RU2811474C2 - Reinforced aerogel compositions compliant with fire safety class requirements - Google Patents

Abstract

FIELD: reinforced aerogel compositions.

SUBSTANCE: proposed composition includes a silica airgel framework reinforced with an open-cell macroporous framework, and includes one or more fire-rated additives containing an endothermic material, wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom , and the additive corresponding to the fire safety class is characterized by the temperature of the onset of thermal decomposition, which is within 50° C on the temperature at which the airgel framework begins to decompose.

EFFECT: proposed reinforced aerogel compositions are durable and easy to handle, demonstrate favorable performance characteristics in aqueous environments, and have favourable insulating and fire-resistant properties.

25 cl, 2 dwg, 2 tbl, 25 ex

Description

[0001] CROSS-REFERENCES TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 62/678,850, filed May 31, 2018, which is incorporated by reference herein in its entirety, subject to any definition of terms herein prevailing.

[0003] BACKGROUND OF THE INVENTION

[0004] 1. Field of technology to which the invention relates

[0005] This invention generally relates to airgel technology. More specifically, it refers to aerogel compositions containing fire rated additives.

[0006] 2. Brief description of the prior art

[0007] Low-density aerogel materials are widely recognized as the best solid insulators available. Aerogels function as insulators primarily by minimizing conductivity (low density structure results in a tortuous path for energy transfer through the solid frame), convection (large pore volumes and very small pore sizes result in minimal convection), and radiation (additives that absorb or scatter IR radiation are easily dispersed throughout the entire volume of the airgel matrix). Aerogels can be used in a wide range of applications, including in connection with heating and cooling insulation, sound insulation, electronic dielectrics, aerospace, energy storage and generation, and filtration. In addition, aerogel materials exhibit a variety of other interesting acoustic, optical, mechanical and chemical properties that make them suitable for use in large quantities in a variety of insulation and non-insulation applications.

[0008] However, what is required are reinforced aerogel compositions that are fire rated and exhibit improved performance in various aspects, including heat resistance, hydrophobicity, fire response, and others, individually and in one or more combinations. The present invention has been made in light of the state of the art considered generally at that time, although it would not be obvious to those skilled in the relevant art of the present invention how the disadvantages of the prior art could be overcome.

[0009] Although certain aspects of conventional technology have been discussed to facilitate the disclosure of the invention, applicants in no way deny these technical aspects, and, as contemplated, the claimed invention may cover one or more of the conventional technical aspects discussed herein.

[00010] In this specification, when referring to or discussing a document, regulation, or item of information, such reference or discussion does not constitute an assumption that the document, regulation, or item of information, or any combination thereof, was available to the public at the priority date, known to the public, part of generally available general knowledge or otherwise constitute prior art within the limits of applicable legal provisions; or are known to be concerned with attempting to solve any problem to which this specification relates.

[00011] SUMMARY OF THE INVENTION

[00012] The long-standing but hitherto unmet need for improved aerogel compositions has now been met with a new, useful and non-obvious invention.

[00013] In one embodiment, the present invention is a reinforced airgel composition comprising a silica-based airgel framework reinforced with an "open cell macroporous framework" ("OCMF") material, and a fire rated additive, wherein the airgel framework based on silicon dioxide contains at least one hydrophobically bonded silicon atom.

[00014] In one general aspect, the present disclosure provides reinforced aerogel compositions that are durable and easy to handle, that exhibit favorable performance in aqueous environments, that have favorable insulating properties, and that also exhibit favorable combustion and fire resistance characteristics. In certain embodiments, the present disclosure provides a reinforced airgel composition that is reinforced with an OCMF material that exhibits favorable performance in aqueous environments, that has favorable insulating properties, and that also exhibits favorable combustion and fire resistance characteristics.

[00015] In yet another general aspect, the present disclosure provides a reinforced airgel composition comprising a silica airgel framework and an OCMF material, and which has the following properties: a) thermal conductivity of 30 mW/m*K or less; b) liquid water absorption of 30% or less; and (c) a heating value of 717 cal/g (3.00 kJ/g) or less. In certain embodiments, the reinforced airgel composition of the present disclosure has the following properties: a) thermal conductivity of 25 mW/m*K or less; b) liquid water absorption of 20% or less; and (c) a heating value of 717 cal/g (3.00 kJ/g) or less. In certain embodiments, the reinforced airgel composition of the present disclosure has a density of 0.40 g/cm3 or less, 0.30 g/cm3 or less, 0.25 g/cm3 or less, or 0.20 g/cm3 or less. In certain embodiments, the reinforced aerogel compositions of the present disclosure have a thermal conductivity of 25 mW/m*K or less, 20 mW/m*K or less, 18 mW/m*K or less, a thermal conductivity in the range of between 15 mW/m* K and 30 mW/m*K or thermal conductivity in the range between 15 mW/m*K and 20 mW/m*K. In certain embodiments, the reinforced airgel composition of the present disclosure is characterized by liquid water absorption of 30% (wt.) or less, 25% (wt.) or less, 20% (wt.) or less, 15% (wt.) and less, 10% (wt.) or less and 5% (wt.) or less. In certain embodiments, the reinforced airgel composition of the present disclosure has a heating value of 717 cal/g (3.00 kJ/g) or less, 700 cal/g (2.93 kJ/g) or less, 675 cal/g ( 2.83 kJ/g) or less, 650 cal/g (2.72 kJ/g) or less, 625 cal/g (2.62 kJ/g) or less, 600 cal/g (2.51 kJ/g) d) or less, or a calorific value between 580 cal/g (2.43 kJ/g) and 717 cal/g (3.00 kJ/g). In certain specific aspects, achieving a combination of the above-described thermal conductivity, water absorption, and heat of combustion values is achieved by varying the composition of the gel precursor, the composition of the additive, catalyst or other agents that activate the precursor, the pH value of the precursor solution, the dosing rate, respectively, of the precursors, catalyst or additives, the time allowed to undergo gelation, gel winding (in certain aspects), the time and pH of aging, any post-gelation treatment, the time and conditions of extraction (temperature, pressure) and any subsequent drying steps.

[00016] In yet another general aspect, the present disclosure provides reinforced aerogel compositions comprising a silica airgel framework, a melamine-based OCMF material, and a fire rated additive, and which have the following properties: a) thermal conductivity in the range between 15 mW/m*K and 30 mW/m*K; b) liquid water absorption of 30% (w/w) or less; and c) calorific value between 580 cal/g (2.43 kJ/g) and 717 cal/g (3.00 kJ/g). In certain preferred embodiments, the OCMF material is an organic OCMF material. In still further certain preferred embodiments, the OCMF material is a melamine-based OCMF material. In certain embodiments, the reinforced aerogel compositions of the present disclosure are characterized by a hydrophobic organic matter content in the range of between about 1% by weight and about 30% by weight, between about 1% by weight and about 25% by weight. , between about 1% (wt.) and about 20% (wt.), between about 1% (wt.) and about 15% (wt.), between about 1% (wt.) and about 10% (wt.) ) or between about 1% (wt.) and about 5% (wt.).

[00017] In yet another general aspect, the present disclosure provides a method for producing a reinforced airgel composition, comprising a) producing a precursor solution containing silicic acid gel precursor materials, a solvent, and optionally a catalyst; b) combining the precursor solution with a reinforcing material including OCMF material; c) allowing the silicic acid gel precursor materials in the precursor solution to transfer into the gel material or composition; and d) extracting at least a portion of the solvent from the gel material or composition to obtain an airgel material or composition. In certain embodiments, the methods of the present disclosure include incorporating a fire-rated additive material into a reinforced airgel composition by combining the fire-rated additive material with a precursor solution either before or during the transition of the silicic acid gel precursor materials into solution precursor into the gel composition. In one preferred embodiment, the reinforcing material includes a melamine-based OCMF material. In certain embodiments, the methods of the present disclosure include introducing at least one hydrophobically bonded silicon atom into the airgel material or composition using one or both of the following: i) incorporating a precursor solution of at least one precursor material a silicic acid gel containing at least one hydrophobic group, or ii) exposing the precursor solution, gel composition or airgel composition to a hydrophobizing agent. In certain embodiments, the methods of the present disclosure include the step of introducing at least one hydrophobically bonded silicon atom into the airgel composition, causing the hydrophobic organic matter content of the airgel composition to range between about 1 wt% and about 25 wt%. wt.), between about 1% (wt.) and about 20% (wt.), between about 1% (wt.) and about 15% (wt.), between about 1% (wt.) and about 10% (wt.) or between about 1% (wt.) and about 5% (wt.). In one preferred embodiment, the methods of the present disclosure provide for the production of a reinforced airgel composition. In certain embodiments, the methods of the present disclosure provide the production of a reinforced airgel composition comprising a silica airgel frame, a melamine-based OCMF material and a fire rated additive, and which has the following properties: a) thermal conductivity in the range of between 15 mW /m*K and 30 mW/m*K; b) liquid water absorption of 30% (w/w) or less; and c) calorific value between 580 cal/g (2.43 kJ/g) and 717 cal/g (3.00 kJ/g).

[00018] In addition, the following specific non-limiting embodiments/examples are disclosed. The listed examples are presented to illustrate a certain range of embodiments that are provided herein, including combinations of such embodiments or examples. The invention, as described in the claims, demonstrates a scope beyond the scope of these non-limiting examples.

[00019] Embodiment 1 is a reinforced airgel composition including a silica airgel frame reinforced with an OCMF material and a fire rated additive; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) liquid water absorption of 20% by weight or less; ii) thermal conductivity of 30 mW/m*K or less; and iii) a calorific value of less than 717 cal/g (3.00 kJ/g).

[00020] Embodiment 2 is a reinforced airgel composition comprising a silica-based airgel frame reinforced with an OCMF material having a density ranging between 2 kg/m ³ and 25 kg/m ³ and an additive corresponding to a fire rating; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) liquid water absorption of 20% by weight or less; ii) thermal conductivity of 30 mW/m*K or less; and iii) a calorific value of less than 717 cal/g (3.00 kJ/g).

[00021] Embodiment 3 is a reinforced airgel composition comprising a silica-based airgel frame reinforced with an OCMF material having a density ranging between 2 kg/m ³ and 25 kg/m ³ and an additive corresponding to a fire rating; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) absorption of liquid water in the range between 1% (wt.) and 10% (wt.); ii) thermal conductivity of more than 8 and less than 25 mW/m*K; and iii) a calorific value of less than 717 cal/g (3.00 kJ/g) and more than 400 cal/g (1.67 kJ/g).

[00022] Embodiment 4 is an OCMF reinforced composition reinforced with a silica airgel composition and a fire rated additive; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) liquid water absorption of 20% by weight or less; ii) thermal conductivity of 30 mW/m*K or less; and iii) a calorific value of less than 717 cal/g (3.00 kJ/g).

[00023] Embodiment 5 is an OCMF reinforced composition reinforced with a silica airgel composition and a fire rated additive; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) liquid water absorption of 20% by weight or less; ii) thermal conductivity of 30 mW/m*K or less; and iii) a calorific value of less than 717 cal/g (3.00 kJ/g).

[00024] Embodiment 6 is an OCMF reinforced composition reinforced with a silica airgel composition and a fire rated additive; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) absorption of liquid water in the range between 1% (wt.) and 10% (wt.); ii) thermal conductivity of more than 8 and less than 25 mW/m*K; and iii) a calorific value of less than 717 cal/g (3.00 kJ/g) and more than 400 cal/g (1.67 kJ/g).

[00025] Embodiment 7 is a set of embodiments comprising the reinforced airgel composition of any one of embodiments 1-3 or the reinforced OCMF material composition of any one of embodiments 4-6, wherein the OCMF material includes or is an organic OCMF material.

[00026] Embodiment 8 is a set of embodiments comprising the reinforced airgel composition of any one of embodiments 1-3 or the reinforced OCMF material composition of any one of embodiments 4-6, wherein the OCMF material includes or is a material Melamine based OCMF.

[00027] Embodiment 9 is a set of embodiments comprising the reinforced airgel composition of any one of embodiments 1-3 or the reinforced OCMF composition of any one of embodiments 4-6, wherein the OCMF material includes or is a sheet OCMF material.

[00028] Embodiment 10 is a set of embodiments including the reinforced airgel composition of any one of embodiments 1-3 or the reinforced OCMF composition of any one of embodiments 4-6, wherein the OCMF material is an organic foam.

[00029] Embodiment 11 is a set of embodiments comprising the reinforced airgel composition of any one of embodiments 1-3 or the reinforced OCMF material composition of any one of embodiments 4-6, wherein the OCMF material is a foam on melamine basis.

[00030] Embodiment 12 is a set of embodiments including the reinforced airgel composition or the reinforced OCMF material composition from any one of embodiments 1 to 11, where the OCMF material is neither a retardant material nor a non-flammable material.

[00031] Embodiment 13 is a set of embodiments including the reinforced airgel composition or the reinforced OCMF material composition from any one of embodiments 1 to 11, where the OCMF material is neither a refractory material nor a non-flammable material.

[00032] Embodiment 14 is a set of embodiments including a reinforced airgel composition or a reinforced OCMF material composition from any one of embodiments 1 to 11, wherein the OCMF material is from 2% by weight to 10% by weight. ) from the composition.

[00033] Embodiment 15 is a set of embodiments including a reinforced airgel composition or a reinforced OCMF material-based composition from any one of embodiments 1 to 14, wherein the content of hydrophobically bonded silicon atom in the composition is in the range of between 2% (wt. .) and 10% (mass.).

[00034] Embodiment 16 is a set of embodiments including a reinforced airgel composition or a reinforced OCMF material-based composition from any one of embodiments 1 to 14, wherein the hydrophobically bonded silicon atom content of the composition is in the range of between 2% (wt. .) and 8% (mass.).

[00035] Embodiment 17 is a set of embodiments including a reinforced airgel composition or a reinforced OCMF material-based composition from any one of embodiments 1 to 14, wherein the content of hydrophobically bonded silicon atom in the composition is in the range of between 2% (wt. .) and 6% (mass.).

[00036] Embodiment 18 is a set of embodiments comprising a reinforced airgel composition or a reinforced OCMF composition from any one of embodiments 1 to 17, wherein the composition has a heating value of 700 cal/g (2.93 kJ/g). d) or less.

[00037] Embodiment 19 is a set of embodiments comprising a reinforced airgel composition or a reinforced OCMF composition from any one of embodiments 1 to 17, wherein the composition has a calorific value of 675 cal/g (2.83 kJ/g). d) or less.

[00038] Embodiment 20 is a set of embodiments comprising a reinforced airgel composition or a reinforced OCMF composition from any one of embodiments 1 to 17, wherein the composition has a heating value of 650 cal/g (2.72 kJ/g). d) or less.

[00039] Embodiment 21 is a set of embodiments comprising a reinforced airgel composition or a reinforced OCMF composition from any one of embodiments 1 to 17, wherein the composition has a calorific value of 625 cal/g (2.62 kJ/g). d) or less.

[00040] Embodiment 22 is a set of embodiments including the reinforced airgel composition or the reinforced OCMF material composition from any one of embodiments 1 to 21, wherein the composition has a thermal conductivity of 22 mW/m*K or less.

[00041] Embodiment 23 is a set of embodiments including a reinforced airgel composition or a reinforced OCMF material composition from any one of embodiments 1 to 21, wherein the reinforced airgel composition has a thermal conductivity of 20 mW/m*K or less.

[00042] Embodiment 24 is a set of embodiments including the reinforced airgel composition or the reinforced OCMF composition of any one of embodiments 1 to 21, wherein the reinforced airgel composition has a thermal conductivity of 18 mW/m*K or less.

[00043] Embodiment 25 is a set of embodiments comprising a reinforced airgel composition or a reinforced OCMF composition from any one of embodiments 1 to 21, wherein the reinforced airgel composition has a density in the range of between 0.15 and 0.40 g /cm3.

[00044] Embodiment 26 is a set of embodiments including the reinforced airgel composition or the reinforced OCMF composition of any one of embodiments 1 to 21, wherein the reinforced airgel composition has an onset of thermal decomposition corresponding to 350° C. or more.

[00045] Embodiment 27 is a set of embodiments including the reinforced airgel composition or the OCMF material-based reinforced composition of any one of embodiments 1 to 21, wherein the reinforced airgel composition has a thermal decomposition onset corresponding to 360° C. or more.

[00046] Embodiment 28 is a set of embodiments including the reinforced airgel composition or the reinforced OCMF composition of any one of embodiments 1 to 21, wherein the reinforced airgel composition has an onset of thermal decomposition corresponding to 370° C. or more.

[00047] Embodiment 29 is a set of embodiments including the reinforced airgel composition or the reinforced OCMF material composition of any one of embodiments 1 to 21, wherein the reinforced airgel composition has an onset of thermal decomposition corresponding to 380° C. or more.

