MXPA99007923A - Polymer composites and methods for making and using same - Google Patents

Abstract

Composites which include a polymer having natural free volume therein and an inorganic or organic material disposed in the natural free volume of the polymer are disclosed. In addition, methods for making a composite are described. A polymer having free volume therein is provided. The free volume is evacuated, and inorganic or organic molecules are infused into the evacuated free volume of the polymer. The inorganic or organic molecules can then be polymerized under conditions effective to cause the polymerized inorganic or organic molecules to assemble into macromolecular networks. Alternatively, where the polymer contains a functionality, the inorganic or organic molecules can be treated under conditions effective to cause the inorganic or organic molecules to interact with the polymer's functionality. Use of the disclosed composites as photoradiation shields and filters, electromagnetic radiation shields and filters, antistatic layers, heterogeneous catalysts, conducting electrodes, materials having flame and heat retardant properties, components in the construction of electrolytic cells, fuel cells, and optoelectronic devices, and antifouling coatings is also described. Oxyhalopolymer composites which include an oxyhalopolymer having free volume therein and an inorganic or organic material disposed in the free volume of the oxyhalopolymer are also disclosed. Also described is a surface-oxyhalogenated non-halopolymer composite. The composite includes a surface-oxyhalogenated non-halopolymer having free volume therein and an inorganic or organic material disposed in the free volume of the surface-oxyhalogenated non-halopolymer. Methods for making and using these oxyhalopolymer composites and surface-oxyhalogenated non-halopolymer composites are also described.

Description

POLYMER COMPOSITE MATERIALS AND METHODS TO MAKE AND USE THEMSELVES The present application claims the benefit of the Provisional Patent Application of E.U.A. Series No. 60 / 039,258, filed on February 26, 1997, Patent Application of E.U.A. Series No. 08 / 833,290, filed April 4, 1997, Patent Application of E.U.A. Series No. 08 / 955,901, filed on October 22, 1997 and Patent Application of E.U.A. Series No. 08 / 997,012, filed on December 23, 1997. Each of the previously identified applications is incorporated herein by reference.

FIELD OF THE INVENTION The present invention relates generally to composite materials and, more particularly, to polymer compositions containing inorganic or organic materials disposed in the free volume of the polymer and to oxyhalopolymer and oxyhalogenated compounds on the surface of non-halopolymer, and to methods for making them and using them.

BACKGROUND OF THE INVENTION Hybrid Materials Inorganic-organic materials have been used with varying degrees of success for a variety of applications. In some of these materials, the organic polymers are blended with inorganic fillers to improve certain properties of those polymers or to reduce the cost of the polymer compositions by replacing cheaper inorganic materials with expensive organic materials. Typically, inorganic fillers are either particulate or fibrous and are derived from inexpensive materials, such as minerals and natural glass. For example, the patent of E.U.A. 5,536,583 to Roberts et al. ("Roberts") discloses methods for mixing inorganic ceramic powders into polyethersulfones, polyether ketones and polyether ether ketones and methods for including metal, oxide and carbide nitrides in fluoropolymer resins to produce corrosion inhibitor coatings as well as coatings that have improved abrasion resistance and / or improved bonding characteristics. The patent of E.U.A. No. 5,492,769 to Pryor et al. ("Pryor") discloses methods for embedding metal or ceramic materials into organic polymeric materials to increase the abrasion resistance of the polymer. The patent of E.U.A. No. 5,478,878 to Nagaoka et al. ("Nagaoka") discloses a thermoplastic blend of an organic polymer and inorganic metallic fillers, which improve the polymer's discoloration resistance after exposure to ambient light sources. Each of the above inorganic-organic materials was made either by (1) fusing and then mixing the inorganic and organic phases into a homogeneous mixture, which was then cured, or dried, or (2) dissolving the polymer and inorganic material together in a solvent where both materials were miscible, mixing to produce a homogeneous solution, and then evaporating the solvent to extract the hybrid material. The resulting inorganic-organic hybrid materials are essentially macromolecular mixtures, which have separate inorganic and organic domains, which vary in size from nanometers to tenths of microns. All of the above composites are manufactured using inorganic materials, typically naturally occurring minerals, which are thermodynamically stable metallic forms, such as metal oxides, metal nitrides and zero valent metals. These inorganic-organic hybrid materials present a number of disadvantages, which limit their usefulness. For example, the size of the domain that the inorganic materials assume within the hybrid depends on the particle size of the particulate inorganic material or the fiber used to make the hybrid. Furthermore, the homogeneity of the inorganic-organic hybrid material greatly depends either on the solubility of the inorganic material in the polymer melt or on the solubility of the inorganic material in the solvent used to solubilize the polymeric material. further, the properties and molecular structures of these hybrids depend enormously on the methods used to extrude, strain or dry the solid hybrid material of the melted or solubilized mixtures, which give rise to important, undesirable batch-to-batch regional variations, and frequently uncontrollable The inorganic-organic hybrid materials have also been prepared by dispersing powdered or particulate forms of inorganic materials within various polymer matrices. For example, the patent of E.U.A. No. 5,500,759 issued to Coleman ("Coleman") describes electrochromic materials made by dispersing electrically conductive metal particles to polymeric matrices; the patent of E.U.A. No. 5,468,498 issued to Orrison et al. ("Morrison") discloses aqueous base mixtures of colloidal vanadium oxide and dispersed sulfonated polymer, which are useful for producing polymeric antistatic coatings; patent of E.U.A. No. 5,334,292 issued to Rajeshwar et al. ("Rajeshwar") discloses conducting polymeric films containing undispersed inorganic catalyst particles; and patent of E.U.A. No. 5,548,125 issued to Sandbank ("Sandbank") discloses methods for melt forming or thermoforming flexible polymer gloves containing particulate tungsten, which make gloves useful for protecting against X-ray radiation. Although inorganic hybrid materials -organics are homogeneously mixed, they contain separate inorganic and organic phases on a macromolecular scale. These separate phases often give rise to migration of the inorganic material into and / or leaching out of the polymer matrix. In addition, the inorganic phases of these inorganic-organic hybrid materials can be separated from the polymer matrix through simple mechanical processes or through solvent extraction of the polymer. Consequently, after exposure to certain temperatures or solvents, the inorganic phases of these hybrids can migrate and dissipate out of or accumulate in various regions within the polymer matrix, reducing their useful life. Due to the problems associated with the migration and leaching of the inorganic phase