RU2329898C2 - Multi-layer barier system (versions) - Google Patents

Abstract

FIELD: machine building.

SUBSTANCE: invention relates to a multi-layer barrier system including, at least, one inorganic resin compound layer containing a product of interaction of alkaline metal silicate and/or alkaline metal silicate precursor, a reactive acidic glass, water, unnecessarily, one or several acidic oxoanionic compounds, and, unnecessarily, a clay and/or oxide filler, and, at least, one layer of additional material including an isolating material, a bloating material, a foamed material, a reflecting material, a corrugated material, every one of them containing a gas volume. Also, this version of the aforesaid system can incorporate, at least, two layers of the aforesaid inorganic resin composition and, instead of a reactive glass, at least, one compound containing, at least, one polyvalent cation. Here note that one layer of the inorganic resin composition contains a reinforcing compound.

EFFECT: higher heat stability, fire resistance.

36 cl, 12 dwg, 4 tbl

Description

CROSS REFERENCE

This application is based on provisional patent application US 60/476671, filed June 6, 2003 for a fire barrier. This application is also a partial continuation of US patent application 10/777885, filed February 12, 2004, entitled "Inorganic Matrix Compositions, Composites incorporating the Matrix, and Process of Making the Same", which claims the benefit of US patent application 09/871765, filed June 1, 2001, which claims the benefit of provisional patent application US 60/233952, filed September 20, 2000, entitled "Inorganic Matrix Compositions, Composites and Process of Making the Same", and, in addition, US patent application 10 / 777885 claims the benefit of US patent application No. 09/871998, filed June 1, 2001, which It claims the benefit of US Provisional Application No. 60/233985, filed September 20, 2000, entitled "Inorganic Matrix Compositions and Composites Incorporating the Matrix Composition". All of the above applications are hereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to improved fire fighting systems or to multilayer systems comprising at least one layer of an inorganic polymer matrix derived from alkali metal silicate and one or more non-silicate structure-forming substances and / or reactive glass and, optionally, a secondary modifier of the mesh structure . Other layers may be any of the following: an insulating layer, an intumescent layer, a foam layer, a corrugated layer, a reflecting surface layer, and reinforcing materials, either as a separate layer or included inside any of the above layers and, preferably, inside an inorganic polymer matrix layer. More specifically, the above layers can serve as a framework, an intermediate layer or as an outer barrier layer to protect the desired substrates, such as wood, metal and the like, from exposure to high temperature and / or fire.

BACKGROUND

Inorganic matrices are useful as a flame retardant binder for composite materials, backing materials, adhesives, porous materials such as foam materials, or composite materials. As the substrate materials, they are used to obtain molded objects, from which, after curing, a building material is obtained. As a composite material, matrix compositions are used to impregnate a fabric that can be combined with other similarly impregnated fabrics to form a multilayer composite material, which is then molded and cured to form a molded object similar to the substrate material, but with the advantage of reinforcement provided by the fabric.

Most currently well-known composite systems are based on organic polymer matrices such as epoxy / fiberglass, epoxy / carbon fiber, polyurethane / fiberglass, PVC / fiberglass, polyimide / silica fiber, polyester / fiberglass and nylon / fiberglass. Although organic polymeric composite materials exhibit excellent physical and mechanical properties, they are limited in terms of flammability, smoke and gas, and the ability to operate at elevated temperatures. The flammability of composites based on organic polymers can be reduced by the addition of inorganic components and / or additives. Replacing hydrogen atoms with halogen atoms (e.g., chlorine) in hydrocarbons and hydrocarbon polymers can significantly reduce flammability and smoke / gas formation, but they will decompose at temperatures exceeding 250 ° C and ultimately burn out at temperatures exceeding 450 ° C. Organic thermoplastic polymers also deform at relatively low temperatures (approximately 100 ° C-300 ° C), and organic polymers intended for use at higher temperatures are usually unavailable due to the cost of material and processing.

Other composite materials include metal matrix composite materials (MMC), ceramic matrix composite materials (CMC), carbon-carbon composite materials, and other inorganic matrix composite materials. The matrix of the composite material may be 100% inorganic or it may contain some organic matter. Inorganic matrix structures include ceramics, oxide-based ceramics, glass, metals, metal alloys, cementitious materials, and similar materials. Other materials that can be considered include inorganic particles encapsulated with inorganic binders, organic resins filled with inorganic fillers, inorganic-organic hybrids such as silicone, and other inorganic matrix materials known to those skilled in the art.

Alkali metal silicates are used as possible binding materials for the inorganic matrix. See, for example, US patents No. 4472199; 4,599,885; 4,888,311; 5,288,321; 5352427; 5,539,140 or 5,798,307 issued by Davidovits; US patent No. 4936939 issued by Woolum, or US patent No. 4284664 issued by Rauch.

Fireproof doors, which are one form of fire barrier, are a multi-billion dollar dollar market in North America alone and equally large in Europe. The fire-resistant door market is expected to grow with stricter 9/11 government emergency regulations and pressure from insurance companies. The technology used in the manufacture of the fireproof door is based on the limit of fire resistance of the door to be obtained. The performance of these fireproof doors is measured using a fire test, when they measure the time during which the door can resist fire and maintain sufficient strength. The test protocol may vary, but it is typically the US Warnock-Hersey protocol. This protocol consists of an E-119 firing curve with or without flow from the hose at the end of this test. Thus, the door is exposed to a flame in the furnace for a period of time, for example 60 minutes, and then the door is struck by a stream from a fire hose. A door that is kept intact passes the test. Fire doors are classified from 20 minutes to many hours, with most of the doors having a 20, 45, 60 and 90 minute fire resistance. The design and materials of the 20-minute door compared to the 90-minute door are significantly different, which is reflected not only in the degree of fire resistance, but also in the cost of the door.

The 20-minute door can simply be a wooden or plastic door with intumescent stripes at the edges to seal the door. Whereas a 60- or 90-minute door, in addition to the strips at the edges, requires some kind of frame in order to get extra time. The frame serves many purposes depending on the design and materials of the door. Firstly, the frame is a passive protection against fire, preventing the penetration of fire through the door. Secondly, the frame isolates the side where there is no fire, maintaining a low temperature during the test. Thirdly, the frame can help maintain structural integrity during the test using flow from the fire hose after exposure to fire. The frames used in fire doors can perform all of these functions or only one or two of these functions, in addition, the effectiveness of the frames in these three areas can vary depending on the materials and design of the door. Most 90-minute doors are flat metal doors with a mineral frame. The frame in these doors acts primarily as insulation, and the steel functions as a fire barrier and to maintain strength when, after a fire test, the flow from the fire hose follows. There is also a small number of paneled doors (classified as shaped and enclosed doors) that have a 90-minute fire resistance rating. In most cases, their frame contains intumescent material. The frame functions primarily as a fire barrier and insulation on the side of the door with which there is no fire, and to a very limited extent by the structural material. The wood on the side of the door where there is no fire functions as the main structural material to withstand the flow from the fire hose.

Examples of these prior art constructions can be found in prior art patents. For example, US Pat. No. 4,270,326 to Hölter et al describes ceramic or fiberglass fabric for use in a fire door, where felt is made from fibers with similar needle-like fibers, while US Patent No. 4,879,320 to Hastings describes a flame retardant material. coatings, which includes a liquid intumescent and dispersed and suspended in it refractory fibers of various sizes. U.S. Patent Nos. 4,756,945 and 4,936,064 to Gibb describe a fire resistant panel that includes a matrix of refractory material in which a reinforcing material is placed or on a surface. Gibb'945 describes non-combustible blanket materials that are made of inorganic fibers formed into a refractory, porous fabric, and which increases in volume under the influence of heat, the non-combustible layer is attached to one side of the substrate layer. US Patent No. 4,801,496 to Buchacher describes a fire wall constructed of a composite material including a fire retardant layer of intumescent material combined with layers of graphite / epoxy or Kevlar® / epoxy.

Examples of cementitious materials include US Pat. No. 4,159,302, issued to Greve et al, which describes a fire door that includes expanded perlite, gypsum, cured hydraulic cement and an inorganic binder; US Pat. US patent No. 6240691 issued by Holzkaemper et al, which describes a composite panel comprising a foam sheet made of cementitious material.

US Patent Nos. 4,818,595 and 5,101,184, issued to Ellis, describe fire barriers for use on or between wooden or plastic substrates that use paint-like suspensions of an alumina cementitious slurry and colloidal silica dispersions. European patent No. EP 0674089, issued by Wood, describes a fire door made of a wooden three-layer (sandwich) structure and comprising a heat-insulating fire-resistant material, which is a mixture of fire-resistant cement based on calcium aluminate and inorganic fibers.

Intumescent compositions may include sodium silicate compositions which, when exposed to heat, tend to increase in volume due to increasing foaming pressure and tend to form semi-coke, which protects the structure, when exposed to heat. A number of intumescent compositions have been described and are used in fire coatings, including US Pat. No. 4,727,916 issued to Feldman; US patent No. 5476891 issued by Welna; US patent No. 5786095 issued to Batdorf; U.S. Patent No. 4,675,577 to Licht; US Patent No. 5,494,466 issued to Navarro et al and US Patent No. 5,580,648 issued to Castle et al. Castle patent describes a mastic intumescent fireproof coating that can be applied to building elements such as I-beams. Other examples of intumescent layered systems include US patent No. 3934066 issued by Murch et al, US patent No. 5258216 issued by von Bonin et al, US patent No. 5053288 issued by Delvaux et al, US patent No. 4,297,252 issued by Caesar et al, US patent No. 6,340,389 to Klus, U.S. Patent Nos. 6,270,915 and 6,182,470 issued to Turpin et al, U.S. Patent No. 4,799,349 to Luckanuck et al and U.S. Patent No. 5,722,213 to Morency.

Fire barriers and door designs also included additional structural parts such as wire fittings, for example, as described in US Pat. No. 5,215,806 to Bailey, heat-reflecting metal layers, as described in US Pat. No. 4,509,559 to Cheetham et al, and honeycomb materials. or spatial materials, as described in US Pat. No. 4,229,872 issued to Miguel et al, or US Pat. No. 4,767,656 to Chee et al.

SUMMARY OF THE INVENTION

Various multi-layer fire systems or multi-layer laminate materials are described that include one or more layers of a fire barrier. In general, a fire barrier is an inorganic polymer matrix obtained from at least one alkali metal silicate. These materials, which include one or more remaining layers, typically provide one or more of the following properties: increased fire resistance; thermal barrier; a layer that prevents oxidation, reinforcement, residual resistance during and after exposure to fire, prevention of burnout or reduction of smoke levels and the like. The actual design of the fire system is usually based on the required performance. Thus, the various layers typically include one or more insulating materials, one or more intumescent materials, one or more foam materials, one or more corrugated materials, one or more reflective layers, etc., as well as usually one or more reinforcing fillers such as fibers or sheets, which may be present as a separate layer or be included in one of the above layers.

The inorganic polymer matrix of the present invention, as desired, can be made either (1) as a reaction product of an alkali metal silicate, one or more non-silicate structure-forming substances, such as an acid oxoanion compound, and / or reactive glass, water and, optionally, a filler, and one or more secondary structural linking units (such as the multivalent (e) cation (s) selected (e) from groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, for example, an alkaline earth metal salt ), or (2) in the form of a reaction product of an alkali metal base, a source of silica and water, as well as non-silicate structure-forming substances and structure modifiers, or a combination thereof. Moreover, a modified inorganic polymer matrix can be obtained using an aqueous suspension of alkali metal silicate (or its precursor), reactive glass and water, as well as gelation inhibitors and other structure-forming materials and modifiers. The ability to vary these “building blocks” makes it possible to fine-tune the properties of the product so that it is suitable for numerous high-temperature areas of use. The composition may include other structure-forming materials, modifiers and fillers.

Composite materials based on alkali metal silicates can be prepared by applying an aqueous suspension of a modified alkali metal matrix to a reinforcing medium, such as continuous or intermittent fiber in the form of tows or mats of glass, carbon, carbon coated, oxidized carbon coated with a polymer of carbon, coated with a polymer of glass, ceramic-coated carbon, ceramic-coated glass, carbon-coated, metal-coated glass, steel, stainless steel, coated steel, polymer, mine ral or similar. After an optional B-stage period and / or separation (s), designed to remove excess reagents, non-polymer products, impurities and / or other undesirable substances, the composite material is cured in the temperature range from about 15 ° C to 1000 ° C and above and at pressure sufficient to harden the composite material, typically at an external pressure in the range from ambient pressure to about 2000 psi. inch and under vacuum from about ambient pressure to about 10 ^-3 Torr (for example, using a vacuum bag). A preferred temperature range is from 50 ° C to 200 ° C, and the pressure is less than about 200 or about 250 psi. inch with or without a vacuum bag. The term "B-stage" is a general term used in composite technology to describe a practice that allows the polymer matrix precursor to interact and process to the partially polymerized intermediate stage without reaching the fully cured polymer network. It is also possible to pump with a vacuum bag to facilitate water removal and curing. Separation methods include washing with water, solution and / or solvent, chemical steam and / or gases Infiltration The composite material can be molded by various methods, including direct molding, as well as other typical molding methods.

The resulting inorganic matrix composition and / or composite material exhibits thermal stability up to about 1000 ° C and higher depending on the formulation and processing and has excellent flame, smoke and toxicity properties. Moreover, the composite material made according to the present invention has a low weight and good heat-insulating and electrical insulating characteristics.

Instead of, or in addition to, the inorganic polymer matrix, other suitable inorganic fire fighting compounds include oxide-based cementitious substances, mortar, refractory materials, and the like. Suitable oxides include oxides of silicon, aluminum, magnesium and titanium and compounds that include such oxides, for example silicates, aluminates and the like. Additional oxides that may be included with the oxides indicated above include sulfur, calcium, and iron oxides. In addition, naturally occurring oxide minerals of indefinite composition can be included in the inorganic resin. Preferred inorganic resin compositions are alkali metal silicate resin compositions.

BRIEF DESCRIPTION OF THE DRAWINGS

This invention consists of the shown and described new parts, structures, arrangements, combinations and improvements. The accompanying drawings, which are included and form part of the description, illustrate one embodiment of the present invention and together with the description serve to explain the principles of the invention.

