• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to rigid foams mineral and porous, obtainable after stabilization of a mixture between a silicate suspension loaded with particles and / or mineral fibers and a gaseous emulsion, and their applications.
    公开号:FR3027023A1
    申请号:FR1459670
    申请日:2014-10-09
    公开日:2016-04-15
    发明作者:Corfec Yves Le
    申请人:Glaztec'h；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to novel rigid and porous rigid foams and their applications as thermal insulating material and refractory in building construction or industry. The depletion of fossil fuels and primary resources requires the development of new thermal insulation materials that are effective and environmentally acceptable. The materials currently used in building insulation are effective but have weaknesses.
    [0002] Certain materials, such as polyurethane foam, polyester wadding, expanded or extruded polystyrene, or insulating materials of plant or animal origin, are flammable. Some of the insulating materials currently available on the market can be harmful to health or the environment. Others do not improve fire resistance or fire safety and may have recycling constraints. In recent years, the focus of development of new thermal and refractory insulation materials has shifted to mineral-based materials known to be refractory. Several production methods have been proposed in the literature for the production of light mineral materials, often in the form of rigid foam. WO 2007/043022 discloses a method of manufacturing a porous refractory ceramic material, wherein a foaming agent is added in an aqueous suspension of ceramic powders to produce a ceramic foam after mechanical agitation. After stabilization, this foam undergoes a first heat treatment at a temperature between 50 ° C and 110 ° C and a second heat treatment at a temperature above 1500 ° C. WO 2008/146320 discloses a thermal and acoustic insulating material. This material has a cellular structure comprising ceramic fibers, such as glass wool or mineral wool and is formed by a foam emulsion comprising ceramic fibers, at least one silicate binding agent and at least one foaming agent organic emulsifier. The above emulsion first undergoes a first heat treatment of 70 ° C to 120 ° C to consolidate the structure of the foam and obtain a solid body. Said solid body then undergoes a second heat treatment at high temperature, in particular from 400 ° C. to 800 ° C., in order to eliminate the organic components present in said solid body and to obtain the final material. These materials are refractory and effective in terms of thermal insulation. However, their production is energetically expensive because of the need for high temperature heat treatment. There is therefore a need to provide healthy materials, having excellent insulating and refractory character, and low production cost, for use on an industrial scale in building construction or industry. The present invention therefore aims to overcome the aforementioned drawbacks by proposing new rigid foams mineral and porous. The subject of the invention is a rigid, mineral and porous foam capable of being obtained according to the process comprising or consisting of the following steps: (i) the preparation of a suspension loaded with particles or mineral fibers 20 by the mixture between an aqueous solution of at least one alkali metal silicate, an alkali metal aluminate, or mixtures thereof, with particles and / or mineral fibers which are at least partially insoluble in the said solution, optionally at least a functional molecule, and - optionally, organic binders soluble in the above solution and capable of undergoing crosslinking or polycondensation, such as polyvinyl alcohol or acrylic resins; (ii) preparing a foam by dispersing a gas in a second aqueous solution comprising: at least one natural or synthetic foaming agent of animal or vegetable origin, and optionally at least one surfactant other than foaming agent used in said solution; (Iii) the preparation of a foamy mixture by the mixture of the above suspension obtained in step (i) and the said foam obtained in step (ii) (iv) the stabilization of the foamy mixture obtained in the end of step (iii) to obtain said rigid foam. In the context of the present invention, the foam obtained in step (ii) is referred to as a "gaseous emulsion". The invention is based on the fact that the materials of the invention have a macroporous structure, thanks to the perennial stabilization of a gaseous emulsion by adding a suspension of mineral particles in a solution of silicate and / or aluminate of alkali metal. Indeed, the inventor surprisingly finds that the contribution of this suspension does not destabilize the structure of a previously formed gaseous emulsion, which allows a homogeneous dispersion of the gas initially contained in the gaseous emulsion in said suspension, by preserving the swelling ability of the foamy mixture. In addition, the production of the materials of the invention does not require heat treatment at high temperature and values the powders in their initial state and is therefore very economical in terms of energy consumption. The new porous rigid foams of the present invention have excellent thermal and / or sound insulating properties, good heat capacity, and are capable of withstanding high temperatures (above 1000 ° C. or even 1500 ° C. depending on the materials). 