into inorganic-organic hybrids, hybrid materials containing inorganic phases have been developed having a higher solubility. These materials are based on physically trapping large interpenetrating macromolecular networks of inorganic materials in the polymer chains of the organic material. For example, the patent of E.U.A. No. 5,412,016 issued to Sharp ("Sharp") discloses inorganic-organic, polymeric interpenetrating network compositions, which are made by mixing a hydrolysable precursor of an inorganic Si, Ti or Zr gel with an organic polymer and an organic carboxylic acid to form a homogeneous solution. The solution is then hydrolyzed, and the resultant hybrid materials are used to impart added strength to conventional organic polymers as well as to increase their stabilities and abrasion resistance. The patent of E.U.A. No. 5,380,584 issued to Anderson et al. ("Anderson") discloses an image forming element by electro-stetography, which contains an electrically conductive layer made of a colloidal gel of vanadium pentoxide dispersed in a polymeric binder. The patent of E.U.A. No. 5,190,698 issued to Coltrain et al. ("Coltrain I") discloses methods for making polymer / inorganic oxide composite materials by combining a polymer derived from a vinyl carboxylic acid with a metal oxide in a solvent solution, by casting or coating the solution resulting and curing the resulting sample to form a composite material of the polymer and the metal oxide. These composite materials are said to be useful for forming transparent coatings or films having a high optical density, abrasion resistance or antistatic properties. The patent of E.U.A. No. 5,115,023 issued to Basil et al. ("Basil") discloses organic hybrid siloxane polymers, which are made through polymerization of hydrolytic condensation of organoalkyloxysilanes in the presence of film forming polymers. The method is similar to that described by Sharp and, similarly, is used to improve the mechanical strength and stability of the polymer, while maintaining its flexibility and film-forming properties. The patent of E.U.A. No. 5,010,128 issued to Coltrain et al. ("Coltrain II") discloses methods for mixing metal oxides with etheric polyphosphazenes to increase the abrasion resistance and antistatic properties of polyphosphazene films. These methods, like those of Coltrain I, employ inorganic metal precursors, which contain hydrolysable leaving groups. In each of the above, the inorganic-organic interpenetrating network compositions are obtained, (1) by adding hydrolysable metals (or hydrolyzed metal gels) either in a polymer melt bath or a solvent containing a dissolved polymer; (2) adding a hydrolyzing agent or adjusting the pH of the solution to effect hydrolysis; (3) mixing; and (4) healing. However, the described methods have several limitations. For example, they are limited to incorporating interpenetrating metal networks into polymers, which have similar solubilities as precursors of hydrolysable metal or the hydrolyzed metal. In addition, since the method involves first mixing the inorganic hydrolysable metal precursors or the hydrolyzed metal with the organic polymer and then curing the mixture, curing the inorganic phase and the organic phase necessarily occurs immediately. Since both inorganic and organic materials are in intimate contact during the curing process, the organic phase of the resulting hybrid has different physical characteristics from those of the same polymer cured in the absence of an inorganic phase. This makes it difficult, and in many cases, makes it difficult to predict the concentration of inorganic material necessary to preserve the desired properties of the starting organic polymer material or to predict the properties of the resulting hybrid. Typically, the crystallinity and / or free volume in the hybrid materials are significantly different from the starting organic polymer materials cured in the absence of the inorganic phase. The methods also have limited utility, as they provide no control over the spatial distribution of the inorganic and organic phases within the hybrid of inorganic-organic interpenetration network. For example, it is difficult, and in many, impossible to control which phase dominates the surface of the bulk material or the surface of the free volume within the bulk material. This variability can cause quality control problems as well as the utility of hybrid materials with respect to volume versus surface properties. Alternatively, it has been shown that inorganic and organic molecules can be impregnated into solid matrices using supercritical fluids. WO 94/18264 issued to Perman et al. Describes the use of supercritical fluids to impregnate a variety of specific additives into polymer substrates by simultaneously contacting the polymer substrate with the impregnation additive and a carrier liquid, such as water, in the presence of a supercritical fluid. The described method requires that the polymeric material be simultaneously exposed to an impregnation additive and a carrier liquid, and, then, these three components are exposed to a supercritical fluid in a high pressure vessel for a sufficient time for the polymeric material to be inflate, so that the carrier liquid and the impregnation additive can penetrate the swollen polymeric material. In Clarke et al., J. Am. Chem. Soc, 116: 8621 (1994), the supercritical fluid is used to impregnate polyethylene with CpMn (CO) 3, using supercritical C02, which acts both to solvate the CpMn (CO) 3 as to inflate the polyethylene, thus allowing the flow of CpMn (CO) 3 to the space created in the swollen polymer and in the free volume of the polymeric material. Watkins et al., Macromolecules, 28: 4067 (1995) describe methods for polymerizing styrene in supercritical C02-poly (chlorotrifluoroethylene) swelling ("PCTFE"). The methods for impregnating polymeric materials with additives using supercritical fluids present a number of important disadvantages. First, the method requires the use of a high pressure apparatus. Second, the method requires that the supercritical fluid or other suitable carrier solvent be available to solvate the additive that will be impregnated into the polymer matrix. Third, the method requires that the polymeric material be greatly swollen to allow the additive to penetrate and, thus, impregnate the polymeric material. This swelling results in large changes in the surface of the host polymer and in the overall morphology, and also results in a lack of control of the composition of the final hybrid material. Finally, this method does not allow any control on the surface properties resulting from the hybrid materials. Together, these changes and the lack of control leads to a variety of physical and chemical changes in the host polymer, including change in properties such as flexibility, crystallinity, and thermal characteristics. Finally, in most cases where supercritical methods are used to impregnate additives in polymeric materials, the impregnated additive can easily be diffused out of the polymeric material by exposing the polymeric material to supercritical fluid conditions or, in some cases, to various solvents. . For these reasons and other reasons, there is a need for organic-organic polymer composite materials and methods for preparing these inorganic-organic polymer composite materials that do not exhibit the limitations described above, as well as methods for preparing these composite materials that allow control in surface properties (eg, wettability, reactivity, adhesion and physical and chemical resistance). The present invention is directed to satisfy this need.