Figure 1 is an exploded cross-sectional view (cross section) of the flame retardant laminate of the present invention;

Figure 2 is a sectional view (transverse) of the laminate of Figure 1, which is arranged with additional layers to illustrate the layout of the door;

Figure 3 is a perspective view of a flame retardant laminate;

Figure 4 is a perspective view of another embodiment of a flame retardant laminate;

5 is an exploded cross-sectional view of an organic / inorganic composite material of the present invention;

6 is an exploded perspective view of a fire-retardant I-beam structure of the present invention;

Fig.7 is a perspective view of the assembled I-beams of Fig.6;

Fig. 8 is a graph of operating temperature versus time during a fire test;

Fig.9 is a graph of temperature versus time during operation of the layered materials when tested in an oven;

Figure 10 is a graph of temperature versus time during the operation of additional laminate materials when tested in an oven;

11 is a graph of temperature versus time during operation of an I-beam in an oven test;

12 is a block diagram showing some of the many types of laminate systems that can be manufactured according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

An important aspect of the present invention is the use of at least one layer of a system or laminate that comprises a composition of an inorganic polymer matrix, usually in combination with a reinforcing material. The composition of the inorganic polymer matrix of the present invention is obtained by the interaction of a solution of an alkali metal silicate, a nonsilicate structure-forming substance and / or reactive glass, water and, optionally, one or more secondary structural linking units, such as multivalent (e) cation (s) selected from the groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 of the periodic table, such as an alkaline earth metal salt, and, optionally, one or more fillers. Alternatively, the high temperature composition of the inorganic polymer matrix can provide the interaction of a source of silica, an alkali metal base, water, nonsilicate structure-forming substances and / or acid reactive glass and, optionally, one or more structure modifiers and / or one or more fillers. If necessary or desired, additional components may be included, such as functional and / or non-functional fillers, other structure-forming substances and modifiers.

The resulting modified alkali metal silicate composition can be cured at relatively low temperatures (<200 ° C) and at low pressures (<200 psi) to obtain an inorganic polymer structure having dimensional stability and thermal resistance up to 1000 ° C and higher. That is, the design comprising the matrix composition of the present invention does not show any significant permanent resizing at temperatures up to 700 ° C and above. However, it is not limited to a lower temperature or lower pressure and, if necessary or if desired, the properties can be further improved by using increased processing temperatures (up to 1000 ° C and higher) and pressure (up to 20,000 + psi and higher ), and / or including heat treatment after curing.

An exemplary chemical composition according to the invention, which is a qualitative representation of the starting materials, which is obtained from the aqueous mixture before curing to create an inorganic matrix, can be described as follows:

where A = (1-z) K ₂ O or (z) Na ₂ O, where z can vary from 0 to 1, K ₂ O is potassium oxide and Na ₂ O is sodium oxide, Li ₂ can also be introduced O and / or equivalent, such as LiOH, if desired;

SiO ₂ is silicon dioxide, which can be obtained from a source of silica, such as Kasil-1, fine silica powder, silica, silica gel, or combinations thereof,

H ₂ O represents water,

a = molar ratio A ₂ O: SiO ₂ , which is in the range from 0.05 to 1.0,

b = molar ratio B: SiO ₂ , which is in the range from 0.001 to 0.500,

c = molar ratio C: SiO ₂ , which is in the range from 0.0 to 0.250,

d = represents a molar ratio of D: SiO ₂ and is in the range from 0.0 to 2,000,

n = molar ratio of H ₂ O included in the formulation, the desired range of which for the starting formulation is from 0.10 to 0.90, with a range of n = 0.15 to 0.35 being preferred; and after curing, n is less than 0.25, with n <0.05 being preferred.

x = represents the number of additives (D) used to aid in the processing and functioning of the basic formulation, and ranges from about 0 to 20,

B = non-silicate glass-forming material, such as phosphate, sulfate or borate groups derived from an acid precursor, such as H ₃ PO ₄ , H ₂ SO ₄ , H ₃ BO ₃ , a combination thereof and / or reactive glass, such as alkaline borophosphate glass metal or alkali metal phosphoborate,

C = structure modifiers, such as Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , Al ³⁺ , Ti ⁴⁺ , obtained from compounds of multivalent metals of the main group and / or transition metals, such as Mg (NO ₃ ) ₂ , ZnCl ₂ or combinations thereof, or which are a metal component of reactive glass, and

D = optional additives selected from one or more, single or in combination, component, including:

(i) but not limited to reactive and / or non-reactive excipients such as kaolin, smectites, attapulgites, mica, vermiculite, metakaolin, metal oxides, or a combination thereof;

(ii) gelation modifiers, such as organic base (quinoline) and / or organic acid (lactic acid);

(iii) surfactants, such as an anionic, cationic and / or nonionic surfactants, such as alkylaryl sulfonates, quaternary ammonium salts, salts of protonated organic amines, organic-inorganic hybrids, such as silicones, or a combination thereof, but not limited to this; and

(iv) toughness agents and / or organic-based plasticizers, which may be in the form of resins, low molecular weight and / or high molecular weight polymers.

If necessary, technological additives can be added, which include mineral oils, vegetable oils, animal oils, silicone oils, fatty acids and salts, aliphatic alcohols, fluorinated oils, waxes, polyolefins (such as, for example, polyethylene, oxidized polyethylene and polytetrafluoroethylene, but not limited to this) graphites, surfactants and mixtures thereof.

An alternative expression of the chemical composition of the invention, comprising reactive glass, can also be described as follows:

where A = (1-z) K ₂ O or (z) Na ₂ O, where z can vary from 0 to 1, K ₂ O is potassium oxide and Na ₂ O is sodium oxide, Li ₂ can also be introduced O and / or equivalent, such as LiOH, if desired;

SiO ₂ is silicon dioxide obtained from a source of silica, such as Kasil-1, a fine silica powder, silica, silica or silica gel, or combinations thereof,

G = reactive glass, such as alkali metal borophosphate or alkali metal phosphoborate glass,

F _x = optional additives and / or non-silicate (e) glass forming (e) material (s), for example, one or more components, individually or in combination, including:

(i) P ₂ O ₅ , B ₂ O ₃ or SO ₃ derived from acidic precursors such as H ₃ PO ₄ , H ₃ BO ₃ or H ₂ SO _4, or a combination thereof,

(ii) modifier (s) of the structure, such as Mg ²⁺ , Zn ²⁺ , Al ³⁺ , Ti ⁴⁺ , obtained from compounds of multivalent metals of the main group and / or transition metals, such as Mg (NO ₃ ) ₂ , ZnCl ₂ or a combination thereof;

(iii) but not limited to reactive and non-reactive excipients such as kaolin, smectites, attapulgites, mica, vermiculite, metakaolin, metal oxides, or a combination thereof;

(iv) gelation modifiers, such as organic base (quinoline) and / or organic acid (lactic acid);

(v) surfactants, such as an anionic, cationic and / or nonionic surfactants, such as alkylaryl sulfonates, quaternary ammonium salts, salts of protonated organic amines, organic-inorganic hybrids, such as silicones, or a combination thereof, but not limited to this;

(vi) toughness agents and / or organic-based plasticizers, which may be in the form of resins, low molecular weight and / or high molecular weight polymers.

H ₂ O represents water,

a = molar ratio A ₂ O: SiO ₂ , which is in the range from 0.05 to 1.00,

g = molar ratio G: SiO ₂ , which is in the range from 0.01 to 0.500,

f = molar ratio F: SiO ₂ which is in the range from 0,000 to 2,000,

x = 0 to about 20 and represents the number of additives (F) used to aid in the processing and functioning of the basic formulation, and

n = molar ratio of H ₂ O included in the formulation, where for the original formulation, the desired range is from 0.10 to 0.90, with the range n = 0.15 to 0.35 being preferred, and after curing, n is less than 0 , 25, with n <0.05 being preferred.

If necessary, technological additives can be added, which include mineral oils, vegetable oils, animal oils, silicone oils, fatty acids and salts, aliphatic alcohols, fluorinated oils, waxes, polyolefins (such as, for example, polyethylene, oxidized polyethylene and polytetrafluoroethylene, but not limited to this), graphites, surfactants, or combinations thereof.

The alkali metal silicates used in this invention can have a wide range of silica / alkali metal oxide (SiO ₂ / A ₂ O) ratios and% solids levels. Such solutions can be obtained from commercial sources or prepared immediately before use from precursors such as a source of silica and alkali metal hydroxide, alkali metal oxide, carbonate, or combinations thereof. An alkali metal silicate can be prepared from an alkali metal base such as potassium hydroxide or sodium hydroxide, from potash or soda ash and a source of silicon dioxide. The source of SiO ₂ may be amorphous or crystalline SiO ₂ such as silica, fine silica powder, precipitated silica, colloidal silicon dioxide, silica fume, sand, microcrystalline silica, silica gel, colloidal silica, quartz, silica flour, sodium silicate solution, potassium silicate solution, as well as solid silicates of sodium and / or potassium. An example of a commercially available alkali metal silicate is Kasil-1, manufactured by PQ Corporation, Valley Forge, PA. Various sources of silica have desirable as well as undesirable properties. For example, some sources of fine silica powder contain traces of carbon that can cause discoloration of the final product. In addition, the thermal and physical properties of the composition of the inorganic polymer matrix may be affected by the nature of the silica source, for example, the inclusion of a dense α-quartz crystal network can increase dimensional stability, while at the same time, introducing a source of open amorphous silica will give the structure lower density meshes. However, an appropriate alkali metal silicate solution can be obtained by combining various sources of alkali and / or silica. When an alkali metal silicate is obtained from an alkali metal hydroxide and a silica source, the alkali metal hydroxide is present in an amount of from about 3 wt.% To 30 wt.%, Based on the total weight of the composition or mixture, preferably from about 7 wt.% To 20 wt. .%. The silica source is present in an amount of about 10 wt.% To 85 wt.% Or about 90 wt.% Or about 94 wt.%, Preferably from 15 wt.% To 70 wt.%. In some cases, for example, when an alkali metal silicate solution is used, a portion of the alkali metal hydroxide, silica and water that are provided are included in the described ranges.

The alkali metal silicate used in the preparation of the inorganic resin composition is potassium silicate solutions, sodium silicate solutions, crystalline sodium silicate, crystalline potassium silicate, amorphous sodium silicate, amorphous potassium silicate and mixtures thereof. Alternatively, alkali metal silicate precursors are an alkaline base and a silica source. Silica in an alkali metal silicate is an amorphous or crystalline form of silica selected from the group consisting of silica, fine silica powder, silica fume, precipitated silica, sand, quartz, silica flour, silica gels, colloidal silicon dioxide and colloidal silica. Preferably, the alkali metal silicate and / or alkali metal silicate precursors have an SiO ₂ / A ₂ O ratio of from about 2.0: 1.0 to 20.0: 1.0, where A is K (potassium) and / or Na ( sodium) and wherein the alkali metal hydroxide is selected from the group consisting of potassium hydroxide and sodium hydroxide.

Non-silicate structure-forming substances can be introduced, if desired, in the range of from about 2 wt.% To 70 wt.%. The non-silicate structure-forming substance can be added as an acid oxoanionic compound. Examples of acid oxoanionic compounds include boric acid, phosphoric acid, sulfuric acid, monosubstituted sodium phosphate, disubstituted sodium phosphate, disubstituted potassium phosphate, monosubstituted potassium phosphate, ammonium hydrogen phosphate, phosphate salts of metals and / or non-metals, or compounds including borates, sulfates, aluminates vanadates, germanates, and similar ions, and combinations or mixtures thereof. The nonsilicate structure-forming substance can also be added as a non-acidic oxoanionic compound, for example, trisubstituted sodium phosphate, potassium phosphate, sodium borate or similar acid salts, if the pH of the mixture is adjusted by another method. A preferred mixture of acid oxoanionic compounds includes mixtures of monosubstituted potassium phosphate and boric acid; monosubstituted sodium phosphate and boric acid, monosubstituted potassium phosphate, monosubstituted sodium phosphate and boric acid; sodium borate and monosubstituted potassium phosphate, any grade or any concentration of these substances can be used, although a more concentrated substance is preferred to minimize water content. The acid oxoanionic compound is present in an amount of from about 0.01 wt.% To 20 wt.%, Based on the total weight of the composition. The preferred amount of acid oxoanionic compound is from about 2 wt.% To 8 wt.%. You can also include compounds containing multivalent atoms and acid oxoanions. Examples include monosubstituted aluminum phosphate Al (H ₂ PO ₄ ) ₃ , aluminum metaphosphate Al (PO ₃ ) ₃ , monobasic magnesium phosphate, monosubstituted zinc phosphate, monobasic calcium phosphate, calcium hydrogen phosphate, monobasic barium phosphate, dibasic barium phosphate, monosubstituted manganese phosphate, manganese hydrogen phosphate and similar metal phosphates.

Alternatively, a non-acidic oxoanionic compound can be used as a structure-forming substance. Examples of such compounds include trisubstituted sodium phosphate, potassium phosphate, sodium borate or similar acid salts, if the pH of the mixture is adjusted by another method. It is believed that non-acidic oxoanionic compounds can be added in an amount similar to the amount of acidic oxoanionic compounds.

Alternatively, reactive glass in combination with an alkali metal silicate solution can be used to prepare the composition. The phrase “reactive glass” encompasses a wide variety of inorganic acid glasses that can provide an acid group for the condensation reaction between an alkali metal silicate and glass that occurs during the curing reaction. Reactive acid glasses are preferred, and examples of reactive acid glasses include borophosphoric silicate, phosphate, phosphoroborate, borophosphate and borate glasses. Reactive glasses may not be truly acidic, but function in this way. Non-acid glass (pH about 7 to 10) can be used provided that the pH of the reactive glass is less than the pH of the alkali metal silicate component and / or its precursors. including higher temperatures (> 200 ° C) and / or higher pressures (> 200 psi) Reactive glasses differ from essentially non-reactive structural glasses that are used in chemical cups and vessels for drinking, and from optical glasses that are used in windows. Reactive glasses are made according to typical glass production processes by combining oxide reagents. In the case of alkaline borophosphate glass, P ₂ O ₅ , B ₂ O ₃ and one or more alkali metal oxides or their precursors are combined in powder form and the mixture is heated to its melting point of about 700 ° C to 1500 ° C, and then quickly cooling the melt and optionally annealing the glass to a hard, brittle state. The ratio of phosphorus oxide to alkali metal oxide (A ₂ O) will be from about 6.1: 1.0 to 1.5: 1.0. In the case of alkaline phosphoroborate glass, B ₂ O ₃ , P ₂ O ₅ and one or more alkali metal oxides or their precursors are combined in powder form and the mixture is heated to its melting temperature of about 700 ° C to 1500 ° C, and then quickly cooling the melt and optionally annealing the glass to a hard, brittle state. The ratio of phosphorus oxide to alkali metal oxide (A ₂ O) will be from about 5.0: 1.0 to 1.15: 1.0, and the ratio of boron oxide to alkali metal oxide (A ₂ O) will be from about 8 0: 1.0 to 1.5: 1.0.