[00048] Embodiment 30 is a set of embodiments including a reinforced airgel composition or a reinforced OCMF material composition from any one of embodiments 1 to 21, wherein the reinforced airgel composition has an onset of thermal decomposition corresponding to 390° C. or more.

[00049] Embodiment 31 is an organic material reinforced OCMF airgel composition including fire rated additives and a hydrophobic organic matter content wherein the onset of endothermic degradation of the fire rated additives in the composition is within 50 degrees Celsius of the beginning of thermal decomposition of the remainder of the composition in the absence of an additive corresponding to the fire safety class.

[00050] Embodiment 32 is an organic material reinforced OCMF airgel composition including fire rated additives and a hydrophobic material content of at least 5% by weight, wherein the total heat of endothermic decomposition of the rated additives fire safety in the composition is at least 30% of the exothermic heat of decomposition of the remainder of the composition in the absence of an additive corresponding to the fire safety class.

[00051] Embodiment 33 is an organic material reinforced OCMF airgel composition containing at least two fire rated additives with their respective endothermic decomposition onsets spaced apart by at least 10 degrees Celsius .

[00052] Embodiment 34 is an organic material reinforced OCMF airgel composition including fire rated additives and a hydrophobic material content, wherein the total heat of endothermic decomposition of the fire rated additives in the composition is no more than 80% of exothermic heat of decomposition of the composition residue in the absence of an additive corresponding to the fire safety class.

[00053] Embodiment 35 is a set of embodiments including the reinforced airgel composition or the reinforced OCMF material composition from any one of embodiments 1 to 11, wherein the hydrophobic substance content is at least 5% by weight, and the total heat of endothermic decomposition of the additives corresponding to the fire safety class in the composition is at least 30% of the exothermic heat of decomposition of the remainder of the composition in the absence of the additive corresponding to the fire safety class.

[00054] Embodiment 36 is a set of embodiments comprising a reinforced airgel composition or a reinforced OCMF material composition from any one of embodiments 1 to 11, wherein the onset of endothermic decomposition of fire rated additives in the composition is within 50 degrees Celsius from the beginning of thermal decomposition of the remainder of the composition in the absence of an additive corresponding to the fire safety class.

[00055] Embodiment 37 is a set of embodiments comprising a reinforced airgel composition or a reinforced OCMF material composition from any one of embodiments 1-11 containing at least two fire rated additives, wherein the respective endothermic decomposition of two additives corresponding to the fire safety class are separated from each other by at least 10 degrees Celsius.

[00056] Embodiment 38 is a set of embodiments comprising a reinforced airgel composition or a reinforced OCMF material composition from any one of embodiments 1-11, wherein the total heat of endothermic decomposition of the fire rated additives in the composition is no more than , than 80% of the exothermic heat of decomposition of the composition residue in the absence of an additive corresponding to the fire safety class.

[00057] Embodiment 39 is a set of embodiments including the composition of any one of embodiments 1-38, wherein the oven temperature rise for the ISO 1182 composition is about 100°C or less, about 90°C or less , approximately 80°C or less, approximately 70°C or less, approximately 60°C or less, approximately 50°C or less, approximately 45°C or less, approximately 40°C or less, approximately 38°C or less, about 36°C or less, about 34°C or less, about 32°C or less, about 30°C or less, about 28°C or less, about 26°C or less, about 24°C or less, or is in the range between any two of these values.

[00058] Embodiment 40 is a set of embodiments including a composition from any one of embodiments 1-39, wherein the flame time for the ISO 1182 composition is about 30 seconds or less, about 25 seconds or less, about 20 seconds or less, about 15 seconds or less, about 10 seconds or less, about 5 seconds or less, about 2 seconds or less, or between any two of these values.

[00059] Embodiment 41 is a set of embodiments including the composition of any one of embodiments 1-40, wherein the mass loss for the ISO 1182 composition is about 50% or less, about 40% or less, about 30 % or less, about 28% or less, about 26% or less, about 24% or less, about 22% or less, about 20% or less, about 18% or less, about 16% or less, or between any two of these values.

[00060] Embodiment 42 is a set of embodiments including a composition from any one of the above embodiments, wherein the composition is flame retardant.

[00061] Embodiment 43 is a set of embodiments including a composition from any one of the above embodiments, where the composition is non-flammable.

[00062] Embodiment 44 is a set of embodiments including a composition from any one of the above embodiments, wherein the composition is refractory.

[00063] Embodiment 45 is a set of embodiments including a composition from any one of the above embodiments, where the composition is non-flammable.

[00064] Embodiment 46 is a set of embodiments including a composition of any one of the above embodiments, wherein the onset of endothermic decomposition of the fire rated additive is greater than 280°C, 300°C, 350°C, 400°C, 450°C or 500°C.

[00065] Embodiment 47 is a set of embodiments comprising a composition from any one of the above embodiments, wherein the onset of exothermic decomposition of the composition in the absence of a fire rated additive is greater than 280°C, 300°C, 350 °C, 400°C, 450°C or 500°C.

[00066] Embodiment 48 is a set of embodiments including a composition of any one of the above embodiments, wherein the OCMF material is a melamine-based foam.

[00067] Embodiment 49 is a set of embodiments including a composition of any one of the above embodiments, wherein the OCMF material is a urethane-based polymer foam.

[00068] Embodiment 50 is a set of embodiments including a composition of any one of the above embodiments, wherein the OCMF material is a reticulated foam.

[00069] Additionally, the aerogel materials or framework of various embodiments of the present invention may also be practiced using slurries or suspensions of airgel particles infiltrated into the OCMF materials described in the various embodiments. In yet another embodiment, various embodiments of the present invention may be practiced using non-particulate aerogel materials produced "in situ" by infiltrating the OCMF materials with various gel precursors in a suitable solvent and subsequently removing the solvent using various methods involving the use of supercritical fluids, either at elevated ambient temperatures and pressures or at subcritical pressures.

[00070] In certain embodiments, the present invention includes a reinforced airgel composition or a composition reinforced with OCMF material, including one or more - or even all - of the above features and characteristics, including various combinations and methods of making them.

[00071] Data and other important objects, advantages and features of the invention will become clear as the disclosure of the invention progresses.

[00072] Accordingly, the invention includes the features or structure, combination or elements and arrangement of parts which will be exemplified in the disclosure set forth below herein, and the scope of the invention will be set forth in the claims.

[00073] BRIEF DESCRIPTION OF THE DRAWINGS

[00074] Figure 1 depicts the results of measurements using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) for an airgel composition in the absence of any additives, a hydrophobic airgel composition of the present invention reinforced with melamine foam and containing approximately 120% magnesium hydroxide, in this case, 100% in the calculation represents the mass of silicon dioxide and hydrophobic components of the airgel composition (example 3).

[00075] Figure 2 depicts the results of measurements using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) for an airgel composition in the absence of any additives, a hydrophobic airgel composition of the present invention reinforced with melamine foam and containing approximately 120% halloysite clay, in this case, 100% in the calculation represents the mass of silicon dioxide and hydrophobic components of the airgel composition (example 21).

[00076] DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[00077] In the following detailed description of preferred embodiments, reference is made to the accompanying drawings, which form a part thereof, and in which, by way of illustration, specific embodiments are shown in which the invention may be practiced. As will be appreciated, other embodiments may be used and structural changes may be made without departing from the scope of the invention.

[00078] As used in this specification and the accompanying claims, the singular forms “one,” “a certain,” and “given” will include plural counterparts unless the content clearly dictates otherwise. As used in this specification and the accompanying claims, the term “or” is generally used in its meaning to include “and/or” unless the context clearly dictates otherwise.

[00079] As used herein, the term “about” has the meaning of “about” or “almost” and, in the context of the numerical values or ranges presented, means ±15% of the numerical value. In one embodiment, the term “approximately” may include conventional rounding according to significant digits of a numerical value. In addition, the phrase “from about x to about y” includes the phrase “from about x to about y.”

[00080] As used herein, the terms “composition” and “composite” are used interchangeably.

[00081] Aerogels are one class of porous materials having open cells and comprising a framework of interconnected structures, wherein a corresponding network of pores is integrated within the framework and the intermediate phase in the network of pores is primarily formed from gases such as air. Aerogels are typically characterized by low density, high porosity, large specific surface area, and small pore sizes. Aerogels can be distinguished from other porous materials by their physical and structural properties.

[00082] In the context of the present disclosure, the terms "aerogel" or "airgel material" refer to a gel comprising a framework of interconnected structures, a corresponding network of interconnected pores integrated within the framework, and containing gases, such as air, as a dispersed intervening agent. environment; and which is characterized by the following physical and structural properties (as tested using nitrogen porosimetry) ascribed to aerogels: (a) an average pore diameter in the range of about 2 nm to about 100 nm, (b) a porosity of at least , 80% or more, and (c) a specific surface area of approximately 20 m ² /g or more.

[00083] Thus, the aerogel materials of the present disclosure include any aerogels or other open cell compositions that satisfy the defining elements presented in the preceding paragraphs; including formulations that may otherwise be classified as xerogels, cryogels, ambigels, microporous materials and the like.

[00084] Aerogel materials may also be characterized by additional physical properties including: (d) pore volume of about 2.0 ml/g or more, in particular about 3.0 ml/g or more; (f) a density of approximately 0.50 g/cc. cm or less, in particular approximately 0.25 g/cc. cm or less; and (f) at least 50% of the total pore volume comprises pores having a pore diameter in the range between 2 and 50 nm; although satisfaction of these additional properties is not required to characterize the composition as an airgel material.

[00085] As used herein, the term “innovative processing and extraction techniques” refers to methods of replacing a liquid intermediate phase in a wet gel material with a gas, such as air, in a manner that promotes low pore collapse and low shrinkage for the gel framework structure. Drying techniques such as ambient evaporation often introduce high capillary pressures and other mass transfer limitations at the liquid-vapor interface of the intermediate phase being evaporated or removed. Large capillary forces generated as a result of evaporation or removal of liquid can stimulate the occurrence of significant pore shrinkage and collapse of the framework in the gel material. The use of innovative processing and extraction techniques during liquid intermediate phase extraction reduces the adverse effects of capillary forces on the pores and gel framework during liquid extraction (also referred to as "solvent removal" or "drying").

[00086] In certain embodiments, the innovative processing and extraction techniques utilize near-critical or supercritical fluids or near-critical or supercritical conditions to extract the liquid intermediate phase from the wet gel material. This may be accomplished by removing the liquid intermediate phase from the gel near or above the critical point for the liquid or mixture of liquids. To optimize the extraction process when using a near-critical or supercritical fluid, co-solvents and solvent exchanges can be used.

[00087] In certain embodiments, the innovative processing and extraction technique involves modifying the gel framework to reduce the irreversible effects of capillary pressures and other mass transfer limitations at the liquid-vapor interface. This embodiment may include treating the gel framework with a hydrophobizing agent or other functionalizing agents that enable the gel framework to withstand or recover from any collapsing forces during liquid extraction performed below the critical point for the liquid intermediate phase. This embodiment may also include the introduction of functional groups or scaffold elements that provide a scaffold modulus that is high enough to withstand or recover from collapsing forces during liquid extraction performed below the critical point for the liquid intermediate phase.

[00088] As used herein, the terms “framework” or “framework structure” refer to a network of interconnected oligomers, polymers, or particles that form a solid structure of the material. As used herein, the terms “airgel framework” or “airgel framework structure” refer to a network of interconnected oligomers, polymers, or colloidal particles that form a solid gel or aerogel structure. The polymers or particles that make up the airgel framework typically have a diameter of approximately 100 angstroms. However, the framework structures of the present disclosure may also include networks of interconnected oligomers, polymers or colloidal particles of all diameter sizes that form a solid structure in a material such as a gel or airgel. In addition, the terms “silica aerogel” or “silica airgel framework” refer to an airgel framework in which silica constitutes at least 50% by weight of the oligomers, polymers or colloidal particles that form a solid framework structure in a gel or aerogel.

[00089] As used herein, the term “airgel composition” refers to any composite material that includes an airgel material as a component of the composite. Examples of airgel compositions include, but are not limited to: fiber reinforced aerogel composites; aerogel composites that include added elements such as opacifiers; aerogel composites reinforced with open-cell macroporous scaffolds; airgel-polymer composites; and composite materials that incorporate particles, particles, granules, beads or airgel powders into solid or semi-solid material such as binders, resins, cements, foams, polymers or similar solid materials. Aerogel compositions are generally prepared after removal of solvent from the various gel materials disclosed in this invention. The aerogel compositions obtained in this manner may further be subjected to further processing or processing. The various gel materials may also be subjected to further processing or processing otherwise known or suitable for use in the art prior to solvent removal (or liquid extraction or drying).

[00090] As used herein, the term “monolithic” refers to airgel materials in which the majority (by weight) of the airgel included in the airgel material or composition is in the form of a single interconnected airgel nanostructure. Monolithic airgel materials include airgel materials that are initially produced having a single interconnected gel or airgel nanostructure, but which are subsequently cleaved, broken or segmented to produce non-uniform airgel nanostructures. Monolithic airgel materials are different from dispersed airgel materials. The term "particulate airgel material" refers to airgel materials in which the majority (by weight) of the airgel included in the airgel material is in the form of particles, particles, granules, beads or powders that can be combined or pressed together, but which lack an interconnected airgel nanostructure between individual particles.

[00091] In the context of the present disclosure, the term “wet gel” refers to a gel in which the mobile intermediate phase in a network of interconnected pores is primarily formed from a liquid, such as a common solvent, liquefied gases like liquid carbon dioxide, or combinations thereof. Aerogels typically require the initial production of a wet gel, followed by innovative processing and extraction to replace the mobile intermediate liquid in the gel with air. Examples of wet gels include, but are not limited to: alcohols, hydrogels, ketogels, carbonogels, and any other wet gels known to those skilled in the art.

[00092] The aerogel compositions of the present disclosure may include reinforced aerogel compositions. As used herein, the term “reinforced airgel composition” refers to aerogel compositions comprising a reinforcing phase in the airgel material, where the reinforcing phase is not part of the airgel framework itself. The reinforcing phase can be any material that imparts increased flexibility, resiliency, shape-forming or structural stability to the airgel material. Examples of well-known reinforcement materials include, but are not limited to: open cell macroporous frame reinforcements, closed cell macroporous frame reinforcements, open cell membranes, honeycomb reinforcements, polymeric reinforcements, and fibrous reinforcements such as discrete fibers, woven materials, non-woven materials, needle-punched non-woven materials, battings, linens, mats and felts.

[00093] Reinforced aerogel compositions of the present disclosure may include aerogel compositions reinforced with open cell macroporous framework materials. As used herein, the terms "open cell macroporous framework" or "OCMF" refer to a porous material comprising a framework of interconnected structures characterized by a substantially uniform composition, wherein a corresponding network of interconnected pores is integrated within the framework; and which is characterized by an average pore diameter ranging from about 10 μm to about 700 μm. This average pore diameter can be measured using known techniques including, but not limited to: microscopy with optical analysis. Thus, the OCMF materials of the present disclosure include any open cell materials that satisfy the defining elements presented in this paragraph, including compositions that may otherwise be classified as foams, foam materials, macroporous materials, and the like. OCMF materials can be distinguished from materials that include a framework of interlocking structures that demonstrate the presence of volume of cavities in the framework, and which are not characterized by a homogeneous composition, such as aggregations of fibers and binders, demonstrating the presence of volume of voids in the fibrous matrix.

[00094] In the context of the present disclosure, the term “substantially homogeneous composition” refers to the uniformity of the composition of said material within a 10% tolerance.

[00095] As used herein, the term “OCMF-reinforced airgel composition” refers to a reinforced airgel composition comprising an open-cell macroporous framework material as the reinforcing phase. OCMF materials suitable for use in the present disclosure include, but are not limited to: OCMF materials derived from organic polymeric materials. Examples include OCMF materials derived from polyolefins, polyurethanes, phenolic materials, melamine material, cellulose acetate and polystyrene. In the context of the present disclosure, the term "organic OCMF material" refers to OCMF materials including a framework formed primarily from organic polymeric materials. In certain embodiments, OCMF materials derived from melamine or melamine derivatives are also preferred. In the context of the present disclosure, the terms "melamine OCMF material" or "melamine-based OCMF material" refer to organic OCMF materials comprising a framework formed primarily from polymeric materials produced by reacting melamine with a condensation agent such as formaldehyde. Examples of OCMF materials derived from melamine or melamine derivatives for use in the present disclosure are presented in US Patent Nos. 8546457, 4666948 and WO 2001/094436. The term "inorganic OCMF material" refers to OCMF materials comprising a framework formed primarily from inorganic materials. Examples of inorganic OCMF materials include, but are not limited to: cementitious materials, gypsum, and calcium silicate.