Anti-lncrustation Coatings Man-made structures, such as hydro-aviation helmets, buoys, drilling platforms, oil production rigs, bridges, pillars, closures and pipes, which are submerged in or intermittently in contact with the water, are prone to form encrustation by aquatic and marine organisms, such as green algae and brown, barnacles, mussels and the like. Said structures are commonly made of metal, but may also include other materials, such as concrete, wood and plastic. In hydroaviation helmets, scale formation increases frictional resistance to movement through water, with the consequence of reduced speeds and increased fuel costs. In static structures, such as drilling rig poles, oil production rigs, bridges and pillars, the resistance of coarse layers to the formation of scaling to waves and currents can cause unpredictable and potentially dangerous stresses in the structure. In addition, the formation of scale also makes it difficult to inspect the structure to find defects, such as stress cracking and corrosion. In pipes, such as cooling water inlets and outlets, fouling formation reduces the effective cross-sectional area of the pipeline, which results in reduced flow rates. The most commercially successful method for inhibiting scale formation has involved the use of antifouling coatings, which release toxic substances to aquatic or marine life, for example, tributyltin chloride or cuprous oxide. However, said coatings have been considered with great displeasure due to the harmful effects that these toxins can have on the aquatic or marine environment where they are released. Accordingly, there is a need for anti-fouling coatings, which do not release toxic materials.

COMPENDIUM OF THE INVENTION The present invention relates to a composite material. The composite material includes a polymer having a natural free volume therein and an inorganic or organic material disposed in the natural free volume of the polymer. The present invention also relates to a method for making a composite material. A polymer that has a free volume in it is provided. The free volume of the polymer is evacuated, and the inorganic or organic molecules are infused into the free void volume of the polymer. In a particularly preferred embodiment of the present invention, the inorganic or organic molecules are then polymerized under conditions effective to assemble the inorganic or organic molecules to macromolecular networks. In a particularly preferred embodiment of the present invention, the polymer comprises a functionality, and the inorganic or organic molecules are treated under conditions effective to cause the inorganic or organic molecules to interact with the functionality of the polymer. The present invention also relates to a method for preventing the incrustation of a surface by organisms. The method includes applying to the surface a composite material that includes a polymer having a free volume therein and an inorganic or organic material disposed in the free volume of the polymer. The present invention also relates to a method for preventing the incrustation of a polymer surface by organisms. The polymer surface includes a polymer that has a free volume therein. The free volume of the polymer is evacuated, and inorganic or organic molecules are infused into the free volume evacuated. The present invention also relates to an object. The object has a surface, all or a portion of which comprises a polymer. The polymer has a free volume therein, and an inorganic and organic material is disposed in the free volume of the polymer. The present invention also relates to a method for making an oxyhalopolymer composite material. The method includes an oxyhalopolymer, which has a free volume in it. The free volume of the oxyhalopolymer is evacuated, and the inorganic or organic molecules are infused to the voided free volume of the oxyhalopolymer. The present invention also relates to another method for making an oxyhalopolymer composite material. In this method, a halopolymer composite material is provided. The halogen atoms on the surface of the halopolymer composite material are then modified under effective conditions to replace at least a portion of the halogen atoms on the surface of the halopolymer composite with hydrogen atoms and oxygen atoms or radicals containing oxygen. The present invention also relates to a method for making an oxyhalogenated non-halo polymer material on the surface. The method includes providing an oxyhalogenated non-halo polymer material on the surface having a free volume therein. The method further includes evacuating the free volume of the oxyhalogenated non-halo polymer material on the surface, and infusing inorganic or organic molecules to the free volume of the oxyhalogenated non-halo polymer material on the surface. The present invention also relates to another method for making an oxyhalogenated non-halo polymer material on the surface. In this method, a halogenated non-halo polymer material is provided on the surface. The method further includes modifying the halogen atoms of the halogenated non-halo polymer surface surface under effective conditions to replace at least a portion of the surface halogen atoms of the halogenated non-halo polymer material on the surface with halogen atoms and oxygen atoms or radicals that contain oxygen. The present invention, in another aspect thereof, relates to an oxyhalopolymer composite material. The oxyhalopolymer composite material includes an oxyhalopolymer having a free volume therein, and an inorganic or organic material disposed in the free volume of the oxyhalopolymer.

The present invention also relates to an oxyhalogenated non-halo polymer material on the surface. The composite material includes an oxyhalogenated non-haiopolymer material on the surface having a free volume therein, and an inorganic or organic material disposed in the free volume of the halohalogenated non-halo polymer on the surface. The composites of the present invention contain polymeric phases, which have physical properties substantially similar to the properties of the native polymer (i.e., the polymer in the absence of inorganic or organic molecules or macromolecular networks). Consequently, the composite materials of the present invention, in relation to inorganic-organic hybrid materials, have significantly predictable mechanical properties. The composites of the present invention also have controllable, predictable and reproducible levels of optical densities and conductivities of electrical, ionic and charged species, which make them useful in various applications, including protections and photo-radiation filters, protections and filters. electromagnetic radiation, heterogeneous catalytic substrates, and conduction electrodes. These features also make these composite materials useful as components in the construction of electrolytic cells, optoelectronic devices, semiconductors for microelectronic applications, and materials that have flame retardancy and heat properties.