Preferably, the hard glass is ground to a powder form. A preferred powder is powdered reactive borophosphate glass. The use of this preferred powdery glass facilitates adjusting the cure rate and the amorphous nature of the matrix. The thermal and physical properties of the inorganic silicate / glass matrix can be varied by adjusting the ratio of SiO ₂ to reactive glass and / or glass precursors (G). The ratio of G: SiO ₂ can vary from 0.01 to 50.0 by weight. Reactive glass is used in an amount of about 0.01% to 60% by weight based on the total weight of the mixture, with an amount of 3% to 35% being preferred and an amount of 5% to 20% by weight being most preferred.

Since it is desirable that the resulting glass is acidic, the composition of this glass will consist mainly of glass-forming substances such as oxides of phosphorus, boron and optionally silicon. A preferred alkali metal oxide is lithium oxide. If glass with a high phosphorus content is required, then the glass composition before melting will include from about 20 mol.% To 80 mol.% Of phosphorus oxide (V) (P ₂ O ₅ ) or its salts, acids or other precursor forms that provide appropriate or equivalent amounts of phosphorus and oxygen based on the total amount of glass formulation, preferably from 30 mol% to 70 mol%, more preferably from 35 mol% to 65 mol%. Most preferably, 60 mol% to 65 mol% is used. Boron oxide (B ₂ O ₃ ) will comprise from about 1 mol% to 15 mol% of glass, preferably from 2 mol% to 8 mol%, and more preferably from 4 mol% to 6 mol%. Alkali metal oxide (A ₂ O) is from about 5 mol% to 50 mol% of the glass composition, preferably from 20 mol% to 40 mol%, and more preferably from 15 mol% to 30 mol%. Alkaline earth metal oxide (M'O) is used in an amount of about 0.01 mol% to 30 mol% of the total glass mixture, an amount of 5 mol% to 20 mol% is preferred, and an amount of 10 mol % to 15 mol% is more preferred. If desired, other oxides may be included, including, but not limited to, alumina, iron oxide, lanthanum oxide, cerium oxide, molybdenum oxide, and silicon dioxide. These oxides are added in an amount up to 20 mol%.

If glass with a high boron content is needed, then the glass composition before melting will include from about 10 mol.% To 50 mol.% Of phosphorus oxide (V) (P ₂ O ₅ ), or its salts, acids or other precursor forms, which provide equivalent amounts of phosphorus and oxygen based on the total amount of glass formulation, preferably from 20 mol% to 40 mol%, more preferably from 25 mol% to 35 mol%. Boron oxide (B ₂ O ₃ ) will comprise from about 10 mol% to 70 mol% of glass, preferably from 30 mol% to 60 mol%, and more preferably from 45 mol% to 55 mol%. Alkali metal oxide (A ₂ O) is from about 5 mol% to 45 mol% of the glass composition, preferably from 20 mol% to 40 mol%, and more preferably from 15 mol% to 30 mol% . An alkaline earth metal oxide (M'O) is optionally used in an amount of about 0 mol% to 30 mol% of the total glass mixture, an amount of 5 mol% to 20 mol% is preferred, and an amount of 10 mol. % to 15 mol.% is more preferable if used.

The formulation of reactive glass, if used, is critical to the chemistry and implementation of the present invention. It is desirable that the glass react with a mixture of alkali metal silicates to reduce the basicity of the resulting matrix and to connect multiple grid structures. The combination of very different network structures, one based on silicate and the other based on phosphate, leads to a mixture of an amorphous inorganic polymer and a crystalline network, as well as new network units formed by the reaction of alkaline silicate and acid phosphate, such as -Si-OP- . Both silicate and phosphate compounds, which are known to be excellent structure-forming substances, form the basis for this invention.

Reactive glass, which can be used to obtain a composite material, can be briefly described by the following formula:

где Σr_k=1

where Σr _k = 1

k = 1

Formula III

where n = the number of desired glass components,

M = at least one glass-forming component, such as boron, silicon, phosphorus, sulfur, germanium, arsenic, antimony, aluminum and vanadium, and at least one glass modifier that works like a flux, such as lithium, sodium , potassium, rubidium and cesium, and optionally additional structure modifiers such as vanadium, aluminum, tin, titanium, chromium, manganese, iron, cobalt, nickel, copper, mercury, zinc, thulium, lead, zirconium, lanthanum, cerium , praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, act Nij, thorium, uranium, yttrium, gallium, magnesium, calcium, strontium, barium, tin, bismuth and cadmium,

E = oxygen, chalcogenides and / or halogens, such as sulfur, selenium, tellurium and fluorine,

P = valency of cation M, e.g. 5 for phosphorus, which is usually depicted as P ⁵⁺ or P (V),

q = valency of anion E, for example 2 for oxygen, which is usually depicted as O ^2- ,

q '= the number of cations M contained in a unit of the structure, equal to q or q / 2, which is the smallest integer whenever p and q are even numbers, for example 2 for phosphorus in P ₂ O ₅ or 1 for silicon in SiO ₂

p '= the number of E anions contained in the structural unit equal to p or p / 2, which is the smallest integer whenever p and q are even numbers, for example 5 for phosphorus in P ₂ O ₅ or 2 for silicon in SiO ₂

r = molar fraction of each individual structural unit in the component of reactive glass,

n = number of common structural units in the reactive glass component.

Binary glass can be represented as {(M ₁ ^{p +} ) _{q '} ) (E ₁ ^q- ) _p' } _r1 {(M ₂ ^{p +} ) _{q '} ) (E ₂ ^q- ) _p' } _r2 , r ₁ + r ₂ = 1, and the triple glass formula can be generalized in the form {(M ₁ ^{p +} ) _{q '} ) (E ₁ ^q- ) _p' } _r1 {(M ₂ ^{p +} ) _{q '} ) (E ₂ ^q- ) _p' } _r2 { (M ₃ ^{p +} ) _{q '} ) (E ₃ ^q- ) _p' } _r3 , r ₁ + r ₂ + r ₃ = 1. Thus, sodium-calcium-silicate glass can be described as (CaO) _r1 (SiO ₂ ) _r2 (Na ₂ O) _r3 , where r ₁ + r ₂ + r ₃ = 1. Silicon (Si) is a glass-forming component covalently bonded to oxygen to form a glass structure, and sodium (Na) and calcium (Ca) are glass modifiers that are ionically bonded to the silicate structure, contributing to the formation and stability of the glass phase. Therefore, M generally represents at least one structure-forming substance (M _gf ) and at least one glass structure modifier (M _gm ) in the glass formulation.

The clarification time and temperature of the glass also affect its physical and mechanical characteristics. For a constant composition, an increase in the clarification temperature and / or time additionally densifies the glass structure, increasing T _g , T _s and T _m , lowering the activity of the structure and the content of hydroxyl / H ₂ O glass, while improving durability. Thus, with a change in glass composition, glass lightening time, and temperature, different glass formulations can vary greatly with respect to reactivity, durability, acidity, hydrolytic stability, impact strength, and workability. You can optionally add moderate levels of silicon dioxide and / or alumina to limit furnace fouling and / or harden the glass structure if very high temperature resistance is needed (> 900 ° C). Coordination, mixing and adjustment of the properties of glass and alkali metal silicate gives the formulation of a material resistant to high temperature with unique and new properties. In other words, the ability to change data “structural blocks” makes it possible to adapt the properties of the product to numerous areas of use under high temperature conditions.

The particle size of the reactive glass, as well as the particle size of the additional ingredients, is important, but not critical. Obviously, the reactivity of the ingredients increases with decreasing particle size, and if the particles are too small, then the substances may be too reactive, so it may be necessary to make adjustments in the components used to obtain the compositions of the present invention. The powdered components of the composition (silica, reactive glass, etc.) can be granulated, tabletted or densified in another way before being added to the liquid portion of the composition.

Although this invention is a composition of an inorganic polymer matrix obtained by reacting an alkali metal silicate source and a non-silicate structure-forming substance and / or reactive glass, the mechanical, physical and technological characteristics of the matrix can be improved using additional components, if desired. If necessary, you can include additional components, such as fillers, other structure-forming substances and modifiers. They include additives, structure-forming substances and fillers, typically used or known to the person skilled in the art, inorganic, organic or hybrid, and may include additives or fillers to enable processing, manufacture and improvement of performance when used.

Optional additives and / or additional structure-forming substances can be such compounds as borates, sulfates, aluminates, vanadates, boric acid, phosphoric acid, sulfuric acid, nitric acid, phosphorus oxide (V), monosubstituted sodium phosphate, disubstituted sodium phosphate (disodium phosphate ), monosubstituted potassium phosphate, disubstituted potassium phosphate (dipotassium phosphate), ammonium hydrogen phosphate, other phosphate salts of metals and / or non-metals, germanates or the like. Optional structure-forming substances are present in an amount of from 0.0 wt.% To 50 wt.%, Based on the total weight of the composition. If a structure-forming substance is included in the formulation, its preferred amount of F ₁ is from 2 wt.% To about 10 wt.%.

The secondary structural linking units may be multivalent cations selected from groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, preferably from groups 2, 3, 4, 5, 11, 12, 13, 14, 15 or 16 of the periodic table, and they are used in an amount of from zero to about 20 wt.%, Based on the total weight of the mixture, with a range of from about 1.0 wt.% To 5 wt.%. Multivalent cations of Cr, Mo, W, Mn, Fe, Co, Ni, Pd and Pt of groups 6, 7, 8, 9, 10 can also be used, but cations from other groups are preferred. Compounds containing a multivalent cation may include any metal salt of the main group, including nitrates, sulfates and chlorides, although zinc, magnesium and calcium salts are preferred. The optional secondary linking structure may be a multivalent cation, useful for coordination with two oxo compounds, such as the cation of alkaline earth metals, main group metals, transition metals, lanthanides and / or actinides, and any combination thereof that is applicable. Other secondary structural linking units may include compounds containing boron, aluminum, lead, gallium, cadmium, titanium, zirconium, lanthanum, cerium, neodymium, yttrium, strontium, barium, lithium, rubidium, cesium and fluorine.

Optional additives that can be used include clay fillers, oxide fillers, gel modifiers, toughness increasing organic additives, plasticizers, or combinations thereof. Fillers include kaolin, metakaolin, montmorillonites, mica, as well as other smectites and other clay or mineral fillers. When clay fillers are used, calcined kaolin is preferred and can be used in an amount of from zero to 25 wt.% Based on the total weight of the composition, with 3 wt.% To 5 wt.% Being preferred. Calcined kaolin may have some reactivity with silicate matrix materials, although a clay filler has no reactivity, and any of the commercial clay fillers can be used.

Optional oxide fillers that can be used include oxides of boron, aluminum, silicon, zinc, gallium, titanium, zirconium, manganese, iron, molybdenum, tungsten, bismuth, lead, lanthanum, cerium, neodymium, yttrium, calcium, magnesium and barium, and they are present in an amount of about 0.0 wt.% to 20 wt.%, based on the total weight of the composition. Magnesium oxide (MgO, which is preferred) is used in an amount of from zero% to 15% by weight based on the total weight of the composition, from 1% to 10% by weight is preferred, and from 2% to 8% by weight is particularly preferred.

Modifiers may include crosslinking agents and gel inhibitors or activators such as mineral acids, organic acids and bases. Crosslinking agents can also be introduced in the form of metal phosphates, as described previously. These include aluminum phosphate, magnesium phosphate, calcium phosphate, zinc phosphate, iron phosphate, cerium phosphate, lanthanum phosphate, barium phosphate, monosubstituted aluminum phosphate (Al (H ₂ PO ₄ ) ₃ ), aluminum metaphosphate (Al (PO ₃ ) ₃ ) monobasic magnesium phosphate, magnesium hydrogen phosphate, monosubstituted zinc phosphate, monobasic calcium phosphate, calcium hydrogen phosphate, monobasic barium phosphate, dibasic barium phosphate, monosubstituted manganese phosphate, manganese hydrogen phosphate and similar metal phosphates.

An optional gel modifier is an organic acid and / or organic base, typically selected from the group consisting of hydroxy acids and N and P bases. Examples of organic acids include lactic acid and citric acid. Preferably, α-hydroxy acids, β-hydroxy acids, substituted pyridines and quinolines are used. They are used in an amount of from zero to 10 wt.%, Based on the total weight of the composition, and an amount of from 0.05 wt.% To 5 wt.% Is preferred. An optional surfactant is an anionic, cationic and / or nonionic surfactant, such as alkylaryl sulfonates, silicones, quaternary ammonium salts, salts of protonated organic amines, hydroxyl polymers, organic-inorganic hybrids such as silicones, and combinations thereof, but not limited to this. These additives are used in an amount of from zero to 10 wt.%, Based on the total weight of the composition, and an amount of from 0.5 wt.% To 5 wt.% Is preferred.

An optional organic impact enhancing additive and / or plasticizer is an organic based enhancing impact additive, a plasticizer, or a combination thereof. An organic-based impact strength improver can be selected from the group consisting of resins, low molecular weight and / or high molecular weight polymers. These substances are used in an amount of from zero to 10 wt.%, Based on the total weight of the composition.

The rest of the uncured composition is water, and it will be from about 10 wt.% To 75 wt.%, Based on the total weight of the composition. The preferred range is from 15 wt.% To 40 wt.%. Water can be introduced as part of one of the components, for example, as part of an alkali metal silicate solution, an alkaline earth metal salt solution or part of a phosphoric acid solution. Since the water included in this invention can be considered as a reaction medium, a reagent, as well as a reaction product, the concentration of water is generally difficult to quantify. The initial water level in the starting mixture can vary from about 10 wt.% To 70 wt.%, While the B-stage prepreg can contain from about 5 wt.% To 35 wt.% Water. The cured inorganic binder sample itself, as well as the composite material may contain from about 0 wt.% To 10 wt.% Water, depending on the processing conditions.