[00096] In the context of the present invention, the term "foam" refers to a material comprising a framework of interlocking polymeric structures characterized by a substantially uniform composition, with a corresponding network or array of pores integrated into the framework, and which is obtained by dispersing a certain proportion of gas in form of bubbles in a liquid or resin foam so that the gas bubbles are retained as pores as the foam cures to form a solid structure. In general, foams can be produced using a wide range of technological processes - see, for example, US patent Nos. 6,147,134; 5,889,071; 6,187,831; and 5,229,429. Thus, the foam materials of the present disclosure include any materials that satisfy the defining elements presented in this paragraph, including compositions that might otherwise be classified as OCMF materials, macroporous materials, and the like. Foams as defined herein may be of the thermoplastic, elastomer, and thermoset (duromer) types.

[00097] Pores in a solid framework may also be referred to as "cells". Cells may be separated by cell walls or membranes, which creates a cluster of independent closed cells in a porous material. The term "closed cell" refers to porous materials in which at least 50% of the pore volume corresponds to [substantially] isolated cells bounded by membranes or walls. Cells in a material can also be interconnected by opening the cells, which creates a network of interconnected open pores in the material. The term "open cell" refers to porous materials in which at least 50% of the pore volume corresponds to open cells. The open cell material may include an open cell mesh material, a non-mesh open cell material, or a combination thereof. Mesh materials are open-cell materials produced using a mesh manufacturing process that eliminates or punctures cell membranes in a porous material. Mesh materials generally have a higher concentration of open cells than non-mesh materials, but tend to be more expensive and difficult to produce. In general, no porous material exhibits exclusively one type of cell structure (open cell or closed cell). Porous materials can be manufactured using a wide range of manufacturing processes, including the foam manufacturing processes described in US Patent Nos. 6147134, 5889071, 6187831, 5229429, 4454248 and US Patent Application No. 20070213417.

[00098] As used herein, the terms “airgel sheet” or “airgel sheet composition” refer to aerogel compositions reinforced with a continuous sheet of reinforcing material. Aerogel sheet compositions can be distinguished from other reinforced aerogel compositions, which are reinforced with non-continuous reinforcing material, such as individual agglomerates or lumps of reinforcing material. Aerogel sheet compositions are particularly well suited for use in applications requiring flexibility as they are highly shape-shifting and can be used like a sheet to cover surfaces having simple or complex geometries, while also maintaining excellent thermal insulation properties. properties of aerogels.

[00099] In the context of the present disclosure, the terms “flexible” and “flexibility” refer to the ability of a material or airgel composition to bend or flex without macrostructural failure. The aerogel compositions of the present disclosure are capable of bending at least 5°, at least 25°, at least 45°, at least 65°, or at least 85°, without macroscopic failure; and/or have a bend radius of less than 4 feet (1.219 meters), less than 2 feet (0.610 meters), less than 1 foot (0.305 meters), less than 6 inches (0.152 meters), less than less than 3 inches (0.076 meters), less than 2 inches (0.051 meters), less than 1 inch (0.025 meters), or less than 1/2 inch (0.013 meters), in the absence of macroscopic failure. Similarly, the terms “highly flexible” or “highly flexible” refer to materials or aerogel compositions capable of bending through at least 90° and/or having a bend radius of less than 1/2 inch (0.013 meters), in the absence of macroscopic destruction. In addition, the terms “classified as flexible” and “classified as flexible” refer to materials or aerogel compositions that may be classified as flexible in accordance with ASTM C1101 (ASTM International, West Conshohocken, PA).

[000100] The aerogel compositions of the present disclosure may be flexible, highly flexible, and/or classified as flexible. The aerogel compositions of the present disclosure may also be drapeable. As used herein, the terms “drape” and “drapeability” refer to the ability of a material or airgel composition to flex or flex 90° or more over a radius of curvature of approximately 4 inches (0.102 meters) or less without macroscopic failure. The aerogel materials or compositions of certain embodiments of the present invention are flexible such that the composition is non-rigid and can be applied and shaped onto three-dimensional surfaces or objects or preformed into a range of profiles and configurations for ease of installation or application.

[000101] As used herein, the terms “additive” or “added element” refer to materials that may be added to the airgel composition before, during, or after production of the airgel. Additives may be added to change or improve the desired properties of the airgel or to prevent undesirable properties of the airgel from occurring. Additives are typically added to the airgel material either before gelation into a precursor liquid, during gelation into a transition state material, or after gelation into a solid or semi-solid material. Examples of additives include, but are not limited to: microfibers, fillers, reinforcing agents, stabilizers, thickeners, elastic compounds, opacifiers, coloring or pigmentation compounds, radiation absorbing compounds, radiation reflecting compounds, fire rated additives, anti-corrosion inhibitors, thermally conductive components, phase change materials, pH regulators, redox regulators, HCN protectants, exhaust gas protectants, electrically conductive compounds, electrical dielectric compounds, magnetic compounds, radar blocking components, hardeners, anti-shrink agents and other airgel additives known to those skilled in the relevant field of technology.

[000102] As used herein, the terms "thermal conductivity" and "TC" refer to a measurement of the ability of a material or composition to transfer heat between two surfaces on either side of the material or composition when there is a temperature difference between the two surfaces. Thermal conductivity, specifically, is measured as the thermal energy transferred per unit time across a unit surface area divided by the temperature difference. It is usually recorded in SI units as mW/m*K (milliwatts per meter * degree Kelvin). The thermal conductivity of a material can be determined using test methods known in the art, including, but not limited to: Test Method for Steady-State Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus (ASTM C518, ASTM International, West Conshohocken, PA); Test Method for Steady-State Heat Flux Measurements and Thermal Transmission Properties by Means of the Guarded-Hot-Plate Apparatus (ASTM C177, ASTM International, West Conshohocken, PA); Test Method for Steady-State Heat Transfer Properties of Pipe Insulation (ASTM C335, ASTM International, West Conshohocken, PA); Thin Heater Thermal Conductivity Test (ASTM C1114, ASTM International, West Conshohocken, PA); Determination of thermal resistance by means of guarded hot plate and heat flow meter methods (EN 12667, British Standards Institution, United Kingdom); or Determination of steady-state thermal resistance and related properties - Guarded hot plate apparatus (ISO 8203, International Organization for Standardization, Switzerland). As is to be understood in the context of the present disclosure, and unless otherwise expressly stated, due to the use of different methods, it is possible that different results may be obtained, thermal conductivity measurements will be obtained in accordance with ASTM C518 (Test Method for Steady-State). Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus) at a temperature of approximately 37.5°C, ambient atmospheric pressure and a compressive load of approximately ² psi (138 kPa). Measurement results reported in accordance with ASTM C518 generally correlate well with any measurement results obtained in accordance with EN 12667, with any appropriate adjustment to compressive load. In certain embodiments, the aerogel materials or compositions of the present disclosure have a thermal conductivity of about 40 mW/m-K or less, about 30 mW/m-K or less, about 25 mW/m-K or less, about 20 mW/m -K or less, approximately 18 mW/m-K or less, approximately 16 mW/m-K or less, approximately 14 mW/m-K or less, approximately 12 mW/m-K or less, approximately 10 mW/m -K or less, approximately 5 mW/m-K or less, or between any two of these values.

[000103] Thermal conductivity measurements can also be obtained at a temperature of approximately 10°C at atmospheric pressure under compression conditions. The results of thermal conductivity measurements at 10°C are generally 0.5-0.7 mW/m-K less than the corresponding results of thermal conductivity measurements at 37.5°C. In certain embodiments, the aerogel materials or compositions of the present disclosure have a thermal conductivity at 10°C of about 40 mW/m-K or less, about 30 mW/m-K or less, about 25 mW/m-K or less, about 20 mW/m-K or less, approximately 18 mW/m-K or less, approximately 16 mW/m-K or less, approximately 14 mW/m-K or less, approximately 12 mW/m-K or less, approximately 10 mW/m-K or less, approximately 5 mW/m-K or less, or between any two of these values.

[000104] In the context of the present disclosure, the term “density” refers to the measurement of mass per unit volume of an airgel material or composition. The term "density" generally refers to the apparent density for the airgel material as well as the bulk density for the airgel composition. Density is usually recorded as kg/m ³ or g/cu. see Density for an airgel material or composition can be determined using methods known in the art, including, but not limited to: Standard Test Method for Dimensions and Density of Preformed Block and Board-Type Thermal Insulation (ASTM C303, ASTM International, West Conshohocken, PA); Standard Test Methods for Thickness and Density of Blanket or Batt Thermal Insulations (ASTM C167, ASTM International, West Conshohocken, PA); Determination of the apparent density of preformed pipe insulation (EN 13470, British Standards Institution, United Kingdom); or Determination of the apparent density of preformed pipe insulation (ISO 18098, International Organization for Standardization, Switzerland). As will be understood in the context of the present disclosure, due to the use of different methods, possibly different results, density measurements will be obtained in accordance with ASTM C167 (Standard Test Methods for Thickness and Density of Blanket or Batt Thermal Insulations) when 2 psi ² (138 kPa) compression for thickness measurements unless otherwise stated. In certain embodiments, the aerogel materials or compositions of the present disclosure have a density of approximately 0.60 g/cc. cm or less, approximately 0.50 g/cc. cm or less, approximately 0.40 g/cc. cm or less, approximately 0.30 g/cc. cm or less, approximately 0.25 g/cc. cm or less, approximately 0.20 g/cc. cm or less, approximately 0.18 g/cc. cm or less, approximately 0.16 g/cc. cm or less, approximately 0.14 g/cc. cm or less, approximately 0.12 g/cu. cm or less, approximately 0.10 g/cc. cm or less, approximately 0.05 g/cc. cm or less, approximately 0.01 g/cc. cm or less or in the range between any two of these values.

[000105] As used herein, the term “hydrophobicity” refers to a measurement of the ability of a material or airgel composition to repel water.

[000106] The hydrophobicity of an airgel material or composition can be expressed in terms of absorption of liquid water. As used herein, the term “liquid water uptake” refers to a measurement of the potential of a material or airgel composition to absorb or otherwise retain liquid water. Liquid water uptake may be expressed as the percentage (on a weight basis or on a volume basis) of water that is absorbed or otherwise retained by a material or airgel composition when exposed to liquid water under specified measurement conditions. Liquid water absorption of an airgel material or composition can be determined using methods known in the art, including, but not limited to: Standard Test Method for Determining the Water Retention (Repellency) Characteristics of Fibrous Glass Insulation (ASTM C1511, ASTM International, West Conshohocken, PA); Standard Test Method for Water Absorption by Immersion of Thermal Insulation Materials (ASTM C1763, ASTM International, West Conshohocken, PA); Thermal insulating products for building applications: Determination of short term water absorption by partial immersion (EN 1609, British Standards Institution, United Kingdom). As will be understood in the context of the present disclosure, because different methods may result in different results, liquid water absorption measurements will be obtained in accordance with ASTM C1511 (Standard Test Method for Determining the Water Retention (Repellency) Characteristics of Fibrous Glass Insulation) at ambient pressure and temperature unless otherwise stated. In certain embodiments, the aerogel materials or compositions of the present disclosure may have a liquid water uptake of about 50 wt% or less, about 40 wt% or less, about 30 wt% or less, about 20 % (wt.) or less, about 15% (wt.) or less, about 10% (wt.) or less, about 8% (wt.) or less, about 3% (wt.) or less, about 2 % (wt.) or less, about 1% (wt.) or less, about 0.1% (wt.) or less, or between any two of these values. An airgel material or composition that exhibits improved liquid water absorption relative to other airgel materials or compositions will exhibit a lower percentage of liquid water absorption/retention relative to reference materials or aerogel compositions.

[000107] The hydrophobicity of an airgel material or composition can be expressed in terms of water vapor absorption. In the context of the present disclosure, the term “water vapor absorption” refers to a measurement of the potential of a material or airgel composition to absorb water vapor. Water vapor absorption can be expressed as the percentage (on a weight basis) of water that is absorbed or otherwise retained by a material or airgel composition when exposed to water vapor under specified measurement conditions. The water vapor absorption of an airgel material or composition can be determined using methods known in the art, including, but not limited to: Standard Test Method for Determining the Water Vapor Sorption of Unfaced Mineral Fiber Insulation (ASTM C1104, ASTM International , West Conshohocken, PA); Thermal insulating products for building applications: Determination of long term water absorption by diffusion (EN 12088, British Standards Institution, United Kingdom). As will be understood in the context of the present disclosure, because different methods may result in different results, water vapor absorption measurements will be obtained in accordance with ASTM C1104 (Standard Test Method for Determining the Water Vapor Sorption of Unfaced Mineral Fiber Insulation) at 49°C and 95% humidity for 24 hours (which is a modification of 96 hours according to ASTM C1104) at ambient pressure, unless otherwise stated. In certain embodiments, the aerogel materials or compositions of the present disclosure may have water vapor absorption of about 50 wt% or less, about 40 wt% or less, about 30 wt% or less, about 20 % (wt.) or less, about 15% (wt.) or less, about 10% (wt.) or less, about 8% (wt.) or less, about 3% (wt.) or less, about 2 % (wt.) or less, about 1% (wt.) or less, about 0.1% (wt.) or less, or between any two of these values. An airgel material or composition that exhibits improved water vapor absorption relative to other airgel materials or compositions will have a lower water vapor absorption/retention percentage relative to reference materials or aerogel compositions.

[000108] The hydrophobicity of a material or airgel composition can be expressed by measuring the equilibrium contact angle of a drop of water at the interface with the surface of the material. The aerogel materials or compositions of the present disclosure may have a water contact angle of about 90° or more, about 120° or more, about 130° or more, about 140° or more, about 150° or more, about 160° or more , approximately 170° or more, approximately 175° or more, or between any two of these values.

[000109] In the context of the present disclosure, the terms "heat of combustion", "HC" and "ΔHc" refer to the measurement of the amount of thermal energy released during combustion or exothermic thermal decomposition of a material or composition. Heat of combustion is usually reported in calories (4.187 J) of thermal energy released per gram of material or airgel composition (cal/g (4.187 J/g)) or in megajoules of thermal energy released per kilogram of material or composition ( MJ/kg). The heat of combustion of a material or composition may be determined using methods known in the art, including, but not limited to, the following: Reaction to fire tests for products - Determination of the gross heat of combustion (calorific value) (EN ISO 1716, International Organization for Standardization, Switzerland; EN adopted). In the context of the present disclosure, calorific value measurements will be obtained in accordance with the standards of EN ISO 1716 (Reaction to fire tests for products - Determination of the gross heat of combustion (calorific value)), unless otherwise stated. In certain embodiments, the aerogel compositions of the present disclosure may have a heating value of about 750 cal/g (3.14 (kJ/g)) or less, about 717 cal/g (3.00 (kJ/g)) or less , approximately 700 cal/g (2.93 (kJ/g)) or less, approximately 650 cal/g (2.72 (kJ/g)) or less, approximately 600 cal/g (2.51 (kJ/g) )) or less, approximately 575 cal/g (2.41 (kJ/g)) or less, approximately 550 cal/g (2.30 (kJ/g)) or less, approximately 500 cal/g (2.09 (kJ/g)) or less, approximately 450 cal/g (1.88 (kJ/g)) or less, approximately 400 cal/g (1.67 (kJ/g)) or less, approximately 350 cal/g (1.47 (kJ/g)) or less, approximately 300 cal/g (1.26 (kJ/g)) or less, approximately 250 cal/g (1.05 (kJ/g)) or less, approximately 200 cal/g (0.84 (kJ/g)) or less, approximately 150 cal/g (0.63 (kJ/g)) or less, approximately 100 cal/g (0.42 (kJ/g)) or less, approximately 50 cal/g (0.21 (kJ/g)) or less, approximately 25 cal/g (0.10 (kJ/g)) or less, approximately 10 cal/g (0.04 (kJ) /g)) and less than or in the range between any two of these values. An airgel composition that has an improved heating value relative to another airgel composition will have a lower heating value relative to reference aerogel compositions. In certain embodiments of the present disclosure, the TC value of the airgel composite is improved by incorporating a fire rated additive into the airgel composite.