Although the initial formation of these composite materials results in materials having physical properties substantially similar to those of the native polymer, the subsequent thermal, chemical, photochemical or electrochemical treatment of the composite materials produced in accordance with the present invention can lead to physical properties improved. It is believed that these changes in the physical properties of the composite material result from the chemical and / or electronic interactions between the inorganic or organic infused molecules and the polymer. In addition, the composite materials of the present invention may have a surface, which optionally contains halogen atoms, a portion of which has been replaced with hydrogen atoms and oxygen atoms or oxygen-containing groups. The oxyhalopolymer surface retains many of the positive attributes characteristic of halopolymer surfaces, such as the tendency to repel water and other polar solvents, high thermal stability and low coefficients of adhesion and friction. However, unlike the halopolymer surface, the surfaces of the oxyhalopolymer composites have reactive chemical sites, which allow binding with other chemical functionalities, such as organosilicon, organometallic precursors, ions and transition metal compounds, films of transition metal, fluorescent compounds and other dyes, and biological materials, such as proteins, enzymes and nucleic acids. In addition, through appropriate selection of the inorganic infused material and functionality at the surface, polymer composite materials having an inorganic surface, which is equal to, similar to, or different from the inorganic material infused, can be prepared. Such materials are useful, for example, for preparing metal oxide / fluoropolymer composites having a pure metal oxide surface.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram illustrating the infusion results of the halopolymer composite materials. Figure 2 is a diagram illustrating a cross-sectional view of an oxyhalopolymer composite material of the present invention. Figure 3 is a preparation scheme for making an oxyhalopolymer composite material according to the present invention. Figure 4 is another preparation scheme for making an oxyhalopolymer composite material according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite material. The composite material includes a polymer, which has a natural free volume therein, and an inorganic or organic material disposed in the natural free volume of the polymer. The polymer can be an organic base polymer or an inorganic-organic hybrid polymer. Organic-based polymers suitable for use in the composite materials of the present invention may be homopolymers, copolymers, multi-component polymers, or combinations thereof. Suitable organic polymers include halopolymers, such as fluoropolymers and fluorochloropolymers, polyimides, polyamides, polyalkylenes, such as polyethylene, polypropylene, and polybutylene, poly (phenylenediamine terephthalamide) filaments, modified cellulose derivatives, starch, polyesters, polymethacrylates, polyacrylates, alcohol polyvinyl alcohol, copolymers of vinyl alcohol with ethylenically unsaturated monomers, polyvinyl acetate, poly (alkylene) oxides, homopolymers and copolymers of vinyl chloride, terpolymers of ethylene with carbon monoxide and with acrylic acid ester or vinyl monomer, polysiloxanes, polyfluoroalkylenes, polyalkyl (f luoroalkyli i) ethers, homopolymers and copolymers of halodioxoles and substituted dioxoles, polyvinylpyrrolidone or combinations thereof. The halopolymers are organic polymers, which contain halogenated groups, such as fluoroalkyl, difluoroalkyl, trifluoroalkyl, fluoroaryl, difluoroalkyl, trifluoroalkyl, perfluoroaryl, chloroalkyl, dichloroalkyl, trichloroalkyl, chloroaryl, dichloroalkyl, trichloroalkyl, perchloroalkyl, perchloroaryl, chlorofluoroalkyl, chlorofluoroaryl, chlorodifluoroalkyl groups. and dichlorofluoroalkyl. The halopolymers include fluorohydrocarbon polymers, such as polyvinylidine fluoride ("PVDF"), polyvinyl fluoride ("PVF"), polychlorotetrafluoroethylene ("PCTFE'J, polytetrafluoroethylene (" PTFE ") (including expanded PTFE (" ePTFE "). They prefer fluoropolymers for many applications, due to their extreme inertia, high thermal stability, hydrophobicity, low coefficients of friction and low dielectric properties.In addition, to retain these desirable properties, in many applications, particularly catalytic applications, it is advantageous to use highly These fluoropolymers are electronegative to improve the catalytic properties of metals by associating these metals with fluoropolymers Suitable fluoropolymers include perfluorinated resins, such as perfluorinated siloxanes, perfluorinated urethanes, and copolymers containing tetrafluoroethylene and other polymers containing perfluorinated oxygen, as well as luoro-2,2-dimethyl1,2-dioxide (which is sold under the tradename TEFLON-AF). Other polymers that can be used in the composite materials of the present invention include perfluoroalkoxy substituted fluoropolymers, such as MFA (available from Ausimont USA (Thoroughfare, New Jersey)) or PFA (available from Dupont (Wilmington, Del.)), Polytetrafluoroethylene-co hexafluoropropylene ("FEP"), ethylenechlorotrifluoroethylene copolymer ("ECTFE") and polyester-based polymers, examples of which include polyethylene terephthalates, polycarbonates and analogs and copolymers thereof. Polyethylene ethers can also be used. These include (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene) ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-propyl-1,4) phenylene ether), poly (2,6-dibutyl-1, 4-phenylene ether), and the like. Examples of suitable polyamides include polyhexamethylene alipamide (nylon 66), polyhexamethylene azelamide (nylon 69), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanoamide (nylon 612), poly-bis- (p-aminocyclohexyl) methane dodecanoamide, polytetramethylene alipamide (nylon 46) and polyamides produced by ring cleavage of a lactam such as polycaprolactam (nylon 6) and polylauryl lactam. In addition, polyamides produced through the polymerization of at least two amines or acids can be used for the production of the aforementioned polymers, for example, polymers produced from adipic acid, sebacic acid and hexamethylenediamine. The polyamides further include blends of polyamides such as a blend of nylon 66 and nylon 6 including copolymers such as nylon 66/6. Aromatic polyamides can also be used in the present invention. Preferably, these are incorporated into copolyamides, which contain an aromatic component, such as polymerizable polyamides under fusion containing, as a major component, an aromatic amino acid and / or an aromatic dicarboxylic acid, such as para-aminoethylbenzoic acid, terephthalic acid, and isophthalic acid. Typical examples of the thermoplastic aromatic copolyamides include polyamide copolymer of p-aminomethylbenzoic acid and e-caprolactam (AMBA / 6 nylon), polyamides mainly composed of 2,2,4- / 