As noted above, a very important aspect of the present invention is the desirable use of a reinforcing medium, preferably a woven and / or non-woven, continuous and / or discrete fiber, which is used in an alkali metal silicate resin layer. Reinforcement can range from about 2 vol.% To 60 vol.%. Reinforcing fibers may include nickel fiber, glass fiber, carbon fiber, graphite fiber, mineral fiber, oxidized carbon fiber, oxidized graphite fiber, steel fiber, metal fiber, metal coated carbon fiber, metal coated glass fiber, metal coated graphite fiber, metal coated ceramic fiber nickel-plated graphite fiber, nickel-plated carbon fiber, nickel-plated glass fiber, silica fiber, ceramic fiber, silicon carbide fiber, stainless steel fiber, titanium fiber, nickel alloy fiber, brass coated steel fiber, polymer fiber, polymer coated carbon fiber, polymer coated graphite fiber, polymer coated glass fiber, polymer coated aramid fiber such as Kevlar®, ceramic-coated carbon fiber, ceramic-coated graphite fiber, ceramic-coated glass fiber, oxidized polyacrylonitrile fiber, basalt fiber, alkali resistant eklovolokno and / or other fibers known to those skilled in the art. Combinations of data from various fibers may also be used. Preferably, the fiber is graphite fiber, E-glass fiber, S-glass fiber, basalt fiber, stainless steel fiber, titanium fiber, nickel alloy fiber, aramid fiber, polyethylene fiber, SiC fiber and BN fiber. These fibers may also be coated and / or processed. Examples of suitable coatings for use on fibers include vapor deposited metal and metal alloys, chemically deposited metal and metal alloys, metals and metal alloys deposited from the melt, electrolytically deposited metal and metal alloys, organic polymer coatings, inorganic-organic polymer hybrid coatings , metal oxides, phosphates, metal phosphates, silicates, organic polymer silicates and hybrids, organic polymer-silica and functionalized siloxanes.

Reinforcing fibers can be in many forms, including yarn, tow, whiskers, continuous fiber, short fiber, woven materials, woven sheets, knitted fabric, non-woven materials, non-oriented mats, stitched mats, nets, felt, braided materials, wound tow, wire and / or other forms known to the person skilled in the art.

As the reinforcing material, fiberglass reinforcement can be used (including, but not limited to, E-fiberglass, S-fiberglass and alkali-resistant fiberglass). Composite structures may also include hybrid fiber reinforcement, for example, a combination of glass fiber, carbon fiber, organic polymer fiber, oxide, and / or metal. Reinforcement may be in the form of a woven or non-woven material, mesh, sieve, cotton, continuous or discrete fibers. Various fibers and / or tissues can be mixed in a matrix or discretely divided into layers. Examples include alternating layers of carbon fiber and glass fiber reinforcement, as well as a sandwich steel mesh placed in the middle of the glass mesh. Composite materials using the fiberglass reinforcement and matrix binder of the present invention are cost-effective, non-combustible, thermally stable [for example, no measurable (<0.2%) residual resizing after 48 hours of exposure at 700 ° C] composite materials with insulating properties and structural properties that can be processed at lower temperatures using typical processing equipment. Conventional processing can be carried out at relatively low temperatures (<200 ° C) and low pressure (<200 psi). Cross-reinforced glass fiber laminated material can be obtained with high thermal insulation properties (for example, nominal thermal conductivity 1.4 W / m · K), electrical insulation properties (undetectable conductivity when measured with a standard ohmmeter) and moderate mechanical characteristics (bending modulus up to 18 million pounds per square inch, bending strength up to 200+ thousand pounds per square inch and maximum bending deformation up to 1.3%). This combination of properties should be a promising technology for many areas of use.

Ceramic fiber reinforcement (including silicon carbide fibers) is another preferred reinforcement, especially for high temperature applications (above 700 ° C). Although ceramic fibers are expensive, they retain structural integrity well above 1000 ° C. Carbon fiber reinforcement is the preferred reinforcement when electrical conductivity, thermal conductivity, high strength and / or impact strength are desired.

The mechanical properties of the composite structure, including the composition of the inorganic polymer matrix, can be improved provided that there is sufficient interaction between the matrix and the reinforcing component. A composite structure including a composition of an inorganic polymer matrix provides an increased level of mechanical strength if the reinforcing component shows to some extent an oxophilic character at the matrix – reinforcing component interface. The composite structure, including the composition of the inorganic polymer matrix and reinforcing with stainless steel, exhibits an increased level of mechanical characteristics. The improvement is better illustrated by using carbon or graphite fiber as the reinforcing component. Carbon and / or graphite fibers are basically non-polar and hydrophobic, but they can be processed in various ways to create areas with a hydrophilic character, for example by applying a sizing or other coating (usually organic polymers such as epoxies or organic silanes) or the use of surfactants. Typically, increasing the hydrophilic nature of the fiber will also create a more oxophilic surface and improve the interface between the reinforcing component and the matrix, but the reinforcing component can be made more oxophilic in other ways. Metallization of the fiber can create an oxophilic surface, which will significantly increase the interfacial strength of the composite structure. Chemical, thermal, or electrolytic oxidation of the carbon, graphite, and / or polymer reinforcing component can also increase oxophilicity and thus interfacial strength and mechanical properties of the composite structure. Moreover, the fiber can be sized with an organic polymer combined with a powdery inorganic oxide such as glassy frit, reactive glassy frit, silica, alumina, zirconia and similar oxide-based materials. This gives the oxophilic surface character of the reinforcing component. These principles can also be extended to other oxide-based matrix compositions, including, but not limited to, alkali metal silicate resins, metal phosphate resins, cementitious materials, refractory compounds, and other inorganic and / or hybrid inorganic / organic oxide materials. By providing sufficient roughness and surface roughness of the reinforcing medium to promote beneficial mechanical interaction, it is also possible to increase the interface between the matrix and the reinforcing component.

In addition, the composition of the inorganic polymer matrix may include a variety of organic and inorganic fillers commonly used by specialists in this field. The matrix may include filler materials such as ceramic powders, mineral powders, metal powders, silicon carbides, silicon nitrides, silicates, boron nitrides, aluminosilicates, aluminum silicates, mixed sodium and aluminum silicates, mixed potassium and aluminum silicates, carbon, carbon black, carbon nanotubes, molybdenum and its compounds or other fillers known to the person skilled in the art. Organic materials are less preferred when the area of use is such that organic materials will burn and produce gaseous products. The fillers can also be spherical, such as microspheres, macrospheres, hollow and / or solid spheres, and / or particles of a cylindrical, flat and / or regular or irregular shape.

The composition of the inorganic polymer matrix of the present invention affects the pH of a solution containing an alkali metal silicate base by introducing an acidic inorganic component (such as protonated oxoanions, for example phosphoric or boric acid, monosubstituted phosphate or reactive glasses) and an acid salt modifier such as an alkaline earth metal salt. Alkali metal silicate solutions require a high pH to maintain a high concentration of monomeric silicate anions, which are necessary for moderate network formation. The ability to cure under moderate conditions after lowering the pH to a lower value reduces the damage to fiberglass reinforcement caused by the alkaline nature of the matrix. The inorganic matrix binder is cured by a condensation reaction partially driven by the removal of water from the skeleton, and excess water in the binder leads to a lack of dimensional stability, poor physical properties and processing difficulties.

It is understood that the compositions of the inorganic polymer matrix of the present invention can be made and processed into composite materials using direct molding, bulk molding, sheet forming, powder and reinforcing, liquid and reinforcing, prepreg and sintering. Additional methods include pultrusion (an automated process capable of producing a product with a constant cross section), wet layering (a simple manual method for quickly producing prototypes and producing products with low performance), a filament winding (an automated method for producing bodies of revolution), vacuum bag molding ( typical method for high-performance aerospace laminated materials), autoclave or non-autoclave vacuum injection (the method for high-performance parts is large thickness), film infusion of liquid resin or powder infusion, injection molding (the process of forming a mesh-like material with excellent reproducibility of dimensions), extrusion (the way in which non-structural short-fiber products of constant cross section can be obtained), injection molding (an automated way that can be obtained small, non-structural short-fiber products), casting (method for bulk non-structural products), centrifugal casting (method that can be Started pipes of high quality), the stabilized elastomer molding (a method that can produce unusual shapes) and similar processes.

The composite material is cured in a temperature range of from about 15 ° C to 1000 ° C and above, and at a pressure in the range of 0 psig. inch to about 2000 psi inch, preferably at a temperature of from about 50 ° C to 200 ° C and at a pressure of less than about 200 psi. inch.

If desired, the composite may be post-cured and / or chemically treated to further enhance thermal, dimensional or hydrolytic stability, or a combination thereof. This part can be thermally treated in air, under vacuum or in an inert atmosphere in the temperature range from about 15 ° C to 1000 ° C. The composition may be washed with water or another solvent to remove excess reagents. Moreover, this can be done after only partial formation of the inorganic polymer network structure before the completion of the curing process. The composite part can also be brought into contact with acid solutions, solutions of metal salts, solutions of salts of metallic acids, solutions of surfactants, solutions of fluorinated compounds, silicon-based compounds, organic form-polymers, ionomers, polymers and / or other solutions intended to impart hydrophobicity.

For example, dipping or coating a composite structure using a dilute phosphoric acid solution can improve the thermal as well as hydrolytic resistance of the composite structure. The phosphoric acid solution may contain one or more metal salts. A similar improvement can be achieved using a dilute solution of magnesium salt alone or in combination with a solution of phosphoric acid. Other soluble salts of polyvalent metals may also be used, for example, containing aluminum, calcium, zinc, cerium, lanthanum and / or similar salts. The composite structure, if desired, can also be treated with solutions of monovalent metal salts such as lithium hydroxide, lithium acetate, lithium chloride and so on.

These methods have several advantages over the curing / densification methods commonly used in the manufacture of high temperature inorganic polymers, namely ceramics and glasses. Ceramic and glass processing typically requires high temperature processing equipment (above 1000 ° C). The nature of the inorganic matrix formulations of the present invention makes it possible to process composite materials using conventional equipment used in plants for manufacturing composite materials. These methods make it possible to achieve higher productivity in comparison with typical ceramic methods and make it possible to easily produce larger parts in comparison with typical ceramic methods. Using these methods provides large volumes of fiber with structural integrity, which is excellent for the proper processing of concrete.

Alternatively, the composition of the inorganic polymer matrix of the present invention is not limited solely to composite materials. The composition can be used to obtain pure components of resins, coatings and adhesives.

It is valuable that the present invention can be implemented as a non-combustible material. This desirable safety feature distinguishes this invention from most organic materials (such as, for example, but not limited to plastics, wood or rubber), which tend to burn, form smoke and / or toxic gases when exposed to fire. Moreover, the present invention can be implemented as a heat insulator and / or electrical insulator. This desirable feature distinguishes the compositions of the present invention from most metals (such as steel, aluminum or copper), which tend to be conductors of heat and electricity.

The present invention can be implemented for operation at high temperatures (> 1000 ° C) with minor residual changes in size. This desirable property distinguishes the invention from most organic materials (which tend to undergo pyrolysis when exposed to temperatures exceeding 500 ° C), from most cementitious formulations (which tend to crack above 300 ° C) and from many metals (including aluminum) that have tendency to deform or melt at 700 ° C. As a further characteristic feature, the systems of the present invention can achieve high temperature performance (up to 1000 ° C and higher), while being processed at relatively low temperatures (<200 ° C) and low pressures (for example, but not limited to, up to <200 ° C and <200 psi). This property is desirable because the ability to process at low temperatures and pressures makes it possible to process the systems of the invention with more suitable equipment and more acceptable methods. This characteristic feature of chemistry distinguishes the present invention from most ceramic materials, glasses and metals, which usually require very high temperatures and / or high pressures to obtain a molded sample. Of course, the system of the invention can be efficiently processed at higher temperatures and pressures; material was processed at pressures above 10,000 psi. inches and at temperatures above 1500 ° C.

In some cases, the area of use may require a thermal barrier to resist flame and / or elevated temperatures during one service cycle and then replaced or used at lower operating temperatures when it is not necessary to withstand extreme temperatures in excess of 200 ° C. Organic / inorganic hybrids based on the present invention may be used. The organic component may be monomeric, oligomeric or polymeric in nature and impart additional impact strength, ductility and flexibility to the hybrid composition.

The present invention can be carried out by impregnating fibers to obtain a rigid composite material. This desirable feature distinguishes the invention from most materials, since the most rigid materials were not processed as a liquid with a low viscosity, capable of wetting the fibers. Reinforcing the matrix material with fibers provides many advantages, including improved strength, stiffness, crack resistance, fatigue resistance, and impact resistance. While fiber-reinforced composite materials are common in areas of use ranging from the dashboard of an automobile to the elements of an F-22 aircraft, the vast majority of composite materials are made from materials that are organic matrices that are combustible. Non-combustible composites, such as ceramic matrix composites and metal matrix composites, tend to have cost limitations for most applications due to the high processing temperatures required. The present invention can be carried out at a lower cost compared with most composite materials with a ceramic or metal matrix. These desirable features distinguish the present invention from many materials, including numerous metals.

The composition of the present invention can be easily obtained, including a variety of the above generally described excipients, so that the performance characteristics of the material are suitable for specific applications. These fillers, which may include hollow spheres, conductive fillers, additives that increase the coefficient of friction and / or thermal resistance, can be included to modify physical properties, including, but not limited to, density, conductivity, coefficient of friction, or thermal characteristics. These desirable characteristic properties distinguish the present invention from many materials, including many metals. Possessing these features, the present invention is suitable for many applications, including fire barriers, heat shields, high-temperature insulators, high-temperature molds, friction products, tools and structures operating under high temperature conditions.

In addition to the inorganic polymer matrix compositions, other compounds, such as various organic and inorganic fillers, can be used, and the inorganic polymer matrix compositions can be made using a variety of methods, such as compression molding, volume molding, etc., and then harden, process and use in various fields of use, and they may have the desired properties according to numerous ASTM tests formulated in US Pat. No. 10/777885 ″ Fire Testing Inorganic Composite Structures ″, hearth Mr. February 12, 2004, which is hereby incorporated by reference, including all 39 examples.