[000110] In the context of the present disclosure, all thermal analyzes and associated definitions refer to measurements made by starting the operation at 25°C and ramping at a rate of 20°C at a rate of one minute up to 1000°C in air at ambient pressure. Accordingly, any changes in these parameters must be taken into account (or the operation must be re-performed under these conditions) when measuring and calculating the onset of thermal decomposition, peak heat release temperature, peak heat absorption temperature and the like. In the context of the present disclosure, the terms "thermal decomposition onset" and " _TD " refer to the measurement of the lowest temperature for environmental heat at which a material or composition exhibits rapid exothermic reactions from the decomposition of organic material. The onset of thermal decomposition of organic material in a material or composition can be measured using thermogravimetric analysis (TGA). The TGA curve for a material depicts the weight loss (% (wt)) for the material when it is exposed to an increase in ambient temperature, thus indicating thermal decomposition. The onset of thermal decomposition of a material can be correlated with the intersection point of the following tangent lines to the TGA curve: a line tangent to the baseline of the TGA curve and a line tangent to the TGA curve at the point of maximum slope during the rapid exothermic decomposition phenomenon associated with the decomposition of organic material. In the context of the present disclosure, measurements of the onset of thermal decomposition of organic material will be obtained using TGA analysis in accordance with the presentation of the invention in this paragraph, unless stated otherwise.

[000111] The onset of thermal decomposition of a material can be measured using differential scanning calorimetry (DSC) analysis. The DSC curve for a material depicts the thermal energy (mW/mg) released by the material when it is exposed to a gradual increase in ambient temperature. The temperature at which thermal decomposition of a material begins can be correlated with the point on the DSC curve where the Δ mW/mg value (change in thermal energy output) is maximized, thus indicating the production of exothermic heat from the airgel material. In the context of the present disclosure, thermal decomposition onset measurements using DSC, TGA, or both will be obtained using a temperature ramp rate of 20°C/min in accordance with the additional definition of the invention in the preceding paragraph, unless expressly stated otherwise. DSC and TGA methods each provide similar values for a given onset of thermal decomposition, and in many cases tests are carried out in parallel so that results are obtained from both methods. In certain embodiments, the aerogel materials or compositions of the present disclosure are characterized by an onset of thermal decomposition corresponding to about 300°C or more, about 320°C or more, about 340°C or more, about 360°C or more, about 380°C or more more than about 400°C or more, about 420°C or more, about 440°C or more, about 460°C or more, about 480°C or more, about 500°C or more, about 550°C or more , approximately 600°C or more, or between any two of these values. As used herein, for example, a first composition having a thermal decomposition onset that is higher than the thermal decomposition onset of a second composition will be considered an improvement when comparing the first composition and the second composition. As contemplated herein, the onset of thermal decomposition of a composition or material is increased when one or more fire rated additives are added compared to a composition that does not include any fire rated additives.

[000112] As used herein, the terms "onset of endothermic decomposition" and "T _ED " refer to the measurement of the lowest ambient heat temperature at which a material or composition exhibits endothermic reactions from decomposition or dehydration. The onset of endothermic decomposition of a material or composition can be measured using thermogravimetric analysis (TGA). The TGA curve for a material depicts the weight loss (% (wt)) for the material when it is exposed to an increase in ambient temperature. The onset of thermal decomposition of a material can be correlated with the intersection point of the following tangent lines to the TGA curve: a line tangent to the baseline of the TGA curve and a line tangent to the TGA curve at the point of maximum slope during rapid endothermic decomposition or dehydration of the material. In the context of the present disclosure, measurement results of the onset of endothermic decomposition of a material or composition will be obtained using a TGA analysis in accordance with the presentation of the invention in this paragraph, unless stated otherwise.

[000113] In the context of the present disclosure, the terms "oven temperature rise" and "ΔT _R " refer to the result of measuring the difference between the maximum temperature (T _MAX ) for a material or composition under thermal decomposition conditions relative to the baseline temperature for a given material or composition under conditions thermal decomposition (usually final temperature or T _FIN ). The rise in oven temperature is usually recorded in degrees Celsius or °C. The oven temperature rise for a material or composition can be determined using methods known in the art, including, but not limited to, the following: Reaction to fire tests for building and transport products: Non-combustibility test (EN ISO 1182, International Organization for Standardization, Switzerland; EN adopted). In the context of the present disclosure, oven temperature rise measurements will be obtained in accordance with conditions comparable to the EN ISO 1182 standard (Reaction to fire tests for building and transport products: Non-combustibility test), unless otherwise stated. In certain embodiments, the aerogel compositions of the present disclosure may have an oven temperature rise of about 100°C or less, about 90°C or less, about 80°C or less, about 70°C or less, about 60°C or less , approximately 50°C or less, approximately 45°C or less, approximately 40°C or less, approximately 38°C or less, approximately 36°C or less, approximately 34°C or less, approximately 32°C or less, about 30°C or less, about 28°C or less, about 26°C or less, about 24°C or less, or between any two of these values. In the context of compositional stability at elevated temperatures, for example, a first composition having an oven temperature rise that is less than the oven temperature rise of the second composition would be considered an improvement when comparing the first composition and the second composition. As provided herein, the oven temperature rise for a composition is reduced when one or more fire rated additives are added compared to a composition that does not include any fire rated additives.

[000114] In the context of the present disclosure, the terms "flame time" and "T _FLAME " refer to the result of a measurement of persistent ignition for a material or composition under thermal decomposition conditions, where the term "persistent ignition" corresponds to the continued existence of a flame in any part of the visible part of the sample lasting 5 seconds or more. Flame time is usually recorded in seconds or minutes. The flame time for a material or composition can be determined using methods known in the art, including, but not limited to, the following: Reaction to fire tests for building and transport products: Non-combustibility test (EN ISO 1182, International Organization for Standardization, Switzerland; EN adopted). In the context of the present disclosure, flame time measurement results will be obtained in accordance with conditions comparable to the EN ISO 1182 standard (Reaction to fire tests for building and transport products: Non-combustibility test), unless otherwise stated. In certain embodiments, the aerogel compositions of the present disclosure have a flame time of about 30 seconds or less, about 25 seconds or less, about 20 seconds or less, about 15 seconds or less, about 10 seconds or less, about 5 seconds or less, approximately 2 seconds or less, or between any two of these values. As used herein, for example, a first composition having a flame time that is less than the flame time of the second composition will be considered an improvement when comparing the first composition and the second composition. As provided herein, the flame time of a composition is reduced by the addition of one or more fire rated additives compared to a composition that does not include any fire rated additives.

[000115] In the context of the present disclosure, the terms "mass loss" and "ΔM" refer to a measurement of the amount of material, composition or composite that is lost or burned away under thermal decomposition conditions. Weight loss is usually recorded as percent by weight or % (wt). The mass loss for a material, composition or composite can be determined using methods known in the art, including, but not limited to, the following: Reaction to fire tests for building and transport products: Non-combustibility test (EN ISO 1182, International Organization for Standardization, Switzerland; EN adopted). In the context of the present disclosure, mass loss measurements will be obtained in accordance with conditions comparable to the EN ISO 1182 standard (Reaction to fire tests for building and transport products: Non-combustibility test), unless otherwise stated. In certain embodiments, the aerogel compositions of the present disclosure have a mass loss of about 50% or less, about 40% or less, about 30% or less, about 28% or less, about 26% or less, about 24% or less, about 22% or less, about 20% or less, about 18% or less, about 16% or less, or between any two of these values. As used herein, for example, a first composition having a weight loss that is less than the weight loss of a second composition will be considered an improvement when comparing the first composition and the second composition. As contemplated herein, the weight loss of a composition is reduced by the addition of one or more fire rated additives compared to a composition that does not include any fire rated additives.

[000116] In the context of the present disclosure, the term “peak heat release temperature” refers to a measurement result regarding the temperature for ambient heat at which the exothermic heat release from decomposition is at its maximum. The peak heat release temperature for a material or composition can be measured using TGA analysis, differential scanning calorimetry (DSC), or a combination thereof. DSC and TGA methods each provide similar results for the peak heat release temperature, and in many cases tests are run in parallel so that results are obtained from both methods. In conventional DSC analysis, heat flow is plotted against rising temperature, and the peak heat release temperature is the temperature at which the highest peak on such a curve occurs. In the context of the present disclosure, the peak heat release temperature measurement results for a material or composition will be obtained using a TGA analysis in accordance with the presentation of the invention in this paragraph, unless stated otherwise.

[000117] In the context of an endothermic material, the term “peak heat absorption temperature” refers to a measurement of the ambient heat temperature at which endothermic heat absorption from decomposition is at its maximum. The peak heat absorption temperature for a material or composition can be measured using TGA analysis, differential scanning calorimetry (DSC), or a combination thereof. In conventional DSC analysis, heat flow is plotted against rising temperature, and the peak heat absorption temperature is the temperature at which the lowest peak on such a curve occurs. In the context of the present disclosure, the peak heat absorption temperature measurement results for a material or composition will be obtained using a TGA analysis in accordance with the presentation of the invention in this paragraph, unless stated otherwise.

[000118] As used herein, the terms “flammability retardant” and “flammability retardant” refer to a material or composition that satisfies the following combination of properties: i) an oven temperature rise of 50° C. or less; ii) flame time of 20 seconds or less; and iii) a weight loss of 50% (w/w) or less. In the context of the present disclosure, the terms “non-flammability” and “non-flammable” refer to a material or composition that satisfies the following combination of properties: i) an oven temperature rise of 40° C. or less; ii) flame time of 2 seconds or less; and iii) a weight loss of 30% (w/w) or less. As contemplated, the flammability (eg, the combination of oven temperature rise, flame time, and mass loss) of the composition is reduced by the inclusion of one or more fire rated additives as described herein.

[000119] As used herein, the terms “refractory” and “refractory” refer to a material or composition that is refractory to combustion and has a total heating value (HOC) of less than or equal to 3 MJ/kg. In the context of the present disclosure, the terms “non-flammable” and “non-combustible” refer to a non-flammable material or composition that has a heating value (HOC) of less than or equal to 2 MJ/kg. As contemplated, the NOC value of the composition is reduced by the inclusion of one or more fire rated additives as described herein.

[000120] Aerogels are described as a framework of interconnected structures, which are most often formed from interconnected oligomers, polymers or colloidal particles. The airgel framework can be made from a range of precursor materials, including inorganic precursor materials (such as the precursors used in the production of silica-based aerogels); organic precursor materials (such as precursors used in the production of carbon-based aerogels); hybrid inorganic/organic precursor materials; and their combinations. In the context of the present disclosure, the term "amalgam airgel" refers to an airgel produced from a combination of two or more different gel precursors; the corresponding precursors are referred to as “amalgam precursors.”

[000121] Inorganic aerogels are generally prepared from metal oxide or metal alkoxide materials. Metal oxide or metal alkoxide materials may be based on the oxides or alkoxides of any metal that can form oxides. Such metals include, but are not limited to: silicon, aluminum, titanium, zirconium, hafnium, yttrium, vanadium, cerium and the like. Inorganic silica aerogels are traditionally prepared by hydrolysis and condensation of silica alkoxides (such as tetraethoxysilane) or by gelation for silicic acid or liquid glass. Other suitable inorganic precursor materials for silica airgel synthesis include, but are not limited to: metal silicates such as sodium silicate or potassium silicate, alkoxysilanes, partially hydrolyzed alkoxysilanes, tetraethoxysilane (TEOS), partially hydrolyzed TEOS compound, condensed polymers TEOS, tetramethoxysilane (TMOS), partially hydrolyzed TMOS compound, fused TMOS polymers, tetra-n-propoxysilane, partially hydrolyzed and/or fused tetra-n-propoxysilane polymers, polyethyl silicates, partially hydrolyzed polyethyl silicates, monomeric alkylalkoxysilanes, bistrialkoxyalkyl- or -arylsilanes, polyhedral silsesquioxanes or combinations thereof.

[000122] In certain embodiments of the present disclosure, a pre-hydrolyzed TEOS compound, such as Silbond H-5 (SBH5, Silbond Corp.), which is hydrolyzed at a water/silica ratio of approximately 1.9-2, or it can be further hydrolyzed before being introduced into the gelling process. Partially hydrolyzed TEOS or TMOS compounds such as polyethyl silicate (Silbond 40) or polymethyl silicate may also be used as commercially available compounds, or they may be further hydrolyzed before being introduced into the gel process.

[000123] Inorganic aerogels may also include gel precursors containing at least one hydrophobic group, such as alkyl metal alkoxides, cycloalkyl metal alkoxides, and aryl metal alkoxides, which can impart or improve certain gel properties such as stability and hydrophobicity. Inorganic silica aerogels may specifically include hydrophobic precursors such as alkylsilanes or arylsilanes. Hydrophobic gel precursors can be used as primary precursor materials to prepare the framework of the gel material. However, hydrophobic gel precursors are most often used as co-precursors in combination with simple metal alkoxides to prepare amalgam aerogels. Hydrophobic inorganic precursor materials for silica airgel synthesis include, but are not limited to: trimethylmethoxysilane (TMS), dimethyldimethoxysilane (DMS), methyltrimethoxysilane (MTMS), trimethylethoxysilane, dimethyldiethoxysilane (DMDS), methyltriethoxysilane (MTES), ethyltriethoxysilane (ETES) ), diethyldiethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane (PhTES), hexamethyldisilazane and hexaethyldisilazane and the like. Any derivatives of any of the foregoing precursors may be used and, specifically, certain polymeric or other chemical groups may be attached or linked to one or more of the foregoing precursors.

[000124] Aerogels can also be treated to impart or improve hydrophobicity. Hydrophobic treatment can be used for a sol-gel solution, a wet gel before liquid-liquid extraction, or an airgel after liquid-liquid extraction. Hydrophobic treatment is particularly common in the production of metal oxide aerogels such as silica aerogels. One example of hydrophobic gel processing is discussed in more detail below, specifically in the context of wet silica gel processing. However, the specific examples and illustrations presented herein are not intended to limit the scope of the present disclosure by any particular type of hydrophobic treatment technique or airgel substrate. The present disclosure may include any gel or aerogel known to those skilled in the art, as well as related methods for hydrophobically treating aerogels in either wet gel or dried aerogel form.

[000125] Hydrophobic treatment is carried out by a reaction between a hydroxy moiety on the gel, such as a silanol group (Si-OH) present on the silicic acid gel framework, and a functional group of a hydrophobizing agent. The resulting reaction converts the silanol group and the hydrophobizing agent into a hydrophobic group on the silicic acid gel framework. The hydrophobizing agent compound can react with hydroxyl groups on the gel according to the following reaction: R _N MX _4-N (hydrophobizing agent) + MOH (silanol) → MOMR _N (hydrophobic group) + HX. Hydrophobic treatment can take place both on the outer macrosurface of the silicic acid gel and on the surfaces of the internal pores in the porous gel network.

[000126] The gel may be immersed in a mixture of a hydrophobizing agent and an optional hydrophobic treatment solvent in which the hydrophobizing agent is soluble and which is also miscible with the gel solvent in the wet gel. A wide range of solvents for hydrophobic treatment can be used, including solvents such as methanol, ethanol, isopropanol, xylene, toluene, benzene, dimethylformamide and hexane. To impart hydrophobicity, hydrophobizing agents in liquid or gaseous form can also be directly brought into contact with the gel.

[000127] The hydrophobic treatment process may include mixing or stirring to promote penetration of the hydrophobic agent into the wet gel. The hydrophobic treatment process may also include varying other conditions, such as temperature and pH, to further promote and optimize the treatment reactions. After the reaction is complete, the wet gel is washed to remove unreacted compounds and reaction byproducts.

[000128] Hydrophobizing agents for hydrophobic treatment of airgel are generally compounds described by the formula: R _N MX _4-N ; where M represents a metal; R represents a hydrophobic group such as CH ₃ , CH ₂ CH ₃ , C ₆ H ₆ or similar hydrophobic alkyl, cycloalkyl or aryl moieties; and X represents a halogen atom, usually Cl. Specific examples of hydrophobizing agents include, but are not limited to: trimethylchlorosilane (TMCS), triethylchlorosilane (TECS), triphenylchlorosilane (TPCS), dimethylchlorosilane (DMCS), dimethyldichlorosilane (DMDCS), and the like. Hydrophobizing agents can also be described by the formula: Y(R ₃ M) ₂ ; where M represents a metal; Y represents a bridging group such as NH or O; and R represents a hydrophobizing group such as CH ₃ , CH ₂ CH ₃ , C ₆ H ₆ or similar hydrophobic alkyl, cycloalkyl or aryl moieties. Specific examples of such hydrophobizing agents include, but are not limited to: hexamethyldisilazane [HMDZ] and hexamethyldisiloxane [HMDSO]. Hydrophobizing agents may further include compounds having the formula: R _N MV _4-N wherein V represents a reactive or leaving group other than a halogen atom. Specific examples of such hydrophobizing agents include, but are not limited to: vinyltriethoxysilane and vinyltrimethoxysilane.

[000129] The hydrophobic treatments of the present invention can also be carried out during removal, exchange or drying of the liquid in the gel. In one particular embodiment, the hydrophobic treatment can be carried out in a supercritical fluid environment (such as, but not limited to: supercritical carbon dioxide) and can be combined with a drying or extraction step.