2,4,4-trimethylhaxamethylene-diaminoterephthalamide (nylon TMDT) and nylon TMDT / 6I), polyamide composed mainly of hexamethylene diaminoisophthalamide, and / or hexamethylene diaminoterephthalamide and containing, as another component, bis (p-amynocyclohexyl) methanisophthalamide and / or bis (p-aminocyclohexyl) methaneterephthalamide, bis ( p-aminociclohexil) propanisoftalamida and / or bis (p-aminociclohexil) propantereftalamida, (nylon 61 / PACM I, nylon 61 / DMPACM I, nylon 61 / PACP I, nylon 6I / 6T / PACM l / PACM T, nylon 6I / 6T / DMPACM l / DMPACM T, and / or nylon 6I / 6T / PACP l / PACP T). Styrene polymers can also be used. These include polystyrene, rubber modified polystyrene, styrene / acrylonitrile copolymer, styrene / methyl methacrylate copolymer, ABS resin, styrene / alpha methylstyrene copolymer, and the like. Other suitable representative polymers include, for example, poly (hexamethylene alipamide), poly (e-caprolactam), poly (hexamethylene phthalamide or isophthalamide), poly (ethylene terephthalate), poly (butylene terephthalate), ethyl cellulose and methyl cellulose, polyvinyl alcohol, ethylene copolymers / vinyl alcohol, tetrafluoroethylene / vinyl alcohol copolymers, poly (vinyl acetate), partially hydrolyzed poly (vinyl acetate), poly (methyl) methacrylate, poly (ethyl) methacrylate, poly (ethyl) acrylate, poly (methyl), terpolymers of ethylene / carbon monoxide / vinyl acetate, terpolymers of ethylene / carbon monoxide / methyl methacrylate, terpolymers of ethylene / carbon monoxide / n-butyl acrylate, poly (dimethyloxan), poly (phenylmethylsiloxane), polyphosphazenes and their analogs, poly (heptafluoropropyl vinyl ether), homopolymers and copolymers of perfluoro (1,3-dioxole) and perfluoro (2,2-dimethyl-1,3-dioxole), especially with tetrafluoroethylene and optionally with another ethylenically unsaturated comonomer, poly (ethylene oxide), poly (propylene oxide) and poly (tetramethylene) oxide. These and other suitable polymers can be commercially purchased. For example, the filaments of poly (phenylenediamine terephthalamide) can be purchased from Dupont under the trade name of KEVLAR ™. Alternatively, polymers suitable for the practice of the present invention can be prepared by suitable methods, such as those described by Elias, Macromolecules-Structure and Properties I and II. New York: Plenum (19779 ("Elias"), which is incorporated herein by reference.The polymer, alternatively, may be an inorganic-organic hybrid polymer or mixture of an organic polymer and an inorganic hybrid polymer. Suitable organic for the practice of the present invention include those prepared by conventional methods to make hybrid organic-inorganic materials, such as those described by Roberts, Pryor, Nagaoka, Coleman, Rajeshwar, Sandbank, Sharp, Anderson I, Basil and Coltrain I and II, which are incorporated herein by reference. The polymer in addition to an organic-based polymer or an inorganic-organic hybrid polymer, may contain a variety of materials, which are known in the art to modify the properties of the polymer. These include fillers, entangling agents, stabilizers, radical sweepers, compatibilizers, antistatic agents, dyes and pigments. Its inclusion or exclusion will depend on, of course, the use that the composite material will have, as will be apparent to one skilled in the art. The materials that make the polymer, whether an organic polymer or an inorganic-organic hybrid polymer, contain a natural free volume. The polymer may have any shape suitable for the use to which the composite material is placed. For example, the polymer can be an organic-based polymer resin, powder or particles or, alternatively, an inorganic-organic hybrid polymer resin, powder or particles. Such particulate forms include sheets, fibers, or beads. As used herein, the sheets include films, the fibers include filaments, and the beads include pellets. Pearls having diameters from about 0.1 mm to about several mm (eg, from about 0.1 mm to about 0.5 mm) and powders having diameters from about 10 mm to about 0.1 mm and made from PVDF, PTFE, FEP, ECTFE , PFA, or MFA with particularly useful in many applications. Alternatively, the polymer may be of a form that is different from that desired for the composite material. The inorganic or organic materials are infused to resins in the form of powders, polymer beads or the like. The powders, infused polymer beads, etc., can then be processed through conventional polymer processing methods to the desired shape. For example, powders, beads, etc., of infused polymer can be extruded to finished sheets or fibers. Alternatively, powders, beads, etc., of infused polymer can be applied to solid objects, such as walls and hydro-aviation helmets, for example, by spraying, cathodically depositing or painting (eg, brushing or rolling) powders, beads or polymer pellets infused on the object under effective conditions to produce a thin film or coating of the polymer infused on the object. The composite materials of the present invention, particularly those in the form of beads, sheets or fibers, can be infused uniformly or non-uniformly. For example, the present invention includes a sheet having two opposing surfaces, wherein the portion of the sheet near a surface is infused, while the other portion of the sheet near the opposite surface is not. This non-uniform infusion can be carried out, for example, covering one of the surfaces of the sheet with a material that avoids the evacuation of the free volume near the covered surface or, alternatively or additionally, which prevents the infusion material from making contact with the covered surface. For the purposes of this invention, the free volume is used in a manner consistent with the description of the free volume in the Elias document on pages 186-188, which is incorporated herein by reference. In summary, Elias points out that, by definition, no large-scale order can exist in amorphous regions. Elias further notes that these amorphous regions are not crystal clear by X-rays, and, although studies suggest that amorphous polymers by X-rays may have some order, a given number of vacant sites must be present. In this way, free volume, as used herein, refers to vacant sites, which are present in amorphous regions of a polymer and where organic and inorganic molecules are diffused. The free volume is exploited according to the present invention as regions where inorganic or organic materials can be introduced, such as by diffusion, and subsequently assembled to macromolecular networks or stabilized through interaction with the functionality of the polymer. These free volumes are generally formed during the curing process, such as after the evaporation of the solvent in which the polymer is formed, but the present invention is not intended to be limited by the mechanism through which the free volume may exist in the polymer. For the purposes of this invention, the free volumes can be natural free volumes or created free volumes. Natural free volumes, as used herein, refer to vacant sites that are