Fire protection systems or multilayer fire-retardant systems of the present invention typically include two or more layers of different materials, preferably at least one of the layers includes the above inorganic polymer matrix derived from alkali metal silicate, and optionally, but preferably, containing a fibrous reinforcing component . The remaining one or more layers include any of the following component: at least one insulating material, at least one intumescent material, at least one foam material, at least one reflective material, or a reinforcing layer or reinforcing material in any of the above layers. In addition, a corrugated gas-containing layer may exist separately or within any of the above layers. Another fire fighting system may comprise two or more layers of an alkali metal silicate polymer resin.

Insulating materials that have good fire-fighting properties typically include high temperature resistant materials known from the literature and the prior art, such as various silicate compounds, various alumina compounds, or combinations thereof, such as alumina silicates (RCF). Often, such compounds are present in the form of fibers because they are low in weight and are used in many applications, but solid layers of such compounds can also be used. Other suitable insulating materials include various materials and compounds known in the art and literature, which typically contain significant amounts (at least about 30%, or about 50%, or about 70% by weight) of alumina, silica, aluminate, silicate as well as other metal oxides containing calcium, magnesium and the like. Other insulating compounds include various refractory materials such as silicon carbide, carbon-carbon, and the like. You can also use various ceramic materials known from the literature and the prior art, made of various clays, such as tiles, terracotta, and the like, porcelain, porcelain enamels, lime, plaster and gypsum products and the like.

The intumescent layer is usually any material that releases a volatile substance, such as water, when heated during a time when the structure of the material will support cell formation. Intumescent graphite is highly preferred. Other compounds include various alkali metal silicates, such as sodium, potassium or lithium silicate, or alkaline earth metal silicates, such as calcium and magnesium silicates. Vermiculite is another suitable intumescent material.

Reflective layers usually consist of materials that reflect light and thus remove heat from the side of the system that is not exposed to fire. The layer may be thick, but is preferably thin, and is made from a high temperature resistant material. Suitable reflective materials typically reflect at least about 50%, or at least about 65%, and preferably at least about 80%, or at least about 90% of the sunlight falling on it. Examples include polyester film such as Mylar ^®, aluminum foil or sheet material and similar materials. High temperature resistant reflective surfaces typically include intensely reflective metals and alloys such as titanium, chromium, nickel, and the like: stainless steel and similar metals. Reflective surfaces are usually in sheet form and are present on the inner or outer side of the laminate or multilayer fire-retardant system.

Reinforcing materials have been described hereinabove and therefore will not be repeated. While they are usually used in fibrous form, either continuous or discrete, woven or non-woven, they can also be used in sheet form or in the form of a perforated sheet, strip and the like, and thus they form an individual or separate layer. Desirably, as noted above, the reinforcing material is typically used in fibrous form to reinforce the layer of the composite inorganic resin of the present invention. However, the various reinforcing materials mentioned above, in sheet form or in the form of a perforated sheet, or in any other form, such as fibers, can be used to reinforce any of the aforementioned layers, such as an insulating layer, an intumescent layer, a foam layer and even a reflective layer, to impart them strength and structural integrity.

The corrugated layer typically has numerous closed regions of gas, such as air, which act as a flame retardant medium inside any of the above layers except for the surface of the reflective layer. Thus, the above various insulating materials, intumescent materials, and reinforcing materials may have cavities inside them with air or other gas. Alternatively, the corrugated layer may be a layer of gas (eg, air) between the insulating layer.

Porous or foamed materials, such as foamed compositions that can be used in the present invention, are generally non-combustible and are useful for controlling heat transfer, fire protection, and other high temperature applications. The ability of the system of the present invention to withstand temperatures above 800 ° C allows it to be used in areas where organic-based foam materials and / or their derivatives cannot be used. Inorganic porous materials, such as foam compositions made of carbon, glass and ceramic materials, can withstand similar temperatures, but their high cost limits their use for large-scale thermal load management and / or cost-sensitive applications. The porous materials obtained according to the present invention can also be molded into the required complex as well as simple forms, and / or specifically molded using conventional processing equipment. Porous materials, such as foam, can be either structural (solid) or non-structural, obtained with or without a blowing agent. You can also prepare syntactic foam using the present invention and appropriate excipients such as microspheres, microspheres, and / or microcapsules.

Upon receipt of various types of barrier or multilayer composite systems, as a rule, one or more outer layers are made of a material that has good fire resistance and burn resistance, such as an inorganic polymer matrix made from alkali metal silicate, or one or more materials on an inorganic base, such as oxide-based cements, refractory materials, aluminum oxides and the like. Multilayer fire resistant systems may optionally comprise an intermediate layer sandwiched between one or more outer layers and one or more wireframe layers. The skeleton layer may be a substrate to be protected, such as a low melting point metal or combustible material, such as wood or other organic material. Alternatively, in aesthetic applications, an aesthetic exterior material such as wood or wood veneer surface, plastic surface, etc., for example, in a fire door, may contain an intermediate (e) or frame (e) layer (s), for example an insulating layer, an alkali metal silicate layer, to inhibit or prevent the ingress of flame or heat.

The various combinations of layers described above for producing various types of laminate materials can be attributed to hybrid laminate materials or hybrid systems that can be made by bonding, by laminating, etc., a flame-retardant inorganic thin layer or laminate with an organic composite frame. The flame retardant composite material functions as a fire barrier, an oxygen barrier, and to a lesser extent isolation. Unlike typical passive insulation, a flame retardant composite material functions not only as an insulation that prevents the thermal decomposition of organic resin. Instead, the flame retardant inorganic resin acts as a barrier to flame and oxygen.

Many systems or multilayer composites can be made using, in any order, one or more layers comprising an inorganic polymer matrix made from alkali metal silicate, for example, by reacting with a non-silicate structure-forming substance and reactive glass, water and optionally one or more secondary structure modifiers , and at least one layer from any of the following layers: an insulating layer, an intumescent layer, a foam layer, a reflective layer, reinforcing layer or corrugated layer; moreover, preferably, one or more of the above layers inside contain a reinforcing material, for example, as a rule, fiber, etc. The number of layers of the flame retardant laminate materials or systems of the present invention can vary greatly, for example, typically from about 2 to 10 layers, and typically or preferably from about 2 to 3, or up to about 4, or up to about 5 layers, or up to about 7 layers .

Resins of alkali metal silicates or their composite materials, for example, containing reinforcing materials, can be used in a variety of ways to create systems whose purpose is to increase fire resistance or create a fire barrier that can prevent the penetration of flames, the penetration of oxygen, and create thermal insulation (order of magnitude less than steel) and maintain strength during and after exposure to fire (the level of conservation depends on flame temperature and time). For example, an alkali metal silicate resin layer from 0.020 inches thick to thicker structural laminates can be used as a fire barrier over organic composite materials or wood to improve fire resistance of systems. These properties can be further optimized for more critical protection scenarios with the introduction of high-temperature insulation, which takes various forms. The combination of a resin layer of alkali metal silicates or its composite materials and insulation is aimed at overcoming the various disadvantages of the high-temperature insulating materials used individually. A thin, non-structural layer (0.020 ") can improve service life, reduce heat transfer and act as an oxygen-impervious barrier. These systems can then be used as passive fire protection for substrates such as wood, steel or composite materials. Repeated layers can be constructed resins of alkali metal silicate or its composite material and insulation in order to achieve better functioning of the fire system not only in terms of fire resistance, but also physical mechanical, thermal, and thermal properties that are important characteristics for most fire-fighting systems. The incorporation of reflective surfaces on the inner or outer layer of an alkali metal silicate resin or its composite material will further improve system performance by reducing radiative thermal conductivity. Using a thicker layer of alkaline silicate resin metal or composite materials that is capable of supporting the structure alone or with a rigid frame of it flammable insulating material, can allow it to function as a load-bearing structure, which is completely non-combustible. Rigid non-combustible insulation materials capable of performing the function of a frame in a sandwich-type building structure are not widespread, and insulation materials with better characteristics are expensive and difficult to use. Various foam materials offer a good insulating cage capable of good adhesion with alkali metal silicate resin facing sheets and having good performance.

Fire systems are developed on the basis of fire requirements provided by the external boundaries for the system, mechanical requirements, physical requirements, and depending on the market, cost. Some fire barriers may simply be a 0.020 inch thick alkali metal silicate resin or composite material layer to prevent flame penetration (alkali metal silicate resin / carbon laminate — 2 layers used to protect the gondola). Other systems can consist of many layers designed to insulate, prevent flame penetration and keep the cold side cold for a long time (VSV material), i.e. an alkali metal silicate resin layer having a reinforcing metal mesh and outer layers of fiberglass is used as a coating layer over a ceramic blanket to reduce heat transfer and give the system greater durability. In addition, the VSV multi-layer system in the fire door frames can be used to create a shell within which the intumescent material will expand, to reduce heat transfer, and to provide strength to withstand the flow test from the fire hose. The fire barrier operates by various mechanisms: eliminating the penetration of flames, preventing the penetration of oxygen due to combustion of the underlying combustible material and reducing the heat required for combustion. Fire-fighting systems can become very complex based on heat transfer, combustion of materials, preservation of strength during and after exposure to fire, material, physical and thermal properties of the system in environmental conditions.

The alkali metal silicate resin layer or a composite material based thereon is applicable in fire barriers either alone or as part of a system including insulating and / or reflective surfaces. A 90-minute wooden fire door uses a VSV system (i.e. a multi-layer veil / net / veil system) in combination with an intumescent material to protect the wood cold side of the panel for 90 minutes of exposure to fire according to ASTM E-119 and then to pass the test flow from a fire hose. The door frame fire barrier is only 5/8 "thick before exposure, representing the thinnest 90 minute fire frame currently on the market. Another fire system, which is a much simpler system, is a 2-layer alkaline metal resin composite / carbon reinforcing component used as fire protection in jet engine nacelles to prevent flame penetration. Varying properties, vibration resistance and chemical resistance are also required.

The uniqueness of composite materials from alkali metal silicate resins lies in the materials, incombustibility, low thermal conductivity, high temperature properties, low processing temperature and low cost. In combination, these properties provide a unique material that can be used in various fields. Competitive materials exist, but do not have the full range of properties offered by alkali metal silicate resin composites.

Layered materials or multilayer fire protection systems containing at least one layer made from the flame retardant inorganic resins of the present invention can be used to protect organic-based substrates, products from laminated materials, etc. from exposure to fire for a given period of time. Inorganic resin systems are unique in that they do not rely on insulating the organic laminate from heat. Instead, the resin functions as a flame / oxygen barrier, addressing different angles of the fire triangle. Acting as a flame / oxygen barrier, these flame-retardant inorganic layers prevent not the decomposition of organic material, but only its combustion. Thus, a hybrid laminate can be used to improve the performance of the organic laminate as long as attention is paid to the method by which the carcass material is isolated.

While various beneficial features and end-use options are set forth below, important multilayer, fire-resistant systems include alkali metal silicate resin composites per se, VSV systems and fire doors. The composite material itself is used in almost all fields, and it includes modified inorganic polymer matrices made of alkali metal silicate, one or more non-silicate structure-forming substances and / or reactive glass and, optionally, one or more secondary structural linking units, all these components are commonly referred to as alkali metal silicate resin. An important aspect is that the resin contains a reinforcing component, typically in the form of reinforcing fibers, for example carbon fibers. In order to achieve an appropriate thickness and structural integrity, two such layers of an alkali metal silicate resin composite material can be used, and they can simply be stacked on top of each other, be joined together or glued to each other, or attached in any way.

The VSV system typically contains a metal reinforcing element, such as a mesh, a perforated sheet, etc., and is used and built into the alkali metal silicate resin to form a composite material. A thin fiberglass insulating layer is used on either side of one or more layers of this composite material. This multilayer system finds use in certain areas, for example, in the interior of the ship's hull.

In an embodiment of a fire door, an alkali metal silicate resin composite material containing fibers is typically used with an intumescent layer, typically on both sides thereof, all of these components being placed inside a wood panel, etc., forming a wooden fire door. Depending on the degree of protection sought, additional layers of an inorganic alkali metal silicate resin composite material and an intumescent layer can be used.

The various laminates or multilayer systems of the present invention can be used in various fields, such as reinforced rocket shafts, ship decks, jet engine exhaust gas shields and aircraft carrier heat shields, fire barriers, hot gas filters, protective coatings, electrical panels and distribution cabinets (with or without electromagnetic shielding), engine covers, or in any areas in which protection against damage from flame and eploperedachi, corrosion resistance, reduced life cycle cost and weight reduction. In addition, this technology can be used to strengthen insulating inserts for aircraft brakes. This insulating material inside each piston thermally isolates the friction head from the hydraulic system. Compared to traditional resins, some of which decompose below 450 ° C, the matrix binder of the present invention has much higher thermal stability (up to temperatures above 1000 ° C), and in contrast to metals, the composite material of the present invention has excellent insulating characteristics. This protects the hydraulic system and can reduce weight and / or associated costs. Compared to ceramics, the composite material of the present invention is more rigid due to the presence of reinforcing fibers, but less expensive compared to ceramic matrix composites due to the materials and processes used.

The barrier systems of the present invention can also be used in areas where good thermal and physical stability is desirable, for example, in areas where ceramic composite materials are used. These areas will include aerospace, marine, cargo, construction and architecture applications ranging from simple applications requiring fire resistance and / or heat resistance to more complex fire resistant applications, including high temperature and long-term protection, thermal and fire protection for pipelines , cable boxes, power lines, gas and oil pipelines, fire and heat protection of structural steel columns, beams and beam trusses, bulkheads and other surfaces for boats, ships, planes, buses, funiculars, trams and the like. Thus, it is possible to achieve fire protection for 60 or 90 minutes or more at temperatures up to 1700 ° F, and this can be done with relatively small masses of structures.

In accordance with the concepts of the present invention, Table 1 serves as an illustration of the various types of barrier systems that can be used in the present invention.