[000130] In the context of the present disclosure, the term “hydrophobically bonded silicon atom” refers to a silicon atom in a gel or airgel framework containing at least one hydrophobic group covalently bonded to the silicon atom. Examples of hydrophobically bonded silicon atom include, but are not limited to: silicon atoms in silica groups in the gel framework that are formed from gel precursors containing at least one hydrophobic group (such as MTES or DMDS). The hydrophobically bonded silicon atom may also include, but is not limited to: silicon atoms in the gel framework or on the surface of the gel that are treated with a hydrophobizing agent (such as HMDZ) to impart or improve hydrophobicity by introducing additional hydrophobic groups into the composition. Hydrophobic groups of the present disclosure include, but are not limited to: methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, octyl groups, phenyl groups or other substituted or unsubstituted hydrophobic organic groups , known to those skilled in the relevant field of technology. In the context of the present disclosure, the terms "hydrophobic group", "hydrophobic organic material" and "hydrophobic organic material content" specifically exclude readily hydrolyzable organic alkoxy groups associated with a silicon atom on the backbone of the gel material, which are the product of reactions between organic solvents and silanol groups. Such excluded groups can be distinguished from its hydrophobic organic matter content using NMR analysis. The amount of hydrophobically bonded silicon atom contained in the airgel can be analyzed using NMR spectroscopy, such as solid-state ²⁹ Si-NMR with cross-polarization and magic angle spinning of the sample. Airgel NMR analysis makes it possible to obtain characteristics and relative quantities for hydrophobically bonded M-type silica (monofunctional silica such as TMS derivatives); hydrophobically bonded D-type silicon atom (bifunctional silica such as DMDS derivatives); hydrophobically bonded T-type silicon atom (trifunctional silica such as MTES derivatives); and a Q-type silicon atom (tetrafunctional silicon dioxide such as TEOS derivatives). NMR analysis can also be used to analyze the chemical binding mechanism of the hydrophobically bonded silicon atom contained in the airgel by providing a breakdown of specific types of hydrophobically bonded silicon atom into categories into subtypes (such as the breakdown of hydrophobically bonded silicon atom related to type T, categorized into structures T ¹ , structures T ² and structures T ³ ). Specific details regarding NMR analysis for silica materials can be found in the article "Applications of Solid-State NMR to the Study of Organic/Inorganic Multicomponent Materials" by Geppi et al., specifically pages 7-9 (Appl. Spec. Rev. (2008), 44-1: 1-89), which is incorporated herein by reference to the pages specifically cited.

[000131] Characterization of a hydrophobically bonded silicon atom by ²⁹ Si-NMR analysis with cross-polarization and magic angle rotation of the sample can be based on the following chemical shift peaks: M ¹ (from 30 to 10 ppm) ; D ¹ (from 10 to - 10 ppm), D ² (from - 10 to - 20 ppm); T ¹ (from - 30 to - 40 ppm), T ² (from - 40 to - 50 ppm), T ³ (from - 50 to - 70 ppm); Q ² (from - 70 to - 85 ppm), Q ³ (from - 85 to - 95 ppm), Q ⁴ (from - 95 to - 110 ppm). These chemical shift peaks are approximate and illustrative and are not intended to be limiting or determinative. The exact chemical shift peaks attributed to the various silicon-containing structures in the material may depend on the specific chemical components of the material and can generally be interpreted through routine experimentation and analysis by those skilled in the art.

[000132] In the context of the present disclosure, the terms “hydrophobic organic matter content” or “hydrophobic content” or “hydrophobic compound content” refer to the amount of hydrophobic organic material associated with the framework in the airgel material or composition. The content of hydrophobic organic material in the airgel material or composition may be expressed as a weight percentage for the amount of hydrophobic organic material on the airgel framework relative to the total amount of material in the airgel material or composition. The content of hydrophobic organic matter can be calculated by those skilled in the art based on the nature and relative concentrations of the materials used in the production of the airgel material or composition. Hydrophobic organic matter content can also be measured using thermogravimetric analysis (TGA) for the materials of interest, preferably in an oxygen atmosphere (although TGA in alternating gas environments is also suitable for use). Specifically, the percentage of hydrophobic organic material in the airgel may be correlated with the percentage of weight loss in the hydrophobic airgel material or composition when exposed to heat of combustion temperatures during TGA analysis, with adjustments made for moisture loss, residual solvent loss, and readily hydrolyzable loss. alkoxy groups during TGA analysis. Other alternative techniques may be used to measure and determine the hydrophobe content of the aerogel compositions of the present invention, such as differential scanning calorimetry, elemental analysis (particularly carbon atom analysis), chromatographic techniques, nuclear magnetic resonance spectra, and other analytical techniques known in the art. specialists in the relevant field of technology. In certain cases, a combination of known techniques may be suitable or necessary for determining the hydrophobe content of the aerogel compositions of the present invention.

[000133] The aerogel materials or compositions of the present disclosure may have a hydrophobic organic matter content of 50 wt% or less, 40 wt% or less, 30 wt% or less, 25 wt% or less. ) and less, 20% (wt.) and less, 15% (wt.) and less, 10% (wt.) and less, 8% (wt.) and less, 6% (wt.) and less, 5 % (wt.) or less, 4% (wt.) or less, 3% (wt.) or less, 2% (wt.) or less, 1% (wt.) or less, or between any two from the given values.

[000134] The term "fuel content" refers to the cumulative amount of combustible material in an airgel material or composition, which can be correlated with the cumulative percentage weight loss in the airgel material or composition when exposed to temperatures for heating value during TGA or TG-DSC analysis, at In this case, adjustments are made regarding moisture loss. The fuel content of the airgel material or composition may include hydrophobic organic matter content, as well as other flammable residual alcohol solvents, filler materials, reinforcing materials, and readily hydrolyzable alkoxy groups.

[000135] Organic aerogels are generally prepared from carbon-based polymer precursors. Such polymeric materials include, but are not limited to: resorcinol-formaldehyde (RF) materials, polyimide, polyacrylate, polymethyl methacrylate, acrylate oligomers, polyoxyalkylene, polyurethane, polyphenol, polybutadiene, trialkoxysilyl-terminated polydimethylsiloxane, polystyrene, polyacrylonitrile, polyfurfural, melamine -formaldehyde material, cresol-formaldehyde material, phenol-furfural material, polyether, polyol, polyisocyanate, polyhydroxybenzene, polyvinyl alcohol dialdehyde, polycyanurates, polyacrylamides, various epoxides, agar-agar, agarose, chitosan and combinations thereof. As one example, organic aerogels based on RF material are typically prepared by sol-gel polymerization of resorcinol or melamine together with formaldehyde under alkaline conditions.

[000136] Organic/inorganic hybrid aerogels are primarily formed from (organically modified silica (“ormosil”) aerogels). These ormosil materials include organic components that are covalently bonded to a silica network. Ormosils are usually prepared by hydrolysis and condensation of organically modified silanes R-Si(OX) ₃ using traditional alkoxide precursors Y(OX) ₄ . In these formulas, X may represent, for example, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ ; Y may be, for example, Si, Ti, Zr or Al; and R can be any organic moiety such as methyl, ethyl propyl, butyl, isopropyl, methacrylate, acrylate, vinyl, epoxide and the like. The organic components in the ormosil-based airgel can also be dispersed throughout the silica network or chemically bound to it.

[000137] As used herein, the term "ormosil" covers the above materials as well as other organically modified materials sometimes referred to as "ormocers". Ormosils are often used as coatings, where a film of Ormosil is cast over a substrate material using, for example, a sol-gel process. Examples of other organic-inorganic hybrid aerogels of the invention include, but are not limited to: silica-polyether, silica-PMMA, silica-chitosan, carbides, nitrides, and other combinations of compounds forming the aforementioned organic and inorganic airgel. US Patent Application Published No. 20050192367 (paragraphs [0022] - [0038] and [0044] - [0058]) includes disclosures of such hybrid organic-inorganic materials and is incorporated by reference herein as individually cited sections and paragraphs .

[000138] In certain embodiments, the aerogels of the present disclosure are inorganic silica aerogels prepared primarily from prepolymerized silica precursors, preferably in the form of oligomers or hydrolyzed silicic acid esters derived from silicon-containing alkoxides in an alcohol solvent. In certain embodiments, such prepolymerized silica precursors or hydrolyzed silicas can be prepared in situ from other silicas precursors or esters, such as alkoxysilanes or water glass. However, the disclosure of the invention as a whole can be practiced using any other aerogel compositions known to those skilled in the art and is not limited to any one precursor material or amalgam mixture of precursor materials.

[000139] Airgel production generally includes the following steps: i) producing a sol-gel solution; ii) obtaining a gel from a sol-gel solution; and iii) solvent extraction from gel materials using innovative processing and extraction to produce dried airgel material. This process is discussed in more detail below, specifically in the context of the preparation of inorganic aerogels such as silica aerogels. However, the specific examples and illustrations presented herein are not intended to limit the present disclosure to any particular type of airgel and/or production method. The present disclosure may include any airgel produced using any related production method known to those skilled in the art, unless otherwise noted.

[000140] The first step in preparing an inorganic airgel is generally the preparation of a sol-gel solution by hydrolysis and condensation of silica precursors, such as, but not limited to, the following: metal alkoxide precursors in an alcohol-based solvent. Key variables in the preparation of inorganic aerogels include the type of alkoxide precursors included in the sol-gel solution, the nature of the solvent, the processing temperature and pH of the sol-gel solution (which can be altered by the addition of acid or base), and the precursor/solvent/water ratio in sol-gel solution. Controlled maintenance of these variables during the preparation of the sol-gel solution may allow for controlled maintenance of the growth and aggregation of the gel framework during the subsequent transition of the gel material from the “sol” state to the “gel” state. Although the properties of the resulting aerogels are affected by the pH value of the precursor solution and the molar ratio of the reactants, any pH value and any molar ratios that allow the preparation of gels can be used in the present disclosure.

[000141] A sol-gel solution is prepared by combining at least one gelling precursor with a solvent. Solvents suitable for use in preparing the sol-gel solution include lower alcohols containing 1 to 6 carbon atoms, in particular 2 to 4, although other solvents known to those skilled in the art may be used. Examples of suitable solvents include, but are not limited to: methanol, ethanol, isopropanol, ethyl acetate, ethyl acetoacetate, acetone, dichloromethane, tetrahydrofuran and the like. Multiple solvents may also be combined to achieve the desired level of dispersion or optimize the properties of the gel material. Thus, the selection of optimal solvents for the sol-gel and gel formation steps depends on the specific precursors, fillers, and additives introduced into the sol-gel solution; as well as the target processing conditions for gelation and liquid extraction and the desired properties of the final aerogel materials.

[000142] Water may also be present in the precursor solvent solution. Water performs the function of hydrolyzing metal alkoxide precursors to form metal hydroxide precursors. The hydrolysis reaction may be (using TEOS in ethanol solution as an example): Si(OC ₂ H ₅ ) ₄ +4H ₂ O → Si(OH) ₄ +4(C ₂ H ₅ OH). The resulting hydrolyzed metal hydroxide precursors remain suspended in the solvent solution in a “sol” state, either as individual molecules or as small polymerized (or oligomerized) colloidal clusters of molecules. For example, the polymerization/condensation of precursors based on Si(OH) ₄ can have the following form: 2Si(OH) ₄ = (OH) ₃ Si-O-Si(OH) ₃ +H ₂ O. This polymerization can continue until colloidal clusters of polymerized (or oligomerized) SiO ₂ (silicon dioxide) molecules.

[000143] Acids and bases can be added to the sol-gel solution to control the pH of the solution and to catalyze the hydrolysis and condensation reactions of precursor materials. While any acid can be used to catalyze precursor reactions and produce a solution having a lower pH, exemplary acids include HCl, H ₂ SO ₄ , H ₃ PO ₄ , oxalic acid, and acetic acid. Likewise, any base can be used to catalyze the reactions of the precursors and to obtain a solution characterized by an elevated pH value, with an illustrative base including NH ₄ OH.

[000144] The sol-gel solution may include additional co-gelling precursors, as well as filler materials and other additives. Filler materials and other additives can be dosed into the sol-gel solution at any time before or during gel formation. Filler materials and other additives can also be incorporated into the gel material after gelation using various techniques known to those skilled in the art. In certain embodiments, the sol-gel solution containing gelling precursors, solvents, catalysts, water, excipient materials, and other additives is a homogeneous solution that is capable of effective gelation under suitable conditions for use.

[000145] Once the sol-gel solution is prepared and optimized, the gelling components in the sol-gel can be transferred into the gel material. The technological process of transition of the gelling components into the gel material includes the initial stage of gel formation, when the gel hardens up to the gelation point for the gel material. The gelation point for a gel material can be considered as the point at which the gelling solution exhibits resistance to flow and/or forms a substantially continuous polymer framework throughout its volume. A wide range of gelling techniques are known to those skilled in the art. Examples include, but are not limited to: allowing the mixture to rest for a sufficient period of time; adjusting the pH value of the solution; adjusting the solution temperature; direction to a mixture of a certain type of energy (ultraviolet, visible, infrared, microwave, ultrasonic, corpuscular radiation, electromagnetic radiation); or combinations thereof.

[000146] The process of transitioning the gelling components (gel precursors) into the gel material may also include an aging step (also referred to as “curing”) prior to liquid extraction or solvent removal from the gel (also referred to as “drying” the gel). Aging the gel material after reaching its gelation point can further strengthen the gel framework by increasing the number of cross-links in the network. The duration of gel aging can be adjusted to controllably maintain different properties in the resulting airgel material. This aging technique may be suitable for use in preventing potential volume loss and shrinkage during liquid extraction. Aging may involve leaving the gel (prior to extraction) at rest for an extended period, keeping the gel at an elevated temperature, adding crosslinking promoting compounds, or any combination thereof. Preferred aging temperatures typically range between about 10° C. and about 100° C., although other suitable temperatures are contemplated herein. Aging of the gel material typically continues until liquid extraction of the wet gel material occurs.

[000147] The period of time for the transition of gelling materials (gel precursors) into the gel material includes both the duration of initial gel formation (from initiation of gelation up to the gelation point) and the duration of any subsequent curing and aging of the gel material prior to liquid extraction or removal of solvent from the gel (also referred to as gel drying) (from the point of gelation until the initiation of liquid extraction/solvent removal). The cumulative time period for the gelling materials to transition into the gel material typically ranges between about 1 minute and several days, typically about 30 hours or less, about 24 hours or less, about 15 hours or less, about 10 hours or less, about 6 hours or less, about 4 hours or less, about 2 hours or less, and preferably about 1 hour or less, about 30 minutes or less, about 15 minutes or less, or about 10 minutes or less.

[000148] In yet another embodiment, the resulting gel material can be washed in a suitable secondary solvent to replace the primary reaction solvent present in the wet gel. Such secondary solvents may be linear monohydric alcohols containing one or more aliphatic carbon atoms, dihydric alcohols containing 2 or more carbon atoms, branched alcohols, cyclic alcohols, alicyclic alcohols, aromatic alcohols, polyhydric alcohols, ethers, ketones, cyclic ethers esters or their derivatives. In yet another embodiment, the resulting gel material may be washed with additional amounts of the same solvent present in the gel material, which may, among other things, remove any unwanted byproducts or other deposits in the gel material.

[000149] Once the gel material is prepared and processed, thereafter the gel liquid can be at least partially extracted from the wet gel using extraction methods including innovative processing and extraction techniques to produce the airgel material. Liquid extraction, among other factors, plays an important role in developing the characteristics of aerogels such as porosity and density, as well as associated properties such as thermal conductivity. In general, aerogels are produced by extracting liquid from a gel in a manner that encourages small shrinkage to occur in the porous network and framework of the wet gel. This liquid-liquid extraction, among other things, can also be referred to by the terms “solvent removal” or “drying”.

[000150] One example of an alternative method for making silica airgel uses metal oxide salts such as sodium silicate, also known as water glass. First, a liquid glass solution is produced by mixing sodium silicate with water and acid to produce a silicic acid precursor solution. Salt by-products can be removed from the silicic acid precursor by ion exchange, surfactant separation, membrane filtration, or other chemical or physical separation techniques. The resulting sol can then be gelled in a manner similar to the addition of a base catalyst to produce a hydrogel. The hydrogel can be washed to remove any residual salts or reagents. Removal of water from the pores of the gel can then be accomplished by exchange with a polar organic solvent such as ethanol, methanol or acetone. Subsequently, the liquid in the gel is at least partially extracted using innovative processing and extraction techniques in one embodiment.