characteristically present in amorphous regions of a polymer and where organic or inorganic molecules can diffuse. These natural free volumes include those that are formed during the curing process, such as after evaporation of the solvent in which the polymer is formed. In contrast, the free volumes created with those free volumes that are produced or modified after polymer formation, exposing the polymer to supercritical fluids under supercritical conditions. Since the free volumes of the composites of the present invention are natural free volumes and do not contain created free volumes, these natural free volumes substantially contain no carrier liquid or other solvent used in supercritical infusion processes. The total natural free volume available to diffuse inorganic or organic molecules in the particular polymer depends on a variety of characteristics of the natural free volume. These include the size, distribution of size, concentration and spatial distribution of the natural free volume, all of which are not effected by the conditions under which the polymer is formed, including, for example, how the solvent was removed.; the pressure and temperature (and variations thereof) during the solvent removal process; the degree to which the polymer was cured before the start of the solvent removal process; the nature of the solvent; the nature of the organic or inorganic-organic hybrid polymer; the size of the polymer matrix; and similar. Another factor that affects the natural free volume of the polymer is the degree of crystallinity. The polycrystalline regions contained within a polymer having less natural free volume than the amorphous regions, are hermetically packed, inhibit the movement of inorganic molecules towards the polymer. In this way, it is preferred that the polymer has at least some degree of non-crystallinity (i.e., that it has a crystallinity of at least 100%). Suitable polymers (eg, halopolymers and non-halopolymers) are those having crystallinity less than 99%, preferably less than 95%. The total natural free volume of the polymer (ie, the collective volume of the natural free volumes) ("Vs") is preferably greater than about 1 x 10"6 of the total volume of the polymer.Expressed differently, if the total volume of the polymer is designated Vc, then the collective volume of the natural free volume is preferably greater than 1 x 10"6 Vc, most preferably from about 1 x 10" 6 Vc to about 0.1 Vc and still most preferably about 1 x 10"3 Vc at approximately 0.1 Vc. The natural free volume can be an inherent property of the polymer (ie, a property which is stabilized through the method used to initially form the polymer) or, alternatively, can be controlled after polymer formation through any means suitable (other than exposure to supercritical fluids under supercritical conditions), such as by increasing or decreasing the temperature of the polymer when inorganic or organic materials are diffused therein. For example, increasing the temperature at which the inorganic or organic molecules are diffused to the polymer increases the natural free volume of the polymer without substantially altering its physical and mechanical properties. In this way, a higher concentration of the inorganic or organic molecules can be diffused to the polymer, which results, for example, in a higher concentration of the macromolecular network in the polymer. Methods for determining natural free volume as a fraction of the total polymer volume (i.e., Vs / Vc) are well known to those skilled in the art. Illustrative methods can be found in the Elias document on pages 256-259, which is incorporated herein by reference. The natural free volume of the polymer can also be determined by the flow velocity of the gases through the polymer. The natural free volume and its distribution in the polymer can also be determined using a photo-reactive probe, such as that described by Horie, "Dynamics of Electron-Lattice Interactions", in Tsuchida editorial, Macromolecular Complexes: Dynamic Interactions and Electronic Processes. New York: VCH Publishers, pages 39-59 (1991), which is incorporated herein by reference. As indicated above, the composite material of the present invention further includes an inorganic or organic material, which is disposed in the natural free volume of the polymer. The amount of the inorganic or organic material within the natural free volume is typically proportional to the internal surface area of the natural free volume of the starting polymer, which, as described above, can be an inherent characteristic of the polymer or can be controlled through of any suitable medium (different by exposure to supercritical conditions), for example, by increasing or decreasing the temperature at which the inorganic or organic material diffuses therein. The inorganic material can fill the natural free volume of the polymer or occupy a significant portion of it in two or three dimensions. The inorganic material itself can form three-dimensional networks within the natural free volume. These three-dimensional networks can be dense, filling substantially all the natural free volume, or they can be porous, thus allowing the flow of gas molecules in and out of the natural free volume and through the three-dimensional inorganic or organic macromolecular network. Alternatively, the inorganic material may be a two-dimensional layer (such as a coating or film) on or along the surface or a portion of the surface of the natural free volume. In the case where the free volume is small, the inorganic or organic material can follow the template of a dimension of the starting material. This results in a two-dimensional morphology depending on the inherent chemistry and / or the physical morphology on the abutting surfaces of the natural free volume / polymer. Preferably, the inorganic or organic material is homogeneously or substantially and homogenously spread throughout the natural free volume of the polymer. Any suitable inorganic material can be used. Suitable inorganic starting materials for use in the practice of the present invention are those capable of having a vapor pressure greater than zero at a temperature of between room temperature and the thermal decomposition temperature of the polymeric material and / or at pressures of about 0.1. mTorr to approximately 10 Torr. By inorganic material, it is meant that the material contains at least one metal or atom. As used herein, all atoms, other than hydrogen, oxygen, fluorine, chlorine, bromine, helium, neon, argon, krypton, xenon, and radon, are considered metal atoms. The preferred metal atoms are alkali metals, alkaline earth metals, transition elements, lanthanides, actinides, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth , selenium, tellurium, polonium and astatin. In addition, carbon, nitrogen, sulfur, and iodide are considered lethal, particularly in cases where they bind to other atoms through non-covalent bonds (eg, ionic bonds and pi-pi bonds). Particularly useful inorganic materials are those which