25 first chosen). These physico-chemical properties are related to the ability to produce a porous composite structure. The porosity of the material of the invention is attributed both to the gas bubbles initially constituting the gaseous emulsion and to entrained air entrainments on the micrometer particles of the suspension, which produce micropores and nanopores, and to the formation millimeter to centimeter size bubbles resulting from the coagulation of certain constituents during mechanical mixing between the gaseous emulsion and the suspension. Coagulation is likely to occur in contact with the liquid phase of the gaseous emulsion with the suspension charged with mineral particles, causing a change in the pH within said gaseous emulsion and said suspension. Therefore, by controlling the gas supply from the gaseous emulsion and / or by the coagulation reaction, the size of some of the pores can be controlled and varied from one foam to another. The starting minerals of the materials of the invention are minerals at least partially insoluble in an alkali metal silicate or aluminate solution. These minerals are used in the context of the present invention in the form of particles or fibers. For the purposes of the present invention, the term "particle" means powders having a median grain diameter of 1 to 100 pm, ideally between 5 and 50 pm. The term "fiber" is understood to mean any fiber longer than 5 μm, less than 100 μm, and having a length / diameter ratio greater than 3. For example, the particles or mineral fibers that can be used are the particles or fibers of one or more minerals selected from the group consisting of glasses, bricks, sandstones, feldspars, ceramics, slags, clays, dehydroxylated clays, carbonates, phosphates, metal oxides, borides of metals or silicon, carbides of metals or silicon, ashes and silico-aluminous mixtures, nitrides, silica microballoons or cenospheres, silicates such as calcium silicate, elemental carbon such as graphite or coal, kaolin, metakaolin, talc, zircon, chromite, boron or sulfur phosphide, elemental boron, titanium dioxide, apatite, hydroxyapatite, alumina, anthracite, olivine, magnesite, silica, pozzolan, silica pyrogenous, or smoke of silica. It should be noted that these minerals can play a functional role in addition to their structural role within a rigid foam of the invention and possibly confer additional functions to the rigid foams of the invention. For example, some minerals are electrically conductive and can absorb electromagnetic waves. The rigid foam of the invention may be reinforced or reinforced by the addition of fibers longer than one millimeter in length and in a weight ratio of less than 0.5% relative to the final mass of said rigid foam. Said fibers may be polyester, carbon or polypropylene fibers. These fibers may be dispersed in the suspension charged with particles and / or mineral fibers or in the foamy mixture before solidification.
    [0003] As an example of alkali metal silicate, there may be mentioned sodium silicate, magnesium, or potassium. As an example of alkali metal aluminate, there may be mentioned sodium aluminate, magnesium, or potassium. In a preferred embodiment, the slurry of step (i) is obtained on the basis of a sodium silicate solution. In general, the sodium silicate used in the invention has an SiO 2 / Na 2 O molar ratio of from 1.9 to 3.9. The choice of this ratio influences the pH of the suspension obtained in the aforesaid step (i): a ratio of less than 2.8 leads to a strongly alkaline suspension; a ratio greater than 2.9 allows, on the other hand, to produce a suspension closer to neutrality. Indeed, a high pH leads to coagulation of foamy mixtures comprising proteinaceous foaming agents at the time of mixing and therefore to the formation of macroporosities.
    [0004] Those skilled in the art will be able to adapt the concentration of the alkali metal silicate and / or aluminate solution according to the nature and the surface state of the particles and / or fibers used and according to the mechanical characteristics desired for the finished material. Advantageously, the percentage of dry matter of this solution is 28% to 51%. In a particular embodiment, the alkali metal silicate can be produced in situ according to conventional methods known to those skilled in the art. Advantageously, during the preparation of the suspension of step 30 (i), the mass ratio between the weight of particles and / or mineral fibers contained in the suspension and that of the alkali metal silicate and / or aluminate solution is from 1: 0.5 to 1: 20. Those skilled in the art will be able to adapt this mass ratio according to the density, the surface condition of particles and / or mineral fibers used or their affinity for silicate and / or aluminate of alkali metal. Within the meaning of the invention, the term "functional molecule" means a component which is not necessarily present in a rigid foam of the invention and makes it possible to confer additional functions or applications on a foam containing said functional molecule. , in addition to those related to its thermal insulation property, refractory and porous and shared by all the rigid foams of the invention. In a particular embodiment, said functional molecule 10 is chosen from a catalyst, a dye, a compound having the properties of gas sorption or electromagnetic wave absorption. A particular embodiment of the invention relates to an electrically conductive rigid foam, which is obtained from a suspension comprising, as a functional molecule, particles and / or mineral fibers either naturally conductive or made conductive after specific treatment, or metal powders. For example, a metal deposit can make the particles and / or inorganic fibers conductive.