The following table 1 is presented as an illustration of the areas of use of the present invention, but should not be construed as exhaustive or limiting the application of the invention:

Table 1 Example Application Structure (Composite material = composite, which is a reinforced inorganic resin) Inorganic Laminates Comments A fire wall or light barrier Inorganic composite Carbon Fiber / Alkali Metal Silicate Resin Thickness can range from 1 layer to many layers B thermal / fire barrier - light weight, low cost Inorganic composite / insulating material / composite Carbon Fiber or Fiberglass / Alkali Metal Silicate Resin The framework may be insulating materials, including a honeycomb structure C thermal / fire barrier, door design meets the 90-minute test Wood / inorganic composite / intumescent mat / inorganic composite / intumescent mat / inorganic composite / wood Stainless Steel Fiber / Alkali Metal Silicate Resin Layers can be optimized in terms of performance D thermal / fire barrier for maritime applications Intumescent coating / inorganic composite / 8 lbs. mineral blanket / bulkhead construction Fiberglass or stainless steel fiber / alkali metal silicate resin Provides fire and thermal barrier E fire barrier including air cavities corrugated inorganic composite Alkali Silicate Fiber / Resin The composite is molded as corrugated material F improved flame retardant organic composite Inorganic composite / organic composite / inorganic composite Alkali Silicate Fiber / Resin Adds fire resistance and improved strength to the organic composite. G material with high thermal and fire resistance Inorganic composite / inorganic foam / inorganic composite Alkali Silicate Fiber / Resin The foam material may be a glass, carbon and similar flame retardant foam system. H high-strength fire barrier Inorganic composite / mineral frame / inorganic composite Stainless Steel Fiber Composite / Alkali Metal Silicate Resin The mineral skeleton is a well-known fire-resistant skeleton, and the composite improves fire performance

Other examples of suitable laminate materials or systems include examples 1-8 of table 2, where the material of the type "composite material" is an inorganic polymer composite material containing an alkali metal silicate resin and a reinforcing material.

table 2 Etc. Layer Material Material type Advantage Comments one one FR / C Composite fire wall or light barrier; Thickness can range from 1 layer to many layers 2 one FR / C (or G) Composite thermal / fire barrier The frame may be any insulating material, including a honeycomb structure 2 Balsa Insulation (wood) light weight, low cost 3 FR / C (or G) Composite 3 one MDF Wood thermal / fire barrier FR / SS and Palusol layers can be optimized for any performance 2 FR / SS Composite frame 3 Palusol Intumescent mat thin 90 minute door four FR / SS Composite frame 5 Palusol Intumescent mat Intumescent mats can be of any type 6 FR / SS Composite 7 MDF Wood four one Coating Intumescent coating thermal / fire barrier The system is priced for the US Navy 2 FR / G (or SS) Composite superior performance 3 Blanket 8 pounds. mineral blanket twice the blanket four Steel Bulkhead Structure 5 one FR / any Corrugated material Air cavities improve thermal performance Any method for creating air cavities works - you can easily optimize 6 one FR / any Composite FyreRoc - fire barrier FyreRock Composite Improves Strength and Fire Resistance of Organic Laminates 2 RP Organic composite Improving the fire resistance of any organic composite 3 FR / any Composite 7 one FR / any Composite High level of thermal insulation and fire resistance Foamed materials can be glass, carbon, etc. With proper foam, it can be a fire system 2 Foam Inorganic foam Insulating qualities and fire resistance 3 FR / any Composite Performance 8 one FR / SS Composite Improved durability after fire on the mineral skeleton Mineral framework is a well-known mineral framework - FR / SS improves inherent fragility 2 Min frame Mineral skeleton 3 FR / SS Composite

Material Codes

FR = Inorganic polymer matrix derived from alkali metal silicate C = Carbon fiber G = Glass Any = Any fiber SS = Stainless steel fiber MDS Medium density wood RP = Reinforced plastic

Tables 1 and 2 demonstrate that many different types of layered materials or structures can exist, consisting of at least one inorganic polymer layer including alkali metal silicate material and other layers, for example at least one insulating layer, an intumescent layer, a foamed layer, a corrugated layer, a layer of reinforcing material and the like.

The resulting composite materials show dimensional stability up to a temperature of about 900 ° C and higher depending on the final formulation and the treatment chosen and have excellent flame, smoke and toxicity properties. A composite material made using the inorganic resin composition of the present invention has light weight and good thermal insulation characteristics. Various forms are relatively inexpensive to manufacture, primarily due to the low temperatures and pressures required to effect the curing of the composite material.

Inorganic resin compositions are useful as flame retardant binders, bulk molding materials, sheet forming compositions, adhesives, coatings, pure resin compositions, cellular materials such as foam compositions, or flame retardant composite materials. As composite materials, the inorganic resin composition can be formed into objects of a certain shape after curing. Alternatively, as a composite material, the composition is used to impregnate a fabric that can be combined with other similarly impregnated fabrics to form a pack of sheets, which, in turn, is then molded and cured to form a molded composite material or object, similar to the material in volume, but with an advantage reinforcement provided by the fabric. The compositions of the present invention are applicable in those applications where good heat and physical resistance are desired, for example, in those applications for which ceramic composite materials are used.

When using omnidirectional fiber, new flame-retardant inorganic resins have mechanical properties comparable to composite resins based on organic resins. Tissue-fiber composites using a resin-based system are somewhat more problematic due to the difficulty of penetrating fiber bundles. However, the FST characteristics of inorganic systems with an organic-based structural component are believed to provide some mitigation.

Thermal properties, consisting of thermal conductivity, thermal expansion, and specific heat, were evaluated for flame-retardant inorganic resin composite materials reinforced with glass, stainless steel, and carbon. The thermal characteristics evaluated by these methods showed consistent operational parameters for the new flame retardant inorganic composite materials at temperatures from room temperature to 800 ° C, which is not feasible in the case of systems based on organic resins.

Composite materials can also be laminated using standard laminating techniques such as inorganic high temperature adhesion or high strength organic adhesion depending on the desired system properties. In addition, hybrid composite materials can be made by attaching, by lamination, a flame retardant inorganic composite material or laminate to a frame of an organic laminate or composite material. A fire-resistant composite material or laminate functions as a fire barrier, an oxygen-impermeable barrier and, to a lesser extent, insulation. Unlike passive insulation, a flame retardant composite does not function primarily as an insulation that prevents decomposition of organic resin. Instead, a flame retardant inorganic resin composite material acts as a barrier to flame and oxygen. In addition, the flame retardant composite material increases the strength of the hybrid composite.

Composite materials made from flame-retardant inorganic resins can be used to protect composites and layered materials on an organic basis from exposure to fire for a fixed period of time. The inorganic resin composition used to create the composite material is unique in that it does not simply rely on insulating the organic composite material from heat. Instead, the inorganic resin composition functions as a flame / oxygen barrier, addressing various angles in the fire triangle. Acting as a flame / oxygen barrier, these flame-retardant inorganic layers prevent combustion, but not decomposition. Thus, it is possible to use a hybrid composite material to improve the performance of the organic composite material, while attention is paid to the method by which the frame material is insulated.

Fire-resistant composite material alone or with frame materials can be used, for example, with wood panels for the manufacture of fire doors. The fireproof composite material can be used alone as a barrier or it can be molded with air cavities, for example, corrugated material, a cellular structure or hollow spheres can be added to an inorganic resin composition to increase fire resistance, improve insulating properties or structural characteristics without adding carcass material. Moreover, fireproof composite materials can be used with single frames or multi-frame structures to improve a variety of properties. The flame-retardant composite material can be applied to any substrate or connected to any substrate, the fire resistance of which must be improved, for example, by additional lamination of other substrates that are not fire-resistant, to increase the operational characteristics of the overall composite material. An additional base can be added to the structure, such as, for example, but not limited to wire mesh, metal sieves, glass nets, etc. The invention can be applied to any design that serves as a fire barrier, although its use in fire doors is an example of an advantage. Since inorganic flame-retardant composite materials are designed to allow barriers such as doors to withstand flow from the hose and maintain the skeleton sheath without weight restrictions, the skeleton can now meet operational properties that were previously impossible without inorganic fire-resistant composite materials. The mass of fire-resistant composite material in comparison with its strength is important in the manufacture of fire barriers. As noted, thinner barriers that weigh less while meeting the 60- and 90-minute fire resistance limits will provide barriers for use in more architectural areas.

Layered materials or barrier systems of the present invention have been tested against two main types of methods. The first method is a flammability test, which is used to evaluate a portion of the combustible components of a fire triangle for a test material. Flammability testing is described in various protocols of ASTM (American Society for Testing Materials), NFPA (National Fire Protection Association), IMO (International Maritime Organization), ISO (International Organization for Standardization), UL (safety laboratory) and others. to measure the time before ignition, flame propagation, heat and smoke. These tests are used to characterize the material for FST operation. Organic composite materials that are modified to obtain good fire resistance will generally improve their fire resistance while impairing other properties of the system.

The second method exposes the material to an approximate temperature schedule that will actually occur in a fire. In this type of test, the material is subjected to a firing curve for a predetermined time, after which the material is evaluated based on how well it has withstood the impact. Two common firing curves are typically used: ASTM E-119 and UL-1709. ASTM E-119 is designed to follow the temperature profile of a building fire and is used in evaluating most products for building construction. The ASTM E-119 firing curve is designed to simulate a real fire in a building, and it is used with various destruction criteria to determine the resistance of a given part to exposure to fire. Based on this thickness, the wooden parts will withstand the E-119 fire exposure scenario for 20 or more minutes in certain cases. To improve fire resistance, for example, a tree can be placed between layers of fire-resistant insulation or a fire barrier / insulation can be used between two layers of wood. Time periods are measured after 30, 45, 60 and 90 minutes of exposure to a sample of a specific surface temperature. UL-1709 follows the fuel flame temperature profile and is used for aerospace and military products. In the case of an I-beam assessment, the criterion for destruction will be the complete destruction of the structure.

Figure 1 illustrates an example of a laminate that can be manufactured according to the present invention. As shown, the layout of the laminate 1 may be, for example, a door or a barrier. The laminate 1 is obtained from an intumescent material layer 2, each side of the intumescent layer being laminated with alkali metal silicate resin layers 3, and it has an outer layer 4, which may be wood or other materials necessary to obtain the desired architectural appearance. Further, as shown in FIG. 2, additional profiling can be added by attaching or gluing the molded metal face 5 and back 6 to the outer layer 4 of the laminate 1.

Figures 3 and 4 illustrate two conventional fire resistant arrangements for improving the fire resistance of wood. As shown in FIG. 3, the fire-resistant laminate 7 is laminated between two wooden parts 8 and 9. In FIG. 4, the fire-resistant laminate 7 is applied to the surface of the wood 10.

FIG. 5 illustrates a hybrid laminate 11, in which an organic composite frame 12 is attached to or coated with a flame retardant laminate 13. The frame 12 may be, for example, an epoxy or phenolic composite or laminate, while the flame retardant laminate 13 may be, for example, a nonwoven glass fiber mat that is impregnated with an alkali metal silicate resin. The mat may be a single layer or laminate material containing more than one layer, depending on the required characteristics or desired configurations.

6 and 7 illustrate yet another configuration of an embodiment of the concept of the present invention, in which a structure, such as an I-beam 15, has a sleeve of a flame-retardant laminate, such as a non-woven fiberglass mat impregnated with an alkali metal silicate resin of the present invention, placed on the beam and molded along the profile of the beam, to obtain a fire-resistant I-beam 17, shown in Fig.7.

To further understand the invention, a number of composite layered structures were made and their performance characteristics evaluated as flame retardant materials. The frames were made of fire-resistant inorganic resins, representing a material with a dual ability to function both as a barrier to fire and as a structural element after exposure to fire. The insulating performance of the new frame system is much better than that of steel (thermal conductivity 2.5 British thermal units inch per hour ft ² F compared to 325 British thermal units inch per hour foot ² F). In order to be sufficiently insulating, in accordance with the E-119 cold side test protocols, intumescent materials are added to the frame structures. The intumescent material used in the test panel designs functions as an insulator as well as a heat sink. The material expands during the fire test, leaving the temperature on the cold side below the ignition temperature of the wood. Then the layer of wood on the cold side can remain structural to withstand the flow test from the fire hose. The disadvantage of intumescent material is that with an increase in the duration of exposure to fire, its effectiveness as insulation decreases until the material on the cold side is destroyed. Then the tree on the cold side will no longer pass the test by flow from the fire hose.

The rated flame-retardant laminates consist of an inorganic resin (alkali metal silicate resin), which has been pre-impregnated with stainless steel mats, directly molded from 27 ° C to 66 ° C. The mats consisted of two layers, 0 ° and 90 ° stitched together in one layer. The porosity of the mats results in approximately 80% by volume of resin in the final product. The resulting laminate has a thickness of 0.102 cm and a density of 2.5 g / cm ³ (inorganic laminate ″ A ″). The additional flame-retardant laminate materials consisted of a flame-retardant inorganic resin impregnated in fiberglass, resulting in a thickness of 0.064 cm and a density of 1.90 g / cm ³ (inorganic laminate “B”), and a fire-resistant inorganic resin impregnated in a fiberglass mat , which resulted in a thickness of 0.089 cm and a density of 2.3 g / cm ³ (inorganic laminate ″ C ″).

The systems evaluated in this study essentially consisted of two layers of wood, in the middle of which a fire barrier was placed. The tested fire barriers were both single-component systems and sandwich systems. The fire barriers tested were varied to optimize fire performance for the overall system. Different designs had different levels of insulation and fire resistance of layered materials, so that the effect of these two variables on the characteristics of the system could be estimated. The intumescent material used was 0.318 cm thick with a degree of expansion of 4 to 1 during heating. All samples were approximately 4.45 cm thick. The wood used in the evaluation was a medium density fiberboard (MDF), although high density fiberboard (HDF) could also be used. The thickness of the wood ranged from 3/4 inch in thick section to 1/4 inch in thin section, where the door was machined to style. The total thickness of the door was 3/4 inches, with the frame allowing one inch to be machined 1/2 inch per side. The 90-minute door frame was approximately 1/4 inch thick. The evaluated samples were as follows:

The first furnace charge consisted of:

I. wood panel used as a control sample,

II. ″ sandwich ″ type specimen, which is a layer of wood / fire-resistant laminate ″ A ″ / layer of wood,

III. a sandwich type specimen of a tree layer / intumescent layer / tree layer and

IV. a sandwich type specimen of a wood layer / fireproof laminate ″ A ″ / intumescent layer / fireproof laminate ″ A ″ / wood layer.