contain a metal selected from the group consisting of V, W, Fe, Ti, Si, Al, P, Sb, As, Ba, B, Cd, Ca, Ce, Cs, Cr, Co , Cu, Ga, Ge, In, Pb, Mg, Hg, Mo, Ni, Nb, Re, Ta, TI, Sn, Go, Rh, Th, Ru, Os, Pd, Pt, Zn, Au, Ag, and combinations thereof. Illustrative inorganic materials contemplated for use in the present invention also include metal ions or metal atoms, which contain at least one active ligand. These metal ions or metal atoms, which include at least one active ligand, can be polymerized to form a bond to a surrounding metal atom or ion, thus forming a macromolecular complex, or they can be treated so as to interact with the functionality contained in the polymer to form, for example, a kind of metal stabilized through complex formation by the functionality of the polymer. Said metal ions or metal atoms include metallo-oxo species, metallo-nitro species, pi-allyl and arene complexes of the Illa, IVa, Va, Via, Vlla and Villa metals group, and organometallic complexes linked to organic functionalities. such as chlorides, bromides, alkyls, aryls, carboxylic acids, carbonyls, alkoxides, pyridines, tetrahydrofurans, and the like. Preferably, the inorganic material is in the form of a macromolecular network or interacts with a functionality contained within the polymer. The macromolecular networks and inorganic interacting materials are preferably stable to diffusion out of the polymer at temperatures at which the composite material is to be employed. For example, when the composite material of the present invention is to be used as a catalyst, it is advantageous that the inorganic macromolecular network or inorganic material interacts with a functionality contained within the polymer that will be stable to diffusion at temperatures employed to carry out the particular catalytic reaction. Suitable functionalities with which the inorganic material can interact include halogens (such as fluorides or chlorides), amines, alkenes, alkynes, carbonyls (such as keto groups, aldehyde groups, carboxylic acid groups, ester groups, amide groups, and the like), alcohols and thiols. The inorganic molecules, which interact with functionalities on the polymer, can have the formula My-Xj, where X is a functionality contained within the polymer (for example, halogen, such as F or Cl, NH2, NH, 0-C = 0, C-OH, C = C, C = C, or C = 0), and it is the oxidation state of the metal, which can vary from zero to the highest oxidation state of the particular metal, and j is the number of ligands to which the particular metal can be bound within a given polymer. For example, when M is Pd and X is Cl, j can be 2. Inorganic macromolecular networks, which are stable to diffusion, include metal atoms and macromolecular networks. Macromolecular networks, as used herein, are molecules that contain three or more, preferably more than about 20, most preferably more than about 100 metal atoms that are directly or indirectly linked together. Suitable macromolecular networks include polycondensates, such as those having the formula: [X (0) n-Oy-X (0) n] m, wherein m is an integer from about 1 to about 10,000 or more; X represents a metal ion that has a charge of + s; s is an integer of 1 to the oxidation state that can be obtained higher than the metal; and is an integer from 0 to s; and n is between zero and s / 2. The well-known silica, titania and zirconia structures, wherein each metal atom is bonded to four oxygen atoms and each oxygen is bonded to two metal atoms, are examples of such macromolecular networks. Other macromolecular networks are also contemplated, such as those in which one or two of the links to some metal atoms in a silica, titania or zirconia network are occupied by other portions, such as alkyl groups. Other macromolecular networks include those formed from pi-allyl compounds, such as pi-allyl compounds of metals from Group Illa, IVa, Va, Via, Vlla and Villa. Illustrative p-allyl compounds suitable for use in the practice of the present invention are described, for example, Wiike et al., Angewandte Chemie, International Edition. 5 (2): 151-266 (1996), which is incorporated herein by reference. In particular, these compounds are contemplated as being useful for forming zero-valent, macromolecular metal networks, conductors (eg, macromolecular networks of conducting metals in the zero oxidation states), such as those having the formula M °) n, where n is from about 1/2 to about 10,000 and M ° is a metal of the Illa Group, IVa, Va, Via, Vlla or Villa. Any suitable organic material can also be used. Preferred organic materials for use in the practice of the present invention are those capable of having a vapor pressure greater than zero at a temperature of between ambient and the temperature of thermal decomposition of the polymeric material. It is preferred that it also be capable of polymerizing a macromolecular network (eg, macromolecular networks having the formula - (RR ^ -n, where n is an integer from about 1 to about 10,000 and R is a monomer radical), such as through an oxidation, hydrolysis, chemical, electrochemical or photochemical process Organic molecules, such as pyrrole, aniline and thiophene, which can be oxidatively polymerized, such as to form poly pyrrole, polyaniline or polythiophene, are also suitable Other suitable organic molecules are those that can be polymerized through exposure to actinic radiation (e.g., ultraviolet radiation), such as acetylene, which when polymerized forms polyacetylene Even more illustrative organic molecules include organic monomers, which can be converted to organic macromolecules (ie, polymers) .These include the entire monomer class s organic, which can be polymerized to form polymers, such as driving polymers. A list of these materials, their properties and their application to the construction of polymer batteries, electrical capacitors, electrochromic devices, transistors, solar cells and non-linear optical devices and sensors can be found in Yamamoto, "Macromolecular Complexes: Dynamic Interactions and Electronic Processes" , in E. Tsuchida, ed., Sequential Potential Fields in Electrically Conducting Polvmers, New York: VCH Publishers, p. 379-396 (1991) ("Yamamoto"), which is incorporated herein by reference. Due to the close proximity of the polymer and the inorganic or organic network, which exists within the natural free volume in it, the chemical functionality contained in the surface of the free volume within the polymer can, in some cases, influence the chemical and electronic characteristics of the inorganic or organic macromolecular network and vice versa. In this way, by altering the polymer, the properties of the inorganic or organic macromolecular network can be influenced. The degree of this influence depends on the nature of the chemical and electronic properties of the starting polymer. For example, strongly electronic withdrawal atoms, such as fluorine atoms, have an influence on the catalytic properties of many metals. More particularly, Kowalak et al., Collect. Czech Chem. Commun., 57: 781-787 (1992), which