    [0005] Some functional molecules may also be incorporated into the foamy mixture obtained in the aforementioned step (iii). In another particular embodiment, the aforementioned suspension in step (i) for the preparation of a mineral foam of the invention further comprises organic binders, such as polyvinyl alcohol or acrylic resins, at low levels. dose, which avoids a possible powdery initial behavior of the materials of the invention related to slow reaction kinetics. Those skilled in the art will know how to find the appropriate dose to add to said suspension according to the teachings of the prior art. According to the invention, the aforementioned foam in step (ii) is prepared from one or more natural or synthetic foaming agents of animal or vegetable origin. These foaming agents are chosen in particular from the group comprising optionally halogenated surfactants, sucroesters, fatty acids and alcohols, egg white, lecithins, and optionally hydrolysed natural or synthetic proteins, such as serum proteins, including albumin, caseins, halogenated proteins, protein-halogenated emulsifiers, or mixtures of these agents with each other. In a particularly advantageous embodiment, the foaming agent used to prepare the foam of step (ii) is chosen from the group consisting of egg white, lecithins, serum proteins, in particular albumin, caseins, or mixtures of these agents with each other.
    [0006] By way of example, the gas used in the aforesaid stage (ii) for the preparation of foam may be air, argon, azote, or any other inert gas or mixtures thereof on the one hand, carbon dioxide on the other hand, or their mixtures. Carbon dioxide initiates, if present, the stabilization process. Those skilled in the art will be able to choose the gas according to its affinity for water, silicates, aluminates or according to its own physical properties. Suitably and advantageously, the second aqueous solution used in the aforesaid step (ii) further comprises at least one surfactant which is different from the foaming agent used in said solution, which makes it possible to stabilize and improve the texture of the foam by adapting the porosity characteristics to the needs. Said surfactant may be selected from a conventional surfactant. The foamy mixture mentioned in step (iii) can be obtained either by adding the suspension obtained according to step (i) into the foam obtained according to step (ii), or by dispersing the foam. obtained according to step (ii) in the suspension obtained according to step (i). By "stabilization of the foamy mixture" is meant in the sense of the present invention, an evolution of a plastic foam structure to a rigid foam structure.
    [0007] The foamy mixture obtained according to the above-mentioned step (iii) can be stabilized by several methods known in the prior art. By way of example, this foamy mixture can be stabilized thermally, in particular by heating at a temperature between 30 ° C. and 200 ° C., which leads to the coagulation of the constituents of said foamy mixture, such as proteinaceous foaming agents. or organic binders, in said foamy mixture, and precipitating silica in solid form by evaporation of the water contained in said foamy mixture. The heating of the foamy mixture can be carried out by any conventional method, in particular by a microwave oven.
    [0008] This stabilization mode can be easily integrated into an industrial process. The production of a gaseous emulsion can be carried out in a few tens of seconds. The particle suspension can also be obtained in a few tens of seconds. It can also be prepared beforehand and can be easily preserved provided it is protected from CO2 in order to prevent any carbonation. Stabilization, by heating with a microwave oven, to obtain a "ready-to-use" rigid foam and drying from a gaseous emulsion and a slurry loaded with mineral particles can take as few as ten seconds, which allows industrial production on site or even obtaining a rigid foam having a desired three-dimensional structure using known technologies, for example "3D printing".