The second furnace charge consisted of:

V. a sample representing a layer of wood / fire-resistant laminate ″ A ″ / intumescent layer / fire-resistant laminate ″ A ″ / wood layer,

VI. a sample representing a layer of wood / fireproof laminate ″ B ″ / intumescent layer / fireproof laminate ″ B ″ / wood layer,

VII. a sandwich type specimen, which is a wood layer / fireproof laminate ″ C ″ / intumescent layer / fireproof laminate ″ C ″ / intumescent layer / fireproof laminate ″ C ″ / wood layer.

The fire resistance test was carried out at the Southwest Research Institute on the test panels 61 cm × 61 cm. Using the initially identified annealing curve E-119, it was observed that the heat emitted by the burning wood was in excess of the original curve. In order to collect more usable data, the temperature was compared with the UL-1709 curve, which more closely corresponds to the observed behavior (Fig. 8). In the case of this study, a surface temperature of 232 ° C was used.

To control the internal temperature and the temperature of the cold side at many points on the test panel used thermocouples. The test was carried out on four panels per furnace company. The test procedure was performed until each panel in the test is destroyed. The destruction of the panel occurs at a time when the flame penetrates through the sample. The results are summarized in figures 9 and 10.

During the first test in the furnace, it was observed that the wood sample without the frame collapses in 25:45 minutes. Wood with a fire-resistant laminate skeleton collapses in 29:00 minutes, an intumescent skeleton collapses in 32:45 minutes, and a sandwich-type fireproof laminate / intumescent / fire-resistant laminate material breaks in 39:00 minutes.

The fire-resistant inorganic framework functions as a barrier to flame and vapor during exposure to fire and as a structural material after extinguishing a fire. As a structural component, the framework allows the wood to break down during the fire test, but still withstand the test by flow from the fire hose. The fire-resistant inorganic framework also holds the intumescent material in place during the later stages of the fire and reduces the rate of water vapor emission during the fire. Thus, the synergistic effects of the sandwich framework of the intumescent and fire-resistant inorganic laminate material give a significant advantage over any of these materials taken separately. Moreover, the intumescent material expands between the bounding layers of the inorganic laminate, and does not expand isotropically, as would be the case with an unlimited intumescent sheet.

The use of flame-retardant inorganic frameworks together with insulating material meets the E-119 test protocols for up to 90 minutes in areas of use that require maintaining strength after exposure to flame. The results for the samples observed in the second test in the furnace demonstrate the performance of the inorganic resin / fiberglass frame compared to the inorganic resin / stainless steel frame. The test demonstrates that the fiberglass laminate breaks down about 12 minutes earlier than the laminate containing a stainless steel mesh. It is believed that the low thermal properties of fiberglass / flame retardant laminate and the loss of strength with increasing temperature compared to samples reinforced with stainless steel are reasons for differences in performance. A sample with three layers of flame retardant laminate and two layers of intumescent material improves the fracture time by 50 minutes compared to flame retardant laminate / intumescent material / flame retardant laminate. The data show that 0.040 "thick flame retardant laminate can improve the time to failure for combustible wood. Insulating wood is not responsible for improving performance. Instead, it is believed that the reason for these results is a laminate that acts as an oxygen barrier and slows combustion The combination of flame-retardant laminate / intumescent / flame-retardant laminate in the framework gives a result that can be expected from the data obtained on one flame retardant laminate and one intumescent. It is believed that the improvement seen during the use of the intumescent framework is a function of its ability to isolate wood. Thus, the combination of the flame retardant laminate and the intumescent works as expected. An additional 20 minutes before destruction of the sample show a synergistic effect from the presence of repeated intumescent and fire-resistant layers in the frame.

A framework consisting of repeating layers of flame retardant laminate in combination with repeating layers of intumescent material with a thickness of 0.953 cm included in a treated panel of wood with a thickness of 4.45 cm can meet the 90-minute ASTM E-119 test. Fire-resistant laminates made from flame-retardant inorganic resins are unique because they function as a flame / oxygen barrier, addressing different angles of the fire triangle. Acting as a flame / oxygen barrier, these flame-retardant inorganic layers prevent not the destruction of organic material, but only its ignition. Since insulating the “cold side” of wood panels from heat is important in obtaining the fire resistance limit of ASTM E-119, the insulation functionality is increased by using an intumescent layer. In addition, the intumescent material extends between the bounding layers of the inorganic laminate, rather than as isotropically as would be the case with an unlimited intumescent sheet.

As a further example, a hybrid composite laminate was evaluated. The materials used consist of organic composite structures supplied by Electric Boat Corporation (EBC) and inorganic composite materials supplied by Goodrich Corporation. The inorganic polymer composite has been designed to meet MIL-STD-2031 in the areas of thermal regulation. The hybrid laminate of the flat panel consists of an organic resin composite material located between two layers of an inorganic resin composite material. A flammability test on an epoxy composite system was carried out using flame-retardant inorganic layered materials having different thicknesses, as will be discussed hereinafter.

In addition to the hybrid structures in the form of a flat panel, hybrid samples in the form of an I-beam were created and evaluated to approximate the functioning of a real frame that can be used on a submarine. I-beam hybrid samples were prepared by curing an inorganic resin composite material on an abrasive-treated surface of an I-beam of an organic resin composite material that is an epoxy or phenolic composite material. Both I-beams of an organic resin-based composite material were fabricated using pultrusion reinforced with twisted fiber. The inorganic composite material was made by impregnating a carbon fiber sock to position it on top of the beam. The sock is a stitched fabric that can be soaked and then put on the I-beam to close the surface of the I-beam. The thickness of the flame retardant inorganic laminate was approximately 0.07 cm. Amplifiers were inserted into the I-beam to provide adequate pressure on the inside of the I-beam during curing. The hybrid composite beam was then vacuum bag molded and autoclaved.

The first series of evaluated hybrid samples consisted of inorganic laminates in the form of a flat panel with different thicknesses, and they were evaluated for their ability to protect epoxy or phenolic composite laminates, such as those shown in FIG. The types of reinforcement used in this assessment were both fiberglass and carbon fiber impregnated with an inorganic resin. The test evaluated the effect of thickness and type of reinforcement on fire properties. The test protocol selected was cone calorimetry, ASTM 1354, which is applicable for determining time to ignition, heat release rates, peak heat release rates and smoke generation. This test is carried out when measuring heat flux of 75 and 100 kW / m ² .

The flammability test on a hybrid composite system in the form of a flat panel was carried out at different thicknesses of the carbon / epoxy or glass / epoxy composite material protected by a flame retardant inorganic resin. All of these samples have the same thickness of combustible material. The flammability test of the phenolic composite material was carried out only using a 2-layer composite layered material containing an inorganic resin and fiberglass. As shown in tables 3 and 4, the performance in all of these tests was very good.

Table 3 ASTM 1354 data for a heat flux of 75 kW / m ² System: Frame of epoxy laminate with facing sheets of inorganic laminate Material (construction of inorganic laminate) Time to ignition (seconds) Peak heat release rate (kW / m ² ) Average heat release rate (kW / m ² ) Total heat generation (MJ / m ² ) 1-Layer Carbon Fiber Mat 117 271 151 57 2-Layer Carbon Fiber Mat 166 244 155 62 4-ply carbon fiber mat 221 203 123 56 8-Layer Carbon Fiber Mat 306 186 110 63 1-layer fiberglass mat 136 266 157 65 2-layer fiberglass mat 137 230 145 55 4-layer fiberglass mat 232 229 130 67 8-layer fiberglass mat 302 195 81 61 Pure laminate epoxy / fiberglass 28 328 201 60

Table 4 ASTM 1354 data for a heat flux of 75 kW / m ² and 100 kW / m ² System: Frame made of phenolic laminate with 2 layers of carbon inorganic laminate Material (Heat Flow) (kW / m ² ) Time to ignition (seconds) Peak heat release rate (kW / m ² ) Average heat release rate (kW / m ² ) Total heat generation (MJ / m ² ) 2-Layer Carbon Laminate (75) 255.12 40.14 25.74 11.19 2-Layer Carbon Laminate (100) 73.38 64.86 35 14.07 Phenolic Composite Layered Material (75) 163 64 48 N / a Phenolic Composite Layered Material (100) 62 81 53 N / a

A second test protocol evaluated the fire resistance of a hybrid laminate using an I-beam. Beams include an epoxy or phenolic composite framework protected by an inorganic composite surface (FIGS. 6 and 7). The exact protocol used in this test was obtained to better assess the effect of the laminate on the durability of the hybrid beam. Using the E-119 firing curve and a test protocol similar to MIL-G-18015B, this test simulates a valid scenario of exposure to fire under load. During the fire test, an I-beam passed through the furnace, and 20 pounds of weight hung from the beam perpendicular to the length of the beam. During the test, the beam eventually burned out, which led to its destruction.

As can be seen from Fig. 11, the test results show a significant increase in heat resistance and time to structural failure for flame retardant inorganic reinforced hybrid beams. In addition, it was observed that there was no smoke during the test of the I-beam of flame retardant resin.

The characteristics of the flame retardant resin in all these tests gave the same results: non-combustible properties. This is because the resin structure does not act as a fuel source. It is the interaction of the combustible framework, as part of a hybrid laminate, with non-combustible facing sheets that provides useful properties. For the most part, laminated materials in the form of a flat panel and an I-beam worked as expected.

The observed behavior for the hybrid laminate begins with heat transfer through the inorganic composite to the combustible framework. This, in turn, will enable destruction to proceed. Since cladding sheets are not primarily intended to be insulating sheets, the organic laminate can begin to be exposed to destructive temperature in a very short time. Therefore, the main purpose of the facing sheets of the laminate is to prevent oxygen from entering the gases generated by decomposition, thereby preventing fire. In this way, flame retardant inorganic sheets eliminate one important parameter in the fire triangle: oxygen. Despite heat transfer through the fireproof laminate, the inorganic structure will retain some of its strength after exposure to fire.

Theoretically, the proper functioning of the hybrid laminate will increase the time required for the complete destruction of the organic laminate by eliminating oxygen. Decomposition will still occur; it will just take longer. The heat release data for the hybrid laminate has lower peak heat release rates. It is believed that this is due to the lack of oxygen necessary for combustion. If the theory believes that a flame-retardant inorganic resin acts as a barrier to fire and oxygen, the thickness of the flame-retardant laminate should have little effect on fire performance. Interestingly, the data do show a direct correlation between the thickness of the facing sheet in both epoxy and phenolic layered hybrid materials, and the time to ignition and the rates of heat release. An increase in the insulating properties resulting from an increase in the thickness of the layered material could be the reason for this trend; however, this does not seem likely. Another possible explanation could be the stiffening effect of the laminate. A fire-resistant sheet with a greater thickness will enable better bonding to the organic laminate, allowing the oxygen-impervious barrier to remain in place for a longer period.

To attach the facing sheets to all hybrid laminate materials in the form of flat sheets made with an epoxy frame, a high-temperature adhesive was used. For a phenolic skeleton hybrid laminate, glue is not used, but is instead bonded to the rough surface of the skeleton during the curing of the inorganic resin. The data from both of these adhesive methods follow the same trend, showing that binding has little effect on the performance of the hybrid. Hybrid laminates made with an epoxy framework showed an increase in ignition time ranging from a four-fold increase for one layer to a ten-fold increase for 8 layers. In addition, the facing sheets of the flame retardant inorganic resin, acting as a barrier to oxygen, led to a decrease in the peak heat release rate, as well as the speed at 5 minutes. The total heat generation for all tested samples was approximately the same. Hybrid layered materials with a phenolic skeleton contained facing sheets of 2 layers of carbon fiber and yielded comparable results with a hybrid layered material with an epoxy skeleton both in increasing the time before ignition and in reducing the rate of heat release.

The second phase of this assessment was to determine the protection effect of an I-beam made of epoxy resin / fiberglass and phenolic resin / fiberglass using a flame retardant inorganic laminate. The test method used in this assessment was a valid fire-scale test on a reduced scale using the ASTM E-119 annealing curve. The test was first carried out on an I-beam of epoxy resin / fiberglass, which was destroyed in 3 minutes on the annealing curve of E-119. The hybrid epoxy I-beam collapsed after 12.5 minutes on the annealing curve of the E-119 with a 20-pound weight suspended on the I-beam. The phenolic I-beam collapsed after 9 minutes compared to 19 minutes for an I-beam coated with a hybrid laminate. Theoretically, the laminate should prevent the supply of oxygen for combustion and, thus, it increases the time to failure for a hybrid I-beam. The improvement in time to failure for I-beams with a flame retardant inorganic resin protective layer indicates that a thin layer of 0.03 inches can provide a significant improvement in fire performance. Similar to the mode of destruction of flat panels, I-beams, ultimately, are destroyed due to the destructive action of heat.

Other embodiments of the present invention are shown in FIG. As shown in the upper middle part of FIG. 12, the alkali metal silicate resin can be reinforced with any type of material, for example, glass reinforcing material or carbon reinforcing material or steel reinforcing material, to obtain an alkali metal silicate reinforced composite material. The composite material can be used in the form in which it is obtained to obtain a fire structural component, or applied to various substrates, for example, a composite material in the form of an organic resin, wood, steel, etc., to obtain a structural component. Alternatively, an insulating system can be obtained from a composite material of alkali metal silicate by adding various types of insulation to it, for example, ceramic, mineral and the like. Alternatively, an intumescent system can be obtained by adding different types of intumescent material, for example, alkali metal silicate, exfoliating graphite, vermiculite, etc., to an alkali metal silicate composite. Similarly, different types of inorganic foam materials such as glass and carbon can be added to the alkali metal silicate composite to form foam systems. From these systems, as well as other systems that are not shown, it is possible to obtain various types of structures, for example, a structure such as a simple ″ sandwich ″, a structure such as a multilayer ″ sandwich ”, etc., obtaining from this other systems that are then applied to the substrate getting a fire structural system.

The substrate to be protected, as a rule, can be any type of material, which is often aesthetically pleasing, but usually has a low flash point or flash point. Typical substrates include wood, for example, numerous types of hardwood, such as maple, oak, ash, etc., or softwood, for example various types of pine, etc., as well as glued plywood, laminated wood, and so on. Other substrates include organic resins, which typically encompass numerous types of polymers such as polyesters, polyethers, polyolefins, polyvinyl chloride, epoxides, nylons, phenolic resins and the like. Other substrates include metals with a low melting point, such as aluminum, brass, bronze, and even various types of steel. Two or more alkali metal silicate composite materials may be adjacent to each other or separated by another layer and the like.