[000151] Aerogels are generally prepared by removing a liquid mobile phase from a gel material at a temperature and pressure near or above the critical point for the liquid mobile phase. Immediately after reaching the critical point (close to criticality) or exceeding it (supercriticality) (that is, when the pressure and temperature of the system are at a level equal to or greater, respectively, than the critical pressure and critical temperature), a new supercritical phase appears in the fluid, which different from the liquid or vapor phase. The solvent can then be removed without introducing a liquid-vapor interface, capillary pressure, or any associated mass transfer constraints associated with liquid-vapor boundaries. In addition to this, the supercritical phase is generally more miscible with organic solvents, thus demonstrating better extraction capability. To optimize the supercritical fluid drying process, co-solvents and solvent exchanges are also used in most cases.

[000152] If evaporation or extraction occurs well below the critical point, the capillary forces generated by the liquid extraction can stimulate shrinkage and collapse of the pores in the gel material. Maintaining the mobile phase near or above critical pressure and temperature during the solvent extraction process reduces the negative effects of such capillary forces. In certain embodiments of the present disclosure, the use of near-critical conditions immediately below the critical point of the solvent system may enable the production of materials or aerogel compositions that exhibit sufficiently low shrinkage, thereby resulting in the production of a competitive end product.

[000153] Several additional airgel extraction techniques are known in the art, including a wide range of different approaches using supercritical fluids to dry aerogels. For example, Kistler (J. Phys. Chem. (1932) 36 : 52-64) describes a simple supercritical extraction process where the gel solvent is kept above its critical pressure and temperature, thereby reducing capillary forces during evaporation and maintains the structural integrity of the gel network. US Patent No. 4,610,863 describes an extraction process where a gel solvent is exchanged for liquid carbon dioxide and subsequently extracted under conditions in which the carbon dioxide is in a supercritical state. US Pat. No. 6,670,402 discloses the extraction of liquid from a gel using rapid solvent exchange by injecting supercritical (rather than liquid) carbon dioxide into an extraction unit that has been subjected to preheat and prepressure to achieve substantially supercritical or higher conditions. , thereby leading to the production of aerogels. US Pat. No. 5,962,539 describes a process for producing an airgel from a polymeric material that is in the form of a sol-gel in an organic solvent by exchanging the organic solvent for a fluid having a critical temperature lower than the decomposition temperature of the polymer and extracting the fluid/sol -gel when using a supercritical fluid such as supercritical carbon dioxide, supercritical ethanol or supercritical hexane. US Pat. No. 6,315,971 discloses a process for producing gel compositions that includes drying a wet gel containing gel solids and a drying agent to remove the drying agent under drying conditions sufficient to reduce shrinkage of the gel during drying. US Pat. No. 5,420,168 describes a process in which resorcinol/formaldehyde aerogels can be made using a simple air-drying technique. US Pat. No. 5,565,142 describes drying techniques in which the surface of a gel is modified to provide greater strength and greater hydrophobicity so that the gel framework and pores can resist collapse during ambient drying or supercritical extraction. Other examples of liquid extraction from aerogel materials can be found in US Patent Nos. 5,275,796 and 5,395,805.

[000154] In one embodiment, extracting liquid from a wet gel uses supercritical fluids such as carbon dioxide, including, for example, first essentially exchanging the primary solvent present in the pore network of the gel for liquid carbon dioxide; and then heating the wet gel (usually in an autoclave) beyond the carbon dioxide critical temperature (approximately 31.06°C) and increasing the system pressure to a pressure greater than the carbon dioxide critical pressure (approximately 1070 ^psig ) (7.38 MPa(g))). The pressure around the gel material may fluctuate slightly to facilitate removal of liquid from the gel. Carbon dioxide can be recirculated through the extraction system to facilitate continuous removal of primary solvent from the wet gel. Finally, the temperature and pressure are slowly returned to ambient conditions to produce the dry airgel material. The carbon dioxide may also be pre-processed into a supercritical state before being injected into the extraction chamber.

[000155] Another example of an alternative method for producing aerogels involves reducing the damaging capillary pressure forces at the solvent/pore interface by chemically modifying the matrix materials in their wet gel state by converting surface hydroxyl groups to hydrophobic trimethylsilyl ethers, thereby makes liquid extraction possible from gel materials at temperatures and pressures below the solvent critical point.

[000156] In yet another embodiment, the liquid (solvent) in the gel material can be frozen at lower temperatures followed by a sublimation process, whereby the solvent is removed from the gel material. Such removal or drying of solvent from the gel material is understood to fall within the scope of this disclosure. This removal largely preserves the gel structure, thereby producing an airgel with unique properties.

[000157] Large-scale production of aerogel materials or compositions can be complicated by the difficulties associated with the continuous production of gel materials on a large scale; as well as the difficulties associated with liquid-liquid extraction of gels from materials in large volumes using innovative processing and extraction techniques. In certain embodiments, the aerogel materials or compositions of the present disclosure are consistent with large scale production. In certain embodiments, the gel materials of the present disclosure can be produced on a large scale using a continuous casting and gelation process. In certain embodiments, the aerogel materials or compositions of the present disclosure are produced on a large scale, requiring the use of large-scale extraction vessels. Large-scale extraction vessels of the present disclosure may include extraction vessels that have a volume of about 0.1 m ³ or more, about 0.25 m ³ or more, about 0.5 m ³ or more, or about 0.75 m ³ and more.

[000158] The aerogel compositions of the present disclosure may have a thickness of 15 mm or less, 10 mm or less, 5 mm or less, 3 mm or less, 2 mm or less, or 1 mm or less.

[000159] Aerogel compositions can be reinforced with various reinforcing materials to achieve a more flexible, resilient and moldable composite product. Reinforcement materials can be added to the gels at any point during the gelation process to produce a reinforced wet gel composition. The wet gel composition can then be dried to produce a reinforced airgel composition.

[000160] Aerogel compositions can be reinforced with OCMF material using a variety of open cell macroporous framework reinforcements to achieve a more flexible, resilient, and moldable composite product. OCMF reinforcements can be added to gels at any point during the gelation process prior to gelation to produce a reinforced wet gel composition. The wet gel composition can then be dried to produce an OCMF reinforced airgel composition. OCMF reinforcements can be derived from organic polymeric materials, such as melamine-based or melamine derivatives, and are present in the form of a continuous sheet or panel.

[000161] Melamine OCMF materials can be produced from a melamine-formaldehyde precondensation solution. An aqueous solution of the melamine-formaldehyde condensate is produced by combining the melamine-formaldehyde precondensate with a solvent, an emulsifier/dispersant, a curing agent such as an acid, and a foaming agent such as a C5-C7 hydrocarbon. The melamine-formaldehyde solution or resin is then cured at an elevated temperature above the boiling point of the foaming agent to produce an OCMF material comprising a plurality of interconnected three-dimensional branched melamine structures, with a corresponding network of interconnected pores integrated into the framework. Melamine-formaldehyde precondensates are generally characterized by a molar ratio between formaldehyde and melamine in the range of 5:1 to 1.3:1, and usually in the range of 3.5:1 to 1.5:1. Precondensates can be in the form of a powder, spray, resin or solution. The solvent included in the melamine-formaldehyde precondensation solution may include alcohols such as methanol, ethanol or butanol.

[000162] The emulsifier/dispersant included in the melamine-formaldehyde precondensation solution may include an anionic surfactant, a cationic emulsifier, or a nonionic surfactant. Suitable anionic surfactants include, but are not limited to: diphenylene oxide sulfonates, alkane and alkyl benzene sulfonates, alkyl naphthalene sulfonates, olefin sulfonates, alkyl ether sulfonates, fatty alcohol sulfates, ether sulfates, α-sulf fatty acid esters, acylamino alkane sulfonates, acyl isothionates, alkyl ether carboxylates, N-acylsarcosinates, alkyl phosphates and alkyl ether phosphates. Suitable cationic emulsifiers include, but are not limited to: alkyl triammonium salts, alkyl benzyl dimethyl ammonium salts, or alkyl pyridinium salts. Suitable nonionic surfactants include, but are not limited to: polyglycol alkylphenol ethers, polyglycol fatty alcohol ethers, polyglycol fatty acid ethers, fatty acid alkanolamides, ethylene oxide-propylene oxide block copolymers, amine oxides, glycerol esters fatty acids, sorbitan esters and alkyl polyglycosides. The emulsifier/dispersant may be added in amounts ranging from 0.2% to 5% by weight based on the melamine-formaldehyde precondensate.

[000163] The curing agent included in the melamine-formaldehyde precondensation solution may include acidic compounds. The amount of these hardeners is generally in the range of 0.01% to 20% by weight, and typically in the range of 0.05% to 5% by weight, in all cases based on the melamine-formaldehyde precondensate. Suitable acidic compounds include, but are not limited to: organic and inorganic acids, for example selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, oxalic acid, toluenesulfonic acids, amidosulfonic acids, acid anhydrides and mixtures thereof.

[000164] The foaming agent included in the melamine-formaldehyde precondensation solution may include physical foaming agents or chemical foaming agents. Suitable physical blowing agents include, but are not limited to: hydrocarbons such as pentane and hexane; halogenated hydrocarbons, more specifically chlorinated and/or fluorinated hydrocarbons, for example methylene chloride, chloroform, trichloroethane, chlorofluorocarbons and hydrochlorofluorocarbons (HCFCs); alcohols, for example methanol, ethanol, n-propanol or isopropanol; ethers, ketones and esters, for example methyl formate, ethyl formate, methyl acetate or ethyl acetate; and gases such as air, nitrogen or carbon dioxide. In certain embodiments, it is preferred to add a physical blowing agent having a boiling point in the range between 0°C and 80°C. Suitable chemical blowing agents include, but are not limited to: isocyanates mixed with water (releasing carbon dioxide as the active blowing agent); carbonates and/or bicarbonates mixed with acids (releasing carbon dioxide as an active foaming agent); and azo compounds, such as azodicarbonamide. The foaming agent in the melamine-formaldehyde precondensation solution is present in an amount ranging from 0.5% to 60% by weight, in particular from 1% to 40% by weight, and in certain embodiments from 1.5% up to 30% (wt.), based on melamine-formaldehyde pre-condensate.

[000165] The melamine-formaldehyde precondensation solution can be converted into a melamine OCMF material by heating the solution to a temperature generally greater than the boiling point of the blowing agent used, thereby resulting in an OCMF material comprising a plurality of interconnected three-dimensional branched structures. melamine structures, with a corresponding network of interconnected open-cell pores integrated into the frame. The introduction of thermal energy can be carried out using electromagnetic radiation, for example, using high frequency radiation, in the range of 5 to 400 kW, for example 5 to 200 kW, and in certain embodiments from 9 to 120 kW, per kilogram mixture used, in the frequency range from 0.2 to 100 GHz, or, more specifically, from 0.5 to 10 GHz. Magnetrons provide a suitable source of dielectric radiation, and one magnetron or two or more magnetrons can be used simultaneously.

[000166] The OCMF material can be dried to remove residual liquids (water, solvent, blowing agent) from the OCMF material. Post-treatment can also be used to hydrophobize the OCMF material. In this post-treatment, hydrophobic coating agents having high heat resistance and/or low flammability, such as silicones, siliconates or fluorinated compounds, can be used.

[000167] The density of the OCMF melamine material is generally in the range of 0.005 to 0.3 g/cc, such as in the range of 0.01 to 0.2 g/cc, in certain embodiments in the range of 0.03 to 0.15 g/cc or, more specifically, in the range of 0.05 to 0.15 g/cc. The average pore diameter for melamine OCMF material generally ranges from 10 µm to approximately 1000 µm, particularly in the range from 50 to 700 µm.

[000168] In one embodiment, the OCMF reinforcing materials are incorporated into the airgel composition in the form of a continuous sheet. The manufacturing process involves initially producing a continuous sheet of OCMF reinforced gel material by casting or impregnating a gel precursor solution into a continuous sheet of OCMF reinforcement material and causing the sheet material to be formed into a reinforced composite gel. Thereafter, the liquid can be at least partially extracted from the OCMF-reinforced gel composite sheet to produce a sheet-shaped OCMF-reinforced airgel composition.

[000169] Aerogel compositions may include an opacifier to reduce the radiative component of heat transfer. At any time prior to gel formation, the opacifying compounds or their precursors may be dispersed into a mixture containing the gel precursors. Examples of opacifying compounds include, but are not limited to: boron carbide (B ₄ C), diatomite, manganese ferrite, MnO, NiO, SnO, Ag ₂ O, Bi ₂ O ₃ , carbon black, titanium dioxide, iron titanium oxide , aluminum oxide, zirconium silicate, zirconium oxide, iron (II) oxide, iron (III) oxide, manganese dioxide, iron titanium oxide (ilmenite), chromium oxide, carbides (such as SiC, TiC or WC) or mixtures thereof. Examples of opacifier precursors include, but are not limited to: TiOSO ₄ or TiOCl ₂ .

[000170] Aerogel compositions may include one or more fire rated additives. As used herein, the term “fire rated additive” refers to a material that exhibits an endothermic effect in response to fire and can be incorporated into an airgel composition. Additionally, in certain embodiments, fire rated additives exhibit an onset of endothermic decomposition (E _D ) that is no more than 100° C. greater than the onset of thermal decomposition (T _d ) of the airgel composition in which the additive is present , corresponding to the fire safety class, and in certain embodiments, also an E _D value that is no more than 50° C. less than the T _d value for the airgel composition in which the additive corresponding to the fire safety class is present. In other words, the E _D value for fire rated additives ranges from ( T _d - 50°C) to ( T _d +100°C):

Before introducing or mixing with the sol (for example, a silicic acid sol obtained from alkyl silicates or liquid glass in various embodiments in accordance with the understanding of the prior art), simultaneously or even after this, additives corresponding to the fire safety class can be mixed or otherwise dispersed in a medium comprising ethanol and optionally up to 10% (vol.) water. The mixture can be mixed and/or stirred as needed to achieve substantially uniform dispersion of the additives in the medium. As can be said without being bound by theory, the use of the hydrated form of the above-mentioned clays and other additives corresponding to the fire safety class provides an additional endothermic effect. For example, halloysite clay (available commercially under the trade name DRAGONITE from Applied Minerals, Inc. or from Imerys simply under the name Halloysite), kaolinite clay are aluminosilicate clays that, in hydrated form, exhibit an endothermic effect resulting from the release of water of hydration when elevated temperatures (dilution with gas). As another example, carbonates in hydrated form can release carbon dioxide when heated or at elevated temperatures.

[000171] As used herein, the terms “heat of hydration” refer to the amount of heat required to evaporate water (and dehydroxylate when appropriate) from a material that is in hydrated form when not exposed to elevated temperatures. The heat of hydration is usually expressed per unit mass.

[000172] In certain embodiments, the fire rated additives of the present disclosure have an onset of thermal decomposition corresponding to about 350°C or more, about 400°C or more, about 450°C or more, about 500°C or more , about 550°C or more, about 600°C or more, about 650°C or more, about 700°C or more, about 750°C or more, about 800°C or more, or between any two of given values. In certain embodiments, fire rated additives of the present disclosure have an onset of thermal decomposition of approximately 440°C or 570°C. In certain embodiments, the fire-rated additives of the present disclosure are characterized by an onset of thermal decomposition that is no more than 50° C. greater or less than the T _d value for the airgel composition (in the absence of the fire-rated additive) , into which an additive corresponding to the fire safety class is added, no more than 40°C more or less, no more than 30°C more or less, no more than 20°C more or less, no more, more than 10°C more or less, no more than 5°C more or less, or between any two of these values.