is incorporated herein by reference, reports that the fluorination of zeolites containing polyvalent metal cations increases the activity of these zeolites to induce catalyzed acid reactions. Therefore, when the compositions of the present invention are going to be used for their catalytic properties, it may be advantageous to employ polymeric materials that carry strongly electronic removal groups. In some cases, the polymer may contain pendant groups or chemical functionalities located on the abutting surface of the free volume, which may influence the chemical or electronic properties of the inorganic or organic macromolecular network formed in the free volume. The interactions of the pending groups or chemical functionalities with the macromolecular network contained in the natural free volume can be via interactions between space (that is, without any formation of union or real complex between the interaction species), via direct ionic union, of hydrogen or covalent, or, in some cases, via the formation of a bond that is commonly found when metal atoms coordinate with non-metals or other atoms or metal groups. The formation of such bonds between the polymer material and the macromolecular network contained within the natural free volume of the polymer material can be detected using methods well known to those skilled in the art, such as visible ultraviolet light spectroscopy, infrared spectroscopy, spectroscopy nuclear magnetic resonance, and other techniques, including those described in Drago, Physical Methods in Chemistrv, Philadelphia: WB Saunders (1977), which is incorporated herein by reference. One of the advantages of the composite materials of the present invention is that many of the properties of the starting polymer are substantially conserved. In contrast to the results obtained through supercritical impregnation methods (which have an effect on the swelling of the polymeric material), the preferred composites of the present invention (e.g., composite materials containing inorganic or organic macromolecular networks arranged in the natural free volume of a polymer) have dimensions that are substantially equal to the dimensions of the starting polymer (ie, the polymer whose natural free volume does not contain any inorganic or organic macromolecular network disposed therein). Preferred composites of the present invention also have flexibility, crystallinity, or thermal decomposition temperatures ("Td"), which are substantially equal to the flexibility, crystallinity or Td of the starting polymer. As used in this context, properties that differ by less than 10% as being substantially the same are contemplated. Td is described by Elias, in Macromolecules - Structure and Properties. I and II, New York: Plenum Press (1977), which is incorporated herein by reference. In other situations, it may be desirable to modify these properties, so that they are different from those of the starting polymer material. This can be done by selecting an appropriate inorganic or organic molecule. Alternatively or additionally, this can be achieved through subsequent chemical, photochemical, electrochemical or thermal treatments, which can act to initiate interactions between the chemical functionalities of the infused organic or inorganic macromolecular network and the chemical functionalities found in the surface of free volume of the polymer. These interactions can lead, for example, to an improved catalytic activity of the metallic species in the macromolecular network, improved thermal properties of the composite compared to the initial thermal properties of the starting polymer, or improved conductivity of a macromolecular network of organic conduction. To improve the conductivity of macromolecular networks of organic conduction, the macromolecular network can be contaminated, for example, by means of the chemistry contained in the polymeric material (especially the chemical functionalities of the polymer on the adjoining surface of the free volume) or, alternatively, through a subsequent diffusion of dopant, whereby a doping molecule is incorporated into the composite material. Suitable dopants that can be used to improve the conductivity of macromolecular conduction networks arranged in the composite materials of the present invention can be found in, for example, Yamamoto, which is incorporated herein by reference. Although, as indicated above, the preferred inorganic materials are those that are resistant to diffusion, the present invention is not limited thereto. For example, the inorganic material can be a compound that can be converted, such as through chemical methods (eg, oxidation, hydrolysis or hydrogenation), or electrochemical, photochemical or thermal, to an inorganic macromolecular network or to a metallic species that interacts with the functionality of the polymer that resists diffusion. For example, the inorganic material can be a compound selected from the groups consisting of VOCI3, W (CO) ßl Fe (CO) 5, TiCl4, SiCl4, AICI3, PCI3, SbCI5, As (C2H5) 3, Ba (C3H7) 2, borane-pyridine and tetrahydrofuran complexes, Cd (BF4) 2, Ca (OOCCH (C2H5) C4H9) 2, cerium (III), 2-ethylhexanoate, cesium 2-ethylhexoxide, chromium (III) naphthenate, Cr02CI2, Co (CO) 3NO, copper (II) dimethylaminoethoxide, triethylglycol, GeCI4, triethylindium, lead naphthenate, C2H5MgCI, (CH3) 2Hg, MoF6, Ni (CO) 4, Nb (OC2H5) 6, HRe04, Ta ( OC2H5) 5, Ta (OC2H5) 5, C5H5TI, SnCl4, pi-allyl compounds of Group Illa, IVa, Va, Vlla, or Villa and combinations thereof, all of which can be converted to inorganic materials that resist the diffusion. The composite materials of the present invention can be prepared by the method that follows, as well as the present invention. A polymer that has a free volume in it is provided. The free volume is evacuated and the free volume evacuated is infused with the inorganic or organic molecules. The free volume that is evacuated and in which the inorganic or organic molecules are infused, can be natural free volumes (ie, free volumes that are neither created nor modified by the exposure of the polymer to supercritical fluids under supercritical conditions before or during the evacuation or infusion). Preferred inorganic molecules are those that can be converted to inorganic materials, which are resistant to diffusion, such as inorganic molecules that can be polymerized to macromolecular networks or which can be treated so that the inorganic molecules interact with the functionality of the polymer. Suitable inorganic molecules include compounds and complexes of metal atoms (such as alkali metals, alkaline earth metals, transition elements, lanthanides, actinides, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, selenium, tellurium, polonium, and astatin, and, in particular, chaos where they are linked to other atoms through non-covalent bonds (eg, ionic bonds and pi-pi bonds) ), carbon, nitrogen, sulfur, and iodide), especially V, W, Fe, Ti, Si, Al, P, Sb, As, Ba, B, Cd, Ca, Ce, Cs, Cr, Co, Cu, Ga , Ge, In, Pb, Mg, Hg, Mo, Ni, Nb