are abutting each other, forming a larger volume in a way that ensures access to cavities 8.

Fig. 3 is a section in a vacuum insulation wallpaper 12 showing a cubical version of vacuum evacuated beads 4 attached to the wallpaper. The cubes 4 can be made cubical by laser cutting a sheet material, preferably highly porous zeolite, because zeolite also has a getter effect. Other material having the properties needed may be molecular sieves, mesa-porous silica, nano-porous materials, or aluminum phosphate. The water and gasses within these billions of interconnected pores are evaporated and outgassed in vacuum at temperatures above 100 C to speed the process. The getter effect is activated at even higher temperatures when sintered.

The zeolite is sintered into a cube or hexagonal geometry that can pack tight. This 1 x 1 x 1 cm cube is made from a million pores structures in all directions and each surface has 1.000.000.000.000 pores in each of the 6 surfaces. While still in vacuum the surface is coated with in impermeable coating made from metal, carbide, graphene oxide, ceramics or similar covering the entire surface of the cubes.

Fig. 4 shows the cubes glued to each other into a square net structure producing a thin insulation material and Fig. 5 shows a cross section illustrating 1 cm thin insulation material can be protected from wear and punctual load sandwiched between load distributing surfaces made from paper, polymer, metal, wood ceramics.

List of reference numerals

2 - Wallpaper composite

4 - Vacuum evacuated beads

6 - Cavities between beads

8 - Airtight surface of beads

10 - Vacuum insulation wallpaper