[000173] Fire rated additives of this disclosure include clay materials such as, but not limited to: phyllosilicate clays (such as illite), kaolinite (aluminum silicate; Al ₂ Si ₂ O ₅ (OH) ₄ ), halloysite (aluminum silicate; Al ₂ Si ₂ O ₅ (OH) ₄ ), endellite (aluminum silicate; Al ₂ Si ₂ O ₅ (OH) ₄ ), mica (silica-based minerals), diaspores, gibbsite (aluminum hydroxide) , montmorillonite, beidellite, pyrophyllite (aluminum silicate; Al ₂ Si ₄ O ₁₀ (OH) ₂ ), nontronite, bravaisite, smectite, leverrierite, rectorite, celadonite, attapulgite, chloropal, volkonskoite, allophane, racevinite, dillnite, severite, miloshit, collyrite, cymolite and newtonite, magnesium hydroxide (or magnesium dihydroxide, “MDH”), aluminum trihydrate (“ATH”), carbonates such as but not limited to the following: dolomite and lithium carbonate. Among the clay materials, certain embodiments of the present disclosure include clay materials that have at least a partially layered structure. In certain embodiments of the present disclosure, the clay materials as fire rated additives in aerogel compositions contain at least some water, such as in the hydrated form. The additives may be in hydrated crystalline form or may become hydrated during the manufacture/processing of the compositions of the present invention. In certain embodiments, the fire rated additive also includes low melting additives that absorb heat without changing the chemical composition. One example in this class is low-melting glass, such as inert glass beads. Other additives that may be suitable for use in the compositions of the present disclosure include, but are not limited to: wollastonite (calcium silicate) and titanium dioxide (TiO ₂ ). In certain embodiments, other additives may include infrared opacifiers such as but not limited to the following: titanium dioxide or silicon carbide, ceramizers such as but not limited to the following: low melting glass frit, calcium silicate, or chars such as the following , but not limited to: phosphates and sulfates. In certain embodiments, the additives may require special processing considerations, such as techniques to ensure uniform distribution of the additives and avoid significant agglomeration, which would encourage variations in product performance. Processing techniques may include additional static and dynamic mixers, stabilizers, adjustment of process conditions, and other things that are known at the current level of technology. The amount of additives in the final aerogel compositions may depend on various other property requirements and may range from 5% to approximately 70% by weight. In certain embodiments, the amount of additives in the final airgel composition is in the range between 10 and 60% by weight, and in certain preferred embodiments it is in the range of between 20 and 40% by weight. In certain embodiments, additives may be of more than one type. The final aerogel compositions may also contain one or more additives that meet the fire safety class. In certain preferred embodiments that include fire rated aluminum silicate additives, the additives in the final aerogel compositions are present in an amount of approximately 60-70% by weight.

[000174] In certain embodiments of the present disclosure, methods are provided for producing OCMF-reinforced aerogel compositions that exhibit fire rated performance characteristics. The fire rated compositions of these embodiments also have sufficient hydrophobicity for use as thermal insulation in industrial environments as measured by water absorption and low thermal conductivity to help meet increasingly stringent energy conservation requirements. To obtain these combinations of desired properties, simply loading additives or even fire rated additives is not successful. Although it is possible to attempt various permutations and combinations of different additives and achieve an optimized solution, such efforts are not always successful and pose risks to cost-effective manufacturing with reproducible quality control for given desired properties. One important aspect of these embodiments is to evaluate the thermal behavior (assessed using thermogravimetry or differential scanning calorimetry) of a composition that would otherwise provide all the desired properties except fire performance, and consider a fire-rated additive that is well suited to the onset of thermal decomposition of the underlying composition or, alternatively, the temperature at which the main amount of heat is emitted when the thermal decomposition of fire rated additives begins, or the temperature at which the main amount of heat is absorbed.

[000175] In certain embodiments, the desired fire resistance characteristics of the final composition may include not just an intrinsic property, such as heating value (ISO 1716), but also fire resistance characteristics of the system, such as fire response performance characteristics in accordance with ISO 1182. For the case of ISO 1182, the weight loss, furnace temperature increase and flame time are assessed when the furnace is exposed to a temperature of approximately 750°C.

[000176] The OCMF reinforced airgel composition may contain various components that add fuel to the system. In addition to this, it may contain various other components which, while not contributing as fuel, may participate in combustion when exposed to fire. As such, the combustion behavior of such systems cannot be predicted simply based on the constituent elements. In situations in which multiple properties are desired, in certain embodiments, the achievement of the resulting composition must be achieved without regard to its fire resistance characteristics, and the thermal performance characteristics of such resulting composition must be evaluated to find a suitable fire-rated additive that will impart fire resistance characteristics without deterioration of other properties that the original composition is intended to impart.

[000177] In certain embodiments, the onset of thermal decomposition is a critical property of the composition. In certain other embodiments, it corresponds to the temperature at which peak heat release may be a critical property for the purpose of developing OCMF aerogel compositions exhibiting improved fire performance. If there are multiple fuel components in the composition, identified by multiple peaks in the DSC curve, such components will perform their function well as a result of matching the peak heat release temperature for the OCMF reinforced airgel composition with a fire-rated additive exhibiting an endothermic peak heat release temperature within 140°C, 120°C, 100°C or 80°C. In many embodiments, the endothermic peak heat release temperature is in the range of 50°C.

[000178] The aerogel materials and compositions of the present disclosure have been demonstrated to be highly effective as insulating materials. However, the applications of the methods and materials of the present disclosure are not intended to be limited to insulation-related applications. The methods and materials of the present disclosure can be used for any system or application that will benefit from the unique combination of properties or techniques provided by the materials and methods of the present disclosure.

[000179] Examples

[000180] The following examples suggest various non-limiting embodiments and features of the present disclosure. In the examples below, the % (mass) value of the additive is obtained by representing 100% when calculating the mass of silicon dioxide and hydrophobic components of the airgel composition. Thermal TGA and DSC analyzes were performed using a Netzsch STA449 F1 Jupitor simultaneous thermal analyzer by starting at 25°C and ramping at 20°C per minute up to 1000°C in air at ambient pressure. Any reference to the hydrophobic content of a sol refers to the weight of solid materials in the final airgel composition produced from the hydrophobic alkyl silanes in the sols, as a percentage of the weight of the final airgel composition.

[000181] EXAMPLE 1

The polyethylsilicate sol was produced by hydrolyzing TEOS (tetraethoxysilane) in ethanol and water using a sulfuric acid catalyst and then stirring at ambient temperature for approximately 16 hours. Polymethylsilsesquioxane sol was produced by hydrolysis of MTES (methyltriethoxysilane) and DMDES (dimethyldiethoxysilane) (at a molar ratio of approximately 4:1) in ethanol and water using a phosphoric acid catalyst, and then stirred at ambient temperature for at least 16 hours. Polyethylsilicate and polymethylsilsesquioxane (MTES+DMDES) sols were combined (at a weight ratio of approximately 2:1) to produce a precursor sol that had a target total hydrophobe content in the final airgel composition derived from the sol in the range of 30-40% (wt. ). The combined precursor sol was stirred at ambient temperature for at least 2 hours.

[000182] EXAMPLE 2

A sample of melamine material OCMF (BASOTECT UF from BASF) was measured to have a thickness of 10 mm and a density of approximately 6 kg/m ³ . A substantially homogeneous mixture of 70 g of magnesium dihydroxide (fire rated additive; MDH) in approximately 450 mL of ethanol (with up to 10% (v/v) water) was combined with approximately 540 mL of the silicic acid sol from Example 1 and stirred for for at least 5 minutes. Approximately 10 ml of NH ₄ OH solution at 28% by weight was then added, followed by stirring of the sol mixture for at least 1 minute. Subsequently, the sol mixture was infiltrated into the OCMF melamine material and allowed to gel, with gelation occurring within 2 minutes. The resulting gel composition was allowed to settle and cure for approximately 10 minutes. The gel composition was then aged for 16 hours at 68° C. in an ethanol aging fluid containing 10% (v/v) H ₂ O and 1.1% (w/v) NH ₄ OH (1.1 g NH ₄ OH based on 100 ml of fluid), with a fluid to gel composition ratio of approximately 1.5:1. The aging temperature and aging fluid composition can be further varied to vary the overall aging time.

[000183] After this, samples of the gel compositions were subjected to solvent extraction using supercritical CO ₂ , followed by drying at 120°C for 4 hours. The target silica density was 0.07 g/cu.m. cm, and the resulting material density for the airgel composite was 0.159 g/cc. see The hydrophobe content in the airgel composition was approximately 4.34% (wt.).

[000184] EXAMPLE 3

The gel formulation was made using the same procedure as in Example 2, except combining a mixture of 72 g MDH in approximately 529 ml ethanol (in the presence of up to 10% (vol.) water) with approximately 460 ml silicic acid sol from Example 1. The target density of silicon dioxide was 0.06 g/cu.m. cm, and the resulting material density for the airgel composition was 0.185 g/cc. see The hydrophobe content in the airgel composition was approximately 3.97% (wt.).

[000185] EXAMPLE 4

The gel formulation was made using the same procedure as in Example 2, except combining a substantially homogeneous mixture of 96 g MDH in approximately 376 ml ethanol (in the presence of up to 10% (vol.) water) with approximately 614 ml silica sol acids from example 1. The target density of silicon dioxide was 0.08 g/cu. cm, and the resulting material density for the airgel composition was 0.178 g/cc. see The hydrophobe content in the airgel composition was approximately 3.97% (wt.).

[000186] EXAMPLE 5

The gel formulation was made using the same procedure as in Example 2, except combining a substantially homogeneous mixture of 84 g of MDH in approximately 539 ml of ethanol (in the presence of up to 10% (vol.) water) with approximately 460 ml of silica sol acid from Example 1. The target density of silica was 0.06 g/cc and the resulting material density for the airgel composition was 0.142 g/cc. The hydrophobe content of the airgel composition was approximately 3.6% by weight.

[000187] EXAMPLE 6

The gel formulation was made using the same procedure as in Example 2, except combining a substantially homogeneous mixture of approximately 529 ml of ethanol (in the presence of up to 10% (vol.) water; in the absence of fire rated additives) with approximately 460 ml of silicic acid sol from Example 1. The target density of silica was 0.06 g/cc. cm, and the resulting material density for the airgel composition was 0.074 g/cc. see The hydrophobe content in the airgel composition was approximately 8.3% (wt.).

[000188] EXAMPLE 7

The gel formulation was made using the same procedure as in Example 2, except combining a substantially homogeneous mixture of 72 g of inert glass beads (fire rated additive) in approximately 529 ml of ethanol (at up to 10% vol. .) water) with approximately 460 ml of the silicic acid sol from Example 1. The target density of silica was 0.06 g/cc and the resulting material density for the airgel composition was 0.141 g/cc. The hydrophobe content of the airgel composition was approximately 3.93% by weight.

[000189] EXAMPLE 8

The gel formulation was made using the same procedure as in Example 2, except combining a substantially uniform mixture of 60 g of wollastonite (available commercially under the name NYAD) in approximately 529 ml of ethanol solvent with approximately 460 ml of the silicic acid sol of Example 1. The target density of silica was 0.06 g/cc and the resulting material density for the airgel composition was 0.161 g/cc. The hydrophobe content of the airgel composition was approximately 3.95% by weight.

[000190] EXAMPLE 9

The gel formulation was made using the same procedure as in Example 2, except combining a substantially homogeneous mixture of 72 g of titanium dioxide (fire rated additive; TiO ₂ ) in approximately 529 ml of ethanol (with up to 10% (vol.) water) with approximately 460 ml of silicic acid sol from Example 1. The target density of silica was 0.06 g/cc. cm, and the resulting material density for the airgel composition was 0.159 g/cc. The hydrophobe content of the airgel composition was approximately 3.95% by weight.

[000191] EXAMPLE 10

A sample of OCMF polyurethane material was obtained, measured to have a thickness of 10 mm and a density of approximately 23 kg/m ³ . A substantially homogeneous mixture of 60 g of MDH (a fire rated additive) in approximately 529 mL of ethanol (with up to 10% (v/v) water) was combined with approximately 460 mL of the silicic acid sol from Example 1 and stirred for at least , than 5 minutes. Approximately 10 ml of NH ₄ OH solution at 28% by weight was then added, followed by stirring of the sol mixture for at least 1 minute. Subsequently, the sol mixture was infiltrated into the OCMF polyurethane material and allowed to gel, with gelation occurring within 2 minutes. The resulting gel composite was allowed to settle and cure for approximately 10 minutes. The gel composite was then aged for 16 hours at 68° C. in an ethanol aging fluid containing 10% (v/v) H ₂ O and 1.1% (w/v) NH ₄ OH (1.1 g NH ₄ OH based on 100 ml of fluid), with a ratio between fluid and gel composition of approximately 1.5:1.

After this, samples of the gel compositions were subjected to solvent extraction using CO ₂ in a supercritical state, followed by drying at 120°C for 4 hours. The target silica density was 0.06 g/cc and the resulting material density for the airgel composition was 0.165 g/cc. The hydrophobe content of the airgel composition was approximately 3.95% by weight.

[000192] EXAMPLE 11

The polyethylsilicate sol was produced by hydrolysis of TEOS in EtOH and H ₂ O using a sulfuric acid catalyst, and then stirred at ambient temperature for at least 16 hours. The polymethylsilsesquioxane sol was produced by hydrolyzing MTES and DMDES (at a molar ratio of approximately 8:1) in EtOH and H ₂ O using an acetic acid catalyst and then stirring at ambient temperature for at least 16 hours. Polyethylsilicate (TEOS) and polymethylsilsesquioxane (MTES+DMDES) sols were combined (at a weight ratio of approximately 10:1) to produce a silicic acid sol that had a target total sol hydrophobe content of the final airgel composition of approximately 12% (wt.) . The combined silicic acid sol was stirred at ambient temperature for at least 2 hours.

[000193] EXAMPLE 12

A sample of melamine OCMF material was obtained, measured to have a thickness of 10 mm and a density of approximately 6 kg/m ³ . A substantially homogeneous mixture of 60 grams of MDH (fire rated additive) in approximately 718 ml of ethanol (with up to 10% (v/v) water) was combined with approximately 266 ml of the silicic acid sol from Example 11 and stirred for at least , than 5 minutes. Approximately 10 ml of NH ₄ OH solution at 28% by weight was then added, followed by stirring of the sol mixture for at least 1 minute. Subsequently, the sol mixture was infiltrated into the OCMF melamine material and allowed to gel, with gelation occurring within 2 minutes. The resulting gel composite was allowed to settle and cure for approximately 10 minutes. The gel composition was then treated for 16 hours at 68°C in ethanol containing 0.12 mol/L trimethylsilyl hexamethyldisilazane derivatives (“TMS”), 8% (vol.) H ₂ O and 0.8 g NH ₄ OH at based on 100 ml of ethanol, with a ratio between fluid and gel composition of approximately 1.5:1.

[000194] Samples of the gel compositions were then subjected to solvent extraction using supercritical CO ₂ followed by drying at 120°C for 4 hours. The target silica density was 0.05 g/cc and the resulting material density for the airgel composition was 0.176 g/cc.

[000195] EXAMPLE 13

The gel formulation was made using the same procedure as in Example 12, except combining a substantially homogeneous mixture of approximately 718 ml of ethanol solvent (in the absence of a fire rated additive) with approximately 256 ml of the silicic acid sol from Example 8. Target the density of silica was 0.05 g/cc and the resulting material density for the airgel composition was 0.081 g/cc.

[000196] EXAMPLE 14

The gel composite material was produced using the same procedure as in Example 11, except for combining polyethylsilicate (TEOS) and polymethylsilsesquioxane (MTES+DMDES) sols at a weight ratio of approximately 7:1 to produce a silicic acid sol, which was characterized the target total hydrophobe content in the final airgel composition is 16% (wt).

[000197] EXAMPLE 15

The gel formulation was made using the same procedure as in Example 12, except combining a substantially homogeneous mixture of 72 g of MDH (fire rated additive) in approximately 668 ml of ethanol solvent with approximately 317 ml of silicic acid sol from Example 14 The target silica density was 0.06 g/cc and the resulting material density for the airgel composition was 0.195 g/cc. The onset of thermal decomposition was found to be 399.5°C using thermogravimetric curves and the peak heat release temperature was found to be 439.6°C using DSC curves. The extrapolated onset of thermal decomposition of the composition comprising the fire rated additive as measured using thermogravimetric curves was 395.8° C. and the peak heat release temperature as measured using a DSC curve was 560.9° C.

[000198] By way of comparison, the composition of this example, in the absence of any fire rated additive, was found to have an extrapolated onset of thermal decomposition of 369.4° C. as measured using thermogravimetric curves, and a peak heat release temperature of was found to be 607.9°C as measured using DSC curves.

[000199] EXAMPLE 16

The gel formulation was made using the same procedure as in Example 12, except combining a mixture of approximately 668 ml of ethanol solvent (in the absence of fire rated additive) with approximately 317 ml of silicic acid sol from Example 14. Target density of silica was 0.06 g/cc, and the resulting material density for the airgel composition was 0.092 g/cc.

[000200] EXAMPLE 17

The polyethylsilicate sol was produced by hydrolyzing TEOS in ethanol and water using a sulfuric acid catalyst and then stirring at ambient temperature for approximately 16 hours. This hydrophobe-free sol was used without adding any polymethylsilsesquioxane sol or other hydrophobic material.

[000201] EXAMPLE 18

The gel composite material was produced using the same procedure as in Example 12, except combining a mixture of approximately 662 ml of ethanol solvent (in the absence of a fire rated additive) with approximately 328 ml of the silicic acid sol from Example 17 and allowing conversion to gel. The gel was treated with a solution containing 0.3 mol/L TMS in ethanol (8% (v/v) H ₂ O and 0.8 g NH ₄ OH per 100 ml ethanol, with a fluid to gel composite ratio of approximately 1.5:1), for 16 hours at 68°C. The target silica density was 0.06 g/cc and the resulting material density for the airgel composite was 0.086 g/cc.