As can be understood from the present invention, fire-resistant and / or fire-resistant laminated materials or composite materials can be made in various forms from various materials. The alkali metal silicate fire-resistant resins of the present invention are flexible enough to be used in various forms, regardless of whether they are structural objects or combinations that provide improved fire safety in combination with an aesthetic appearance by using, for example, wood laminated plastic.

According to another embodiment of the present invention, the various multilayer fire protection systems described above can be secured together using at least one fastening means and the like. Typical fasteners include a bolt, bracket, rivet, wire, glue, magnet, end groove, screw, nail, or a combination thereof.

The previous embodiments of the present invention have been presented for the purpose of illustration and description. These options for description and implementation in practice are not intended to be exhaustive or to limit the invention to the described exact form and it is obvious that numerous modifications and changes are possible in light of the above description. These embodiments have been selected to better explain the principles of the invention and its practical use, thereby enabling those skilled in the art to better use the invention in its various embodiments and with various modifications that are suitable for the particular intended application. It is implied that the invention is defined by the following claims.

While the best mode and preferred embodiments have been formulated in accordance with patent law, the scope of the invention is not limited to this, but rather to the scope of the attached claims.

Claims (36)

1. A multilayer barrier system, including: at least one layer of an inorganic resin composition containing the reaction product of an alkali metal silicate and / or precursors of an alkali metal silicate, reactive acid glass, water, optionally one or more acid oxoanion compounds and, optionally, a clay and / or oxide filler; and at least one layer of additional material, including insulating material, intumescent material, foam material, reflective material, corrugated material, wherein any of the above materials contains a gas volume, or any combination thereof. 2. The multilayer barrier system according to claim 1, where the specified composition of the inorganic resin includes non-clay filler materials, including reinforcing fibers, spheres or particles, and where these spheres include microspheres, macrospheres or hollow spheres, and the spheres include glass, ceramic, metal, mineral , organic or inorganic materials. 3. The multilayer barrier system of claim 2, wherein said inorganic resin composition comprises a reinforcing fiber including nickel fiber, fiberglass, carbon fiber, graphite fiber, mineral fiber, oxidized carbon fiber, oxidized graphite fiber, oxidized polyacrylonitrile fiber, steel fiber, metal fiber fiber coated metal carbon fiber coated metal fiberglass coated metal graphite coated metal coated ceramic coated nickel graphite fiber, nickel coated carbon fiber, nickel coated glass fiber, quartz fiber, ceramic fiber, silicon carbide fiber, stainless steel fiber, titanium fiber, nickel alloy fiber, brass coated steel fiber, polymer fiber, polymer coated carbon fiber, polymer-coated graphite fiber, polymer-coated glass fiber, ceramic-coated carbon fiber, ceramic-coated graphite fiber, ceramic-coated glass fiber, aramid window, basalt fiber resistant to alkali glass fibers, E-glass fibers, S-glass fibers, basalt fiber, polyethylene fiber, SiC fiber or BN fibers or combinations thereof. 4. The multilayer barrier system according to claim 3, wherein said reinforcing fibers include graphite fiber, E-glass fiber, S-glass fiber, basalt fiber, stainless steel fiber, titanium fiber, nickel alloy fiber, aramid fiber, oxidized polyacrylonitrile fiber, polyethylene fiber, SiC fiber or BN fiber, or combinations thereof. 5. The multilayer barrier system according to claim 1, wherein said alkali metal silicate comprises potassium silicate solution, sodium silicate solution, crystalline sodium silicate, crystalline potassium silicate, amorphous sodium silicate or amorphous potassium silicate, or mixtures thereof, said reactive acid glass including compound of the formula

where Σr _k = 1 k = 1 where n represents the number of desired glass components, M represents at least one glass-forming component, such as boron, silicon, phosphorus, sulfur, germanium, arsenic, antimony, aluminum, vanadium, and at least one glass modifier that works like a flux, such as lithium, sodium , potassium, rubidium and cesium, and optionally additional structure modifiers such as vanadium, aluminum, tin, titanium, chromium, manganese, iron, cobalt, nickel, copper, mercury, zinc, thulium, lead, zirconium, lanthanum, cerium , praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and terbium, actinium, thorium, uranium, yttrium, gallium, magnesium, calcium, strontium, barium, tin, bismuth and cadmium, E represents oxygen, chalcogenides and / or halogens, such as sulfur, selenium, tellurium and fluorine, p represents the valency of cation M, for example 5 for phosphorus, which is usually depicted as P5 ⁺ or P (V), q represents the valency of anion E, for example 2 for oxygen, which is usually depicted as O ^2- , q ′ represents the number of cations M contained in the structural unit, equal to q or q / 2, which is the smallest integer whenever p and q are even numbers, for example 2 for phosphorus in P ₂ O ₅ or 1 for silicon in SiO ₂ p ′ represents the number of E anions contained in a structural unit equal to p or p / 2, which is the smallest integer whenever p and q are even numbers, for example 5 for phosphorus in P ₂ O ₅ or 2 for silicon in SiO ₂ r represents the molar fraction of each individual unit of the structure in the component of reactive acid glass, and said acid oxoanionic compound includes boric acid, phosphoric acid, sulfuric acid, monosubstituted sodium phosphate, and disubstituted sodium phosphate - disodium phosphate, disubstituted potassium phosphate - dipotassium phosphate, monoze ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphate salts of metals and / or nonmetals or compounds including borates, sulfates, aluminates, vanadates or germanate Or combinations thereof. 6. The multilayer barrier system according to claim 5, where the specified filler contains at least one oxide, including oxide of boron, aluminum, silicon, zinc, gallium, titanium, zirconium, manganese, iron, molybdenum, tungsten, bismuth, lead, lanthanum, cerium, neodymium, yttrium, calcium, magnesium or barium, mica, vermiculite and is present in an amount of from 0.0 wt.% or about 0.01 wt.% to about 20 wt.%, based on the total weight of the composition, and wherein said clay filler comprises kaolin, calcined kaolin and / or metakaolin and is present in amounts from 0.0 wt.% or about 0.1 wt.% to about 20 wt.%, based on the total weight of the composition. 7. The multilayer barrier system according to claim 5, where the specified resin composition contains the product of the interaction of the following components: from about 30 to 85 wt.%, At least one of the specified alkali metal silicate; from about 0.01 to 60 wt.%, at least one of the specified reactive acid glass; from about 0 or 0.01 to 20 wt.%, at least one of the specified acid oxoanionic compounds; from 0 or from about 0.1 to 20 wt.%, at least one specified clay filler; from 0 or from about 0.01 to 20 wt.%, at least one of the specified oxide and from about 15 to 60 wt.% water. 8. The multilayer barrier system according to claim 7, where the specified resin composition is obtained by curing the resin at a temperature in the range from about 15 to 1000 ° C, external pressure from ambient pressure to about 20,000 psi. inch and, optionally, under vacuum from about ambient pressure to about 10 ^-3 Torr. 9. The multilayer barrier system according to claim 1, comprising at least one layer of said inorganic resin composition, at least one layer of insulating material. 10. The multilayer barrier system according to claim 5, comprising at least one layer of said inorganic resin composition and at least one layer of insulating material, said layer comprising a silicate compound; aluminum oxide compound; aluminum silicate compound; ceramic material; metal oxide containing silica, silicate, alumina or aluminate; or refractory material, or a combination thereof. 11. The multilayer barrier system according to claim 3, comprising at least one layer of said inorganic resin composition, and at least one layer of insulating material comprising a silicate compound; aluminum oxide compound; aluminum silicate compound; ceramic material; metal oxide containing silica, silicate, alumina or aluminate; or refractory material, or a combination thereof. 12. The multilayer barrier system according to claim 7, comprising at least one layer of said inorganic resin composition and said at least one layer of insulating material comprising a silicate compound; aluminum oxide compound; aluminum silicate compound; ceramic material; metal oxide containing silica, silicate, alumina or aluminate; or refractory material, or a combination thereof. 13. The multilayer barrier system according to claim 9, comprising at least one layer of intumescent material. 14. The multilayer barrier system of claim 10, comprising at least one layer of intumescent material. 15. The multilayer barrier system according to claim 11, comprising at least one layer of intumescent material, said layer comprising exfoliating graphite, alkaline earth metal silicate, vermiculite, or a combination thereof. 16. The multilayer barrier system of claim 12, comprising at least one layer of intumescent material, said layer of intumescent material comprising exfoliating graphite, alkaline earth metal silicate, vermiculite, or a combination thereof. 17. The multilayer barrier system according to claim 1, comprising the specified at least one layer of the specified composition of the inorganic resin, and at least one layer of intumescent material. 18. The multilayer barrier system according to claim 5, comprising said at least one layer of said inorganic resin composition, and at least one layer of intumescent material. 19. The multilayer barrier system according to claim 4, comprising said at least one layer of said inorganic resin composition and at least one layer of intumescent material, said layer comprising exfoliating graphite, alkaline earth metal silicate, vermiculite or their combination. 20. The multilayer barrier system according to claim 7, comprising said at least one layer of said inorganic resin composition and at least one layer of intumescent material, said layer comprising exfoliating graphite, alkaline earth metal silicate, vermiculite or their combination. 21. The multilayer barrier system according to 17, where the specified system is a fire door, comprising at least one outer layer of wood. 22. The multilayer barrier system of claim 18, wherein said system is a fire door comprising at least one outer layer of wood, at least one layer of intumescent material, and at least two of said layers of inorganic resin composition. 23. The multilayer barrier system according to claim 19, wherein said system is a fire door comprising at least one outer layer of wood, said system comprising at least two layers of intumescent material and at least three layers an inorganic resin composition, wherein at least one said layer of the inorganic resin composition comprises a steel reinforcing mat. 24. The multilayer barrier system of claim 20, wherein said system is a fire door comprising at least one outer layer of wood, said system comprising at least two layers of intumescent material, at least three layers of the composition inorganic resin and at least one specified layer of the composition of the inorganic resin contains a steel reinforcing mat. 25. A multilayer barrier system, including: at least two layers of an inorganic resin composition containing the reaction product of an alkali metal silicate and / or alkali metal silicate precursors, one or more acid oxoanion compounds, water, optionally at least one compound containing at least one polyvalent a cation, and optionally a clay and / or oxide filler; and combinations thereof; at least one layer of an inorganic resin composition comprising a reinforcing compound; and at least one layer of any optional material, including insulating material, intumescent material, foam material, reflective material, corrugated material, any of the above materials containing a gas volume or a combination thereof. 26. The multilayer barrier system of claim 25, wherein said reinforcing compound of said inorganic resin composition is a fiber or a plurality of fibers of various types, a sheet, a lattice or a mesh, or a combination thereof. 27. The multilayer barrier system of claim 26, wherein the reinforcing fiber includes nickel fiber, glass fiber, carbon fiber, graphite fiber, mineral fiber, oxidized carbon fiber, oxidized graphite fiber, oxidized polyacrylonitrile fiber, steel fiber, metal fiber coated with carbon fiber metal coated glass fiber metal coated graphite fiber metal coated ceramic fiber nickel coated graphite fiber nickel coated carbon Nickel plated fiberglass, quartz fiber, ceramic fiber, silicon carbide fiber, stainless steel fiber, titanium fiber, nickel alloy fiber, brass coated steel fiber, polymer fiber, polymer coated carbon fiber, polymer coated graphite fiber, coated polymer fiberglass, ceramic coated carbon fiber, ceramic coated graphite fiber, ceramic coated glass fiber, aramid fiber, basalt fiber, crack resistant and glass fibers, E-glass fibers, S-glass fibers, basalt fiber, polyethylene fiber, SiC fiber or BN fibers or combinations thereof. 28. The multilayer barrier system according to item 27, where the specified alkali metal silicate includes a solution of potassium silicate, a solution of sodium silicate, crystalline sodium silicate, crystalline potassium silicate, amorphous sodium silicate or amorphous potassium silicate, and mixtures thereof, where the specified acid oxoanionic compound includes boric acid, phosphoric acid, sulfuric acid, monosubstituted sodium phosphate, disubstituted sodium phosphate, disubstituted potassium phosphate, monosubstituted potassium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphate salts of metals and / or non-metals or compounds sulfates, aluminates, vanadates or germanates, or combinations thereof. 29. The multilayer barrier system of claim 28, wherein said fibers include graphite fiber, E-glass fiber, S-glass fiber, basalt fiber, stainless steel fiber, titanium fiber, nickel alloy fiber, aramid fiber, polyethylene fiber, oxidized polyacrylonitrile fiber , SiC fiber, BN fiber, or combinations thereof, and said cation is an alkaline earth metal or zinc cation. 30. The multilayer barrier system according to clause 29, where the specified composition of the inorganic resin includes the product of the interaction of the following components: from about 30 to 85 wt.%, at least one of the specified alkali metal silicate; from about 0.01 to 20 wt.%, at least one of the specified acid oxoanionic compounds; from 0 or from about 0.1 to 20 wt.%, at least one specified clay filler; from 0 or from about 0.01 to 20 wt.%, at least one of the specified oxide and from about 15 to 60 wt.% water. 31. The multilayer barrier system according to clause 29, where the specified composition of the inorganic resin contains the product of the interaction of the following components: from about 30 to 85 wt.%, at least one of the specified alkali metal silicate; from about 0.01 to 20 wt.%, at least one of the specified connection multivalent cation; from about 0.01 to 20 wt.%, at least one of the specified acid oxoanionic compounds; from 0 or from about 0.1 to 20 wt.%, at least one specified clay filler; from 0 or from about 0.01 to 20 wt.%, at least one of the specified oxide and from about 15 to 60 wt.% water. 32. The multilayer barrier system according A.25, where at least two of these layers of the composition of the inorganic resin are located adjacent to each other; and including at least one of these optional layers. 33. The multilayer barrier system according to claim 28, wherein at least two of said inorganic resin composition layers are adjacent to each other; and including at least one of these optional layers. 34. The multilayer barrier system according to clause 30, where at least two of these layers of the composition of the inorganic resin are adjacent to each other; and comprising at least two of these optional layers. 35. The multilayer barrier system according to claim 1 or 25, comprising at least two layers bonded together by at least one fastener. 36. The multilayer barrier system according to clause 35, where the specified fastener includes a bolt, bracket, rivet, wire, glue, magnet, end groove, screw or nail, or a combination thereof.

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