    [0009] The stabilization can also be carried out by spontaneous coagulation, following the modification of the pH linked to the partial solubilization of CO2, the latter possibly being the atmospheric CO2 initially trapped in the gaseous emulsion obtained according to step (ii) or as during stabilization, or CO2 injected into the foamy mixture before or during stabilization. Coagulation can also be triggered by adding finely divided dry matter powder or alkali metal powder to the unstabilized foamy mixture. This coagulation is the result of the combined increase of the SiO 2 / Na 2 O ratio and of the solid material by adding silicon, ferro silicon, magnesium, aluminum to the foamy mixture or by direct addition of the sodium silicate, which causes a reaction. physico-chemical exothermic which dehydrates the foamy mixture. Stabilization can also be carried out by adding weak acids or organic esters, such as polyhydric alcohol esters, glycerol mono-, di-, or tri-esters, especially mono-, di- or tri-esters of glycerol, -, or glycerol triacetate, or alkylene carbonates, such as propylene carbonate or ethylene carbonate, or acetic esters, such as ethyl acetate. These components can be added to the unstabilized foamy mixture or to the initial gaseous emulsion. Solidification of the foam by adding CO 2, weak acids or esters may require the use of a larger amount of alkali metal silicates. Those skilled in the art will be able to adjust the amount of alkali metal silicates used according to its chosen stabilization mode. The essential advantage of the rigid foams of the invention lies in their excellent heat insulating capacity associated with their porosity and resistance characteristics at very high temperatures. The rigid foams of the invention can be used as thermal and / or phonic insulating material, in the construction or external and / or interior insulation of buildings, in industry, geotechnical applications, transportation, mining. , engineering structures, oil or gas exploration or production. As the stabilization of the foamy mixture by diffusion of CO2 possibly present in the foam or diffusion of atmospheric CO2, the rigid foams of the invention can be used as thermal insulation foam and / or phonic delayed-cure but spontaneous. This property makes it possible to avoid an additional stabilization step by other means, when this spontaneous hardening is compatible with the intended application, such as the case of certain applications to the building. In a particular embodiment, the invention relates to the use of porous rigid foams previously described as a vacuum insulation support by applying an impermeable envelope to the rigid foam panels of the invention. The latter then provide an empty volume of air. A porous rigid foam of the invention can also be used as a heat storage element in the manufacture of a heat exchanger or well, because of its very good heat capacity over a wide range of temperatures and heat. porous character. Another advantageous aspect of the rigid foams of the invention is that they are resistant to very high temperatures. These rigid foams can be used as a fire-resistant material or a material for protection against fire, heat, or radiation, especially infrared radiation, or as a material for the manufacture of industrial elements that require high temperature resistance. According to one embodiment of the invention, said rigid foams can be used in the form of a composite. In particular, the rigid foams of the invention can be used as a material for the manufacture of molds, especially high temperature refractory molds, more particularly, foundry molds or electrolysis molds. According to a particular embodiment, the rigid foams of the invention can be used as a support for pyrolysis. Another particular embodiment of the invention relates to the use of a foamy mixture which is not yet stabilized and is still in plastic form for fire fighting. The foamy mixture, in contact with fire or by diffusion of atmospheric CO2, is solidified and converted into refractory rigid foam, nonflammable and then limits the spread.
    [0010] The rigid foams of the present invention may also be used as a nonflammable core material of composite materials. In addition, the low density of the rigid foams of the invention related to their porous nature allows them to be used as conditioning foam or impact protection, or as a cavity inerting material and explosion proof barrier design. Another particular embodiment is the use of the rigid foams of the invention as a buoyancy reserve.
    [0011] According to another particular embodiment, the rigid foams of the invention can be used as building material, laminating support, core or binder for the constitution of composite or laminated elements.
    [0012] The cellular structure and the physicochemical properties of certain constituents of the rigid foams of the invention also give them specific applications. Thus in a particular embodiment, the rigid foams of the invention are used as air conditioning material or treatment of liquids or gases by filtration or sorption. According to another particular embodiment, the invention relates to the use of a rigid foam of the invention as a catalyst support, either thanks to the minerals contained in said foam and operated as a catalyst; either by adding a catalyst as a functional molecule in the suspension obtained according to the aforesaid step (i). Another aspect of the use of a rigid foam of the invention relates to the use of a foam on the surface of which is deposited a fuel, as infrared radiating material. The invention also relates to the use of an electronically conductive rigid foam previously described as an electromagnetic shielding material. Another aspect of the invention is to provide a process for the preparation of a porous rigid foam.
    [0013] Said method comprises: (i) preparing a suspension charged with particles and / or mineral fibers by mixing: an aqueous solution of at least one alkali metal silicate, an alkali metal aluminate, or mixtures thereof, with Particles or mineral fibers which are at least partially insoluble in the said solution, optionally at least one functional molecule, and, optionally, organic binders which are soluble in the said solution and capable of undergoing crosslinking or polycondensation; (Ii) preparing a foam by dispersing a gas in a second aqueous solution comprising: at least one natural or synthetic foaming agent of animal or vegetable origin, and optionally at least one surfactant different from the foaming agent used in said solution; (iii) preparing a foamy mixture by mixing said suspension obtained in step (i) and said foam obtained in step (ii) (iv) stabilizing the foamy mixture obtained at the end of the step (iii) to obtain said rigid foam. The invention is further illustrated by the following examples. 1. Preparation of a new porous rigid foam 15 1.1. Preparation of a Silicate Suspension Loaded with Mineral Particles 160 g of a sodium silicate solution is prepared. The SiO 2 / Na 2 O molar ratio of said solution is from 3.3 to 3.5. Their weight ratio is 3.2 to 3.4. The density of the sodium silicate solution obtained is 1.33 to 1.45. The percentage of the dry matter of the sodium silicate solution is 50%. 160 g of mineral particles are added in 160 g of the aforesaid sodium silicate solution. 1.2 Preparation of a gaseous emulsion A suitable amount of egg white is mechanically stirred to obtain a plastic foam. 1.3 Preparation of a foamy mixture 320 g of the silicate suspension obtained in 1.1 is added to 11 g of emulsion obtained in 1.2. 1.4 Obtaining a Rigid Foam 3027023 13 After the stabilization of the foamy mixture, the rigid foam obtained has a volume substantially equivalent to that of the initial gaseous emulsion and has a true final density of 0.25. The density of a rigid foam can be varied depending on the macroporosity rate of this foam. It can be noticeably weaker. Several rigid foams containing different starting minerals have been prepared and tested. The formulations of these foams are summarized in Table I below.
    [0014] 14 Table I Formulation 1 2 3 4 6 Emulsion gas (liter) 1 1 1 1 1 1 1 1 1 50% silicate solution MS (g) 200 200 200 140 200 200 200 200 200 KA ... .1: __ . Silica (g) 100 100 10 10 130 40 Alumina (g) 60 20 10 15 100 Metakaolin (g) Glass powder (g) 10 50 100 Microballoons / Cenosphere (g) 15 Pyrogenic Silica (g) 10 Graphite (g) 20 5 Slag Powder (g) 30 Total Solids (g) 160 150 55 15 70 150 100 110 120 Total Sum MS (g) 260 250 155 85 170 250 200 210 220 Final density after dehydration (kg / m3) 260 250 155 85 170 250 200 210 220 3027023 15 2. Refractory properties of the rigid foams of the invention Flame resistance tests were carried out on these aforesaid rigid foams in the form of a 6x15x15 cm thick test specimen, one of whose faces was exposed to the flame of more than 1500 ° C., produced by an electro-burner, for several tens of minutes. These tests show that the integrity of the test piece has been maintained and that a temperature gradient of 200 ° C / cm is easily obtained. The thermal shock resistance capability and the dimensional stability of these foams are also analyzed. The thermal shock resistance capability is tested by high alloy steel casting at 1400 ° C on a rigid foam of the invention. The dimensional stability of a foam is tested by enameling test at 850 ° C.
    [0015] These experiments show that the rigid foams of the invention are very resistant to thermal shock and have very good dimensional stability.
    权利要求:
    Claims (9)
    [0001]
    REVENDICATIONS1. A process for preparing a rigid, mineral-and eremse foam, comprising the following steps: (i) the preparation of a slurry charged with particles and / or mineral fibers, by mixing between - an aqueous solution of at least one silicate of an alkali metal, an alkali metal aluminate, or mixtures thereof, with - mineral particles or fibers which are at least partially insoluble in said solution, - optionally, at least one functional molecule, and - optionally, organic binders soluble in the said solution and capable of undergoing crosslinking or polycondensation, (ii) the preparation of a foam by the dispersion of a gas in a second aqueous solution comprising at least one natural or synthetic foaming agent of origin animal or vegetable, and - optionally at least one surfactant which is different from the foaming agent used in said solution; (iii) the preparation of a soft mixture by mixing said suspension obtained in step (i) and said foam obtained in step (ii); (iv) stabilizing the foamy mixture obtained at the end of step (iii) to obtain said rigid foam. 25
    [0002]
    2. Process for the preparation of a mineral foam according to claim 1, characterized in that the particles or mineral fibers are the particles or fibers of one or more minerals selected from the group consisting of glasses, bricks, sandstones, feldspars, ceramics. , clays, dehydroxylated clays, carbonates, phosphates, metal oxides, borides of metals or silicon, carbides of metals or silicon, slags, ashes and silico-aluminous mixtures, nitrides, silica microballoons or cenospheres, silicates such as calcium silicate, elemental carbon such as graphite or coal, kaolin, metakaolin, talc, zircon, chromite, boron or sulfur phosphide, elemental boron, titanium dioxide, apatite , hydroxyapatite, pozzolan, alumina, anthracite, olivine, magnesite, silica, fumed silica, or silica fume.
    [0003]
    3. Process for the preparation of a mineral foam according to claim 1, wherein said functional molecule is chosen from a catalyst, a dye, a compound having properties of gas sorption or absorption. electromagnetic waves. 10
    [0004]
    4. A method for preparing a mineral foam according to any one of claims 1 to 3, characterized in that said foaming agent is selected from the group comprising optionally halogenated surfactants, sucroesters, fatty acids and alcohols, white of egg, lecithins, and optionally hydrolysed natural or synthetic proteins, such as serum proteins, including albumin, caseins, halogenated proteins, or a mixture of the aforesaid foaming agents.
    [0005]
    5. Process for the preparation of a mineral foam according to any one of claims 1 to 4, characterized in that said foamy mixture is stabilized by heating, by injecting CO2, by adding powder of dry matter or powder of metals, or by addition of weak acids, organic esters, alkylene carbonates, or acetic esters.
    [0006]
    6. rigid foam, mineral and porous, obtainable according to the method of preparation as defined in any one of claims 1 to 5.
    [0007]
    7. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as heat insulating material and / or phonic, in the building, industry, geotechnical applications, transportation, mines , engineering structures, exploration, oil and gas production.
    [0008]
    8. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as a fire-resistant material or material for protection against fire, heat or radiation.
    [0009]
    9. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as air conditioning material, treatment of liquids or gases by filtration or sorption. -10. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as a catalyst support, said foam being obtained from a said suspension optionally comprising at least one catalyst as functional molecule. 11. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as an electromagnetic shielding material, said foam being obtained from a suspension comprising particles and / or mineral fibers electrically. conducting or metal or mineral powders made conductive. 12. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as a material for forming molds, especially molds and refractories at high temperature. 13. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as conditioning foam or impact protection. 14. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as a building material, lamination support, core or binder for the formation of composite or laminated elements. 15. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as a heat storage element in the manufacture of exchanger or heat sink. 16. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as a buoyancy reserve. 17. Use of a foam according to claim 6 or obtained according to any one of claims 1 to 5 as an explosion-proof and cavity-inert material. 18. Use of a foamy mixture as defined in claim 1 as fire fighting foam.
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    同族专利:
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    引用文献:
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1459670A|FR3027023B1|2014-10-09|2014-10-09|NEW POROUS MINERAL RIGID FOAMS AND USES THEREOF|
    FR1459670|2014-10-09|FR1459670A| FR3027023B1|2014-10-09|2014-10-09|NEW POROUS MINERAL RIGID FOAMS AND USES THEREOF|
    EP15189069.6A| EP3006417A1|2014-10-09|2015-10-09|New porous rigid mineral foams and their uses|
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