[000202] EXAMPLE 19

The gel composite material was produced using the same procedure as in Example 12, except combining a mixture of approximately 662 ml of ethanol solvent (in the absence of a fire rated additive) with approximately 328 ml of the silicic acid sol from Example 17 and allowing conversion to gel. The gel was treated with a solution containing 0.6 mol/L MTES (8% (v/v) H ₂ O and 0.8 g NH ₄ OH per 100 ml ethanol, with a fluid to gel composite ratio of approximately 1. 5: 1), for 16 hours at 68°C. The target silica density was 0.06 g/cc and the resulting material density for the airgel composite was 0.103 g/cc.

[000203] EXAMPLE 20

The gel composite material was produced using the same procedure as Example 2, except combining a substantially homogeneous mixture of 112 g of halloysite clay (fire rated additive; DRAGONITE) in approximately 453 ml of ethanol (at up to 8% (vol.) water) with approximately 453 ml of silica sol from Example 1. The target density of silica was 0.07 g/cc, and the resulting material density for the airgel composite was 0.196 g/cc. The hydrophobe content of the airgel composition was approximately 3.37% (wt).

[000204] EXAMPLE 21

The gel composite material was produced using the same procedure as Example 2, except combining a substantially homogeneous mixture of 72 g of halloysite clay (fire rated additive; DRAGONITE) in approximately 529 ml of ethanol (with up to 10% (vol.) water) with approximately 460 ml of silica sol from Example 1. The target density of silica was 0.06 g/cc and the resulting material density for the airgel composite was 0.128 g/cc. The hydrophobe content of the airgel composition was approximately 3.91% by weight. The onset of thermal decomposition was measured to be 492.9° C. using thermogravimetric curves, and the peak heat release temperature was measured to be 565.9° C. using a DSC curve. The extrapolated onset of thermal decomposition of the composition comprising the fire rated additive was measured using thermogravimetric curves to be 370.9° C., and the peak heat release temperature was measured to be 565.9° C. using the DSC curve.

[000205] By way of comparison, the composition of this example, in the absence of any fire rated additive, was found to have an extrapolated onset of thermal decomposition of 369.4° C. as measured using thermogravimetric curves, and a peak heat release temperature of was found to be 607.9°C as measured using DSC curves.

[000206] EXAMPLE 22

The gel composite material was produced using the same procedure as in Example 2, except combining a substantially homogeneous mixture of two fire rated additives - 36 g halloysite clay (DRAGONITE) and 36 g aluminum trihydrate (ATH) - in approximately 529 ml of ethanol (in the presence of up to 10% (vol.) water) with approximately 460 ml of the silicic acid sol from Example 1. The target density of silica was 0.06 g/cc, and the resulting material density for airgel composite was 0.149 g/cc. The hydrophobe content of the airgel composition was approximately 3.94% by weight.

[000207] EXAMPLE 23

The gel composite material was produced using the same procedure as in Example 2, except combining a substantially homogeneous mixture of 72 g of aluminum trihydrate (ATH) in approximately 529 ml of ethanol (in the presence of up to 10% (vol.) water) with approximately 460 ml of the silicic acid sol from Example 1. The target density of silica was 0.06 g/cc and the resulting material density for the airgel composite was 0.152 g/cc. The hydrophobe content of the airgel composition was approximately 3.94% by weight. The onset of thermal decomposition was measured to be 289.8° C. using thermogravimetric curves, and the peak heat release temperature was measured to be 334.1° C. using a DSC curve.

[000208] By way of comparison, the composition of this example, in the absence of any fire rated additive, was found to have an extrapolated onset of thermal decomposition of 369.4° C. as measured using thermogravimetric curves, and a peak heat release temperature of was found to be 607.9°C as measured using DSC curves.

[000209] EXAMPLE 24

The gel composite material was produced using the same procedure as in Example 12, except combining a substantially homogeneous mixture of 100 g of halloysite clay (DRAGONITE) in approximately 558 ml of ethanol (with up to 10% (vol.) water) with approximately 426 ml of the silicic acid sol from Example 11 were combined to give a target hydrophobe content of 28% (w/w). The target silica density was 0.083 g/cc and the resulting material density for the airgel composite was 0.184 g/cc.

[000210] EXAMPLE 25

The gel formulation was made using the same procedure as in Example 2, except combining a substantially uniform mixture of 56 g halloysite clay (DRAGONITE from Applied Minerals, Inc.) and 56 g ATH in approximately 453 ml ethanol (with up to to 8% (vol.) water) with approximately 537 ml of the silica sol from Example 1. The target density of silica was 0.07 g/cc and the resulting material density for the airgel composite was 0.196 g/cc . The hydrophobe content of the airgel composition was approximately 3.36% by weight.

[000211] Table 1 below illustrates the composition of the above examples. The term "wt% loading" refers to the amount of additive loaded into the composition based on the amount of silica present. For example, a "wt% loading" of 120% indicates a loading of 120 g of additive when calculated for every 100 g of silica in the composition.

Example No. Sol hydrophobe content (%) Target Silicon Dioxide Density (g/cc) Additive type Loading in % (wt.) 2 36 0.07 MDH 100 3 36 0.06 MDH 120 4 36 0.08 MDH 120 5 36 0.06 MDH 140 6 36 0.06 Absent 0 7 36 0.06 Inert glass beads 120 8 36 0.06 Wollastonite 120 9 36 0.06 Titanium dioxide 120 10 36 0.06 MDH 120 12 12 0.05 MDH 120 13 12 0.05 Absent 0 15 16 0.06 MDH 120 16 16 0.06 Absent 0 18 0 0.06 Absent 0 19 0 0.06 Absent 0 20 36 0.07 Halloysite clay 160 21 36 0.06 Halloysite clay 120 22 36 0.06 Halloysite clay+ATN 120 23 36 0.06 ATH 120 24 28 0.083 Halloysite clay 120 25 36 0.07 Halloysite clay+ATN 160

Table 1. Composition of examples.

[000212] Table 2 presents the results of measurements of density, TD, liquid water uptake, TC, DFT, flame time and mass loss for the composites of the examples in Table 1.

Example No. Composite Density (g/cc) TP (mW/m-K) Liquid water absorption (% (mass)) TC (cal/g (kJ/g)) Oven temperature rise (°C) Flame time (sec) Weight loss (% (mass)) 2 0.159 18.6 4.4 670.4 (2.81) 32 0 28.8 3 0.185 20.1 5.1 492.7 (2.06) 35.5 0 44.1 4 0.178 17.8 5.6 584.7 (2.45) 40.1 0 19.1 5 0.142 18.4 2.8 668.6 (2.80) 32.7 0 17.7 6 0.074 15.2 8.5 1599.9 (6.70) 194.8 81 18.1 7 0.141 19.5 6.4 714.8 (2.99) 81.7 120 10.9 8 0.161 19.6 4.6 616 (2.58) 41.1 13 20.7 9 0.159 16.1 4.2 797 (3.34) 45 35 43.6 10 0.165 19.2 2.0 1196 (5.01) 81 50 38.5 12 0.176 15.5 4.5 684.1 (2.87) 44.9 0 47.6 13 0.081 14.8 3.7 1920.6 (8.04) 153.9 76 26.5 15 0.195 18.5 8.8 486.1 (2.04) 41.8 0 34.9 16 0.092 14.7 3.1 1886.9 (7.90) 112 110 16.6 18 0.086 14.2 4.5 1966 (8.23) 178.9 100 18.0 19 0.103 14.9 26.1 1433 (6.00) 95.1 109 15.3 20 0.196 17.2 4.8 621 (2.60) 10.0 0 17.8 21 0.128 17.7 3.7 747 (3.13) 40.2 5 16.1 22 0.149 16.3 3.8 785 (3.29) 49.3 70 22.2 23 0.152 16.4 3.1 733 (3.07) 34.0 33 27.2 24 0.184 15.7 2.3 783 (3.28) 38.8 0 19.6 25 0.184 18.5 < 5 600 (2.51) 9.3 10 22.4

Table 2. Resulting properties from examples.

[000213] As can be said, still referring to Table 2, density measurements were made in accordance with ASTM C167. All samples of aerogel compositions had measured densities of less than 0.2 g/cc. TC measurements were performed in accordance with ASTM C518 at a temperature of approximately 37.5° C. and a compression of ² psi (138 kPa). All samples of aerogel compositions were characterized by thermal conductivity measurements equal to or less than 20.1 mW/m-K. Liquid water absorption measurements were performed in accordance with ASTM C1511 (15-minute immersion at ambient conditions). All samples of aerogel compositions exhibited liquid water uptake of less than 5% by weight. TC measurements were carried out in accordance with ISO 1716 measurement standards. All samples of aerogel compositions had a TC value of less than 690 cal/g (2.89 kJ/g). PTP measurements were carried out in accordance with ISO 1182 Criterion A.1. All samples of aerogel compositions were characterized by a PTP value of less than 50°C. Flame time measurements were carried out in accordance with ISO 1182 Criterion A.2. All these samples had a measured flame time of 20 seconds. Mass loss measurements were performed in accordance with ISO 1182 Criterion A.3. All other samples of aerogel compositions exhibited a mass loss of less than 50% (wt).

[000214] The advantages presented above and the advantages made apparent from the above description of the invention are effectively achieved. It is intended that, while certain changes to the above construction may be made without departing from the scope of the invention, all material contained in the above description of the invention or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.

[000215] As should also be understood, the following claims are intended to cover all generic and specific features of the invention described herein and all statements of the scope of the invention that may be stated within the scope of the claims. .

Claims (43)

1. An insulator composition comprising a silica airgel frame reinforced with an open cell macroporous frame material OCMF and a fire rated additive which contains an endothermic material; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) absorption of liquid water, amounting to 20% of the mass. or less; ii) a thermal conductivity of 30 mW/m⋅K or less in accordance with ASTM C518 at a temperature of approximately 37.5°C, in an ambient atmosphere at atmospheric pressure and under a compressive load of approximately ² psi (138 kPa); And iii) calorific value of less than 717 cal/g (3.00 kJ/g) in accordance with EN ISO 1716; And iv) a silica airgel frame reinforced with a macroporous open-cell OCMF frame material has a thermal decomposition onset temperature, and a fire-rated additive has an endothermic decomposition onset temperature that is within 50°C of the thermal onset temperature. decomposition of a silica airgel framework reinforced with a macroporous open-cell OCMF framework material. 2. The composition of claim 1, wherein the OCMF material includes an organic OCMF material. 3. The composition of claim 1, wherein the OCMF material comprises a melamine-based OCMF material. 4. Composition according to any one of paragraphs. 1-3, wherein the OCMF material contains or is a sheet of OCMF material. 5. Composition according to any one of paragraphs. 1-3, where the OCMF material is an organic foam. 6. The composition according to claim 1, where the OCMF material is neither a refractory material nor a non-flammable material; And the composition as a whole is flame retardant or non-flammable. 7. Composition according to any one of paragraphs. 1-5, where the OCMF material is neither a refractory material nor a non-flammable material; And the composition as a whole is either refractory or non-flammable. 8. Composition according to any one of paragraphs. 1-5, where the OCMF material is from 2 to 10% of the mass. from the composition. 9. Composition according to any one of paragraphs. 1-8, where the content of hydrophobically bonded silicon atom in the composition is in the range between 2 wt%. and 10% wt.. 10. Composition according to any one of paragraphs. 1-9, where the composition has a calorific value ranging from 625 cal/g (2.62 kJ/g) to 700 cal/g (2.93 kJ/g) in accordance with the EN ISO 1716 standard. 11. The composition according to claim 1, where the reinforced airgel composition is characterized by the onset of thermal decomposition of the organic content from 350 to 390°C. 12. The composition according to claim 1, including a hydrophobic substance content of at least 5% by weight, and where the total heat of endothermic decomposition of additives corresponding to the fire safety class in the composition is at least 30% of the exothermic heat of decomposition of the remainder of the composition in the absence of the additive , corresponding to the fire safety class. 13. The composition according to claim 1, containing at least two additives corresponding to the fire safety class, and their corresponding beginnings of endothermic decomposition are separated from each other by at least 10°C. 14. The composition according to claim 1, where the beginning of the endothermic decomposition of additives corresponding to the fire safety class in the composition is within 50°C from the beginning of thermal decomposition of the remainder of the composition in the absence of an additive corresponding to the fire safety class. 15. The composition according to claim 1, where the total heat of endothermic decomposition of additives corresponding to the fire safety class in the composition is no more than 80% of the exothermic heat of decomposition of the remainder of the composition in the absence of an additive corresponding to the fire safety class. 16. The composition of claim 1, wherein the flame time for the ISO 1182 composition is about 30 seconds or less, about 25 seconds or less, about 20 seconds or less, about 15 seconds or less, about 10 seconds or less, approximately 5 seconds or less, approximately 2 seconds or less, or between any two of these values. 17. The composition of claim 1, wherein the weight loss for the ISO 1182 composition is about 50% or less, about 40% or less, about 30% or less, about 28% or less, about 26% or less, about 24% or less, about 22% or less, about 20% or less, about 18% or less, about 16% or less, or between any two of these values. 18. The composition according to claim 1, where the onset of endothermic decomposition of the additive corresponding to the fire safety class corresponds to more than 280°C, 300°C, 350°C, 400°C, 450°C or 500°C. 19. The composition of claim 1, wherein the OCMF material is one of a urethane-based polymeric foam or a reticular foam. 20. The composition according to any one of the above claims, wherein the OCMF has a density in the range between 2 kg/m ³ and 25 kg/m ³ , and the composition has a density between 0.15 g/cm ³ and 0.40 g/cm ³ . 21. Composition according to any one of the above points, in which the thermal conductivity is from 8 to 25 mW/m⋅K. 22. The composition according to any one of the above paragraphs, in which the absorption of liquid water is from 1 to 10% of the mass. 23. A reinforced airgel composition for insulators, comprising a silica-based airgel framework reinforced with an open cell macroporous framework material OCMF, and a fire rated additive that contains an endothermic material; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) absorption of liquid water is up to 20% of the mass. or less; ii) The thermal conductivity is 30 mW/m⋅K or less in accordance with ASTM C518 at a temperature of approximately 37.5°C, in an ambient atmosphere at atmospheric pressure and under a compressive load of approximately ² psi (138 kPa). ); And iii) has the onset of endothermic decomposition of organic content from 280 to 500°C; And iv) a silica airgel frame reinforced with a macroporous open-cell OCMF frame material has a thermal decomposition onset temperature, and a fire-rated additive has an endothermic decomposition onset temperature that is within 50°C of the thermal onset temperature. decomposition of a silica airgel framework reinforced with a macroporous open-cell OCMF framework material. 24. A reinforced airgel composition for insulators comprising a silica-based airgel framework reinforced with an OCMF open cell macroporous framework material and a fire rated additive which contains an endothermic material; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) absorption of liquid water is up to 20% of the mass. or less; ii) The thermal conductivity is 30 mW/m⋅K or less in accordance with ASTM C518 at a temperature of approximately 37.5°C, in an ambient atmosphere at atmospheric pressure and under a compressive load of approximately ² psi (138 kPa). ); And iii) the beginning of endothermic decomposition of the additive corresponding to the fire safety class in the composition is within 50°C from the beginning of thermal decomposition of the remainder of the composition in the absence of the additive corresponding to the fire safety class; And iv) a silica airgel frame reinforced with a macroporous open-cell OCMF frame material has a thermal decomposition onset temperature, and a fire-rated additive has an endothermic decomposition onset temperature that is within 50°C of the thermal onset temperature. decomposition of a silica airgel framework reinforced with a macroporous open-cell OCMF framework material. 25. A reinforced airgel composition for insulators, comprising a silica-based airgel framework reinforced with an open cell macroporous framework material OCMF, and a fire rated additive that contains an endothermic material; wherein the silica airgel framework contains at least one hydrophobically bonded silicon atom; and wherein the reinforced airgel composition has the following properties: i) absorption of liquid water is up to 20% of the mass. or less; ii) The thermal conductivity is 30 mW/m⋅K or less in accordance with ASTM C518 at a temperature of approximately 37.5°C, in an ambient atmosphere at atmospheric pressure and under a compressive load of approximately ² psi (138 kPa). ); And iii) the flame time for the composition in accordance with ISO 1182 is 10 s or less, or the oven temperature rise is 40°C or less, or both; And iv) a silica airgel frame reinforced with a macroporous open-cell OCMF frame material has a thermal decomposition onset temperature, and a fire-rated additive has an endothermic decomposition onset temperature that is within 50°C of the thermal onset temperature. decomposition of a silica airgel framework reinforced with a macroporous open-cell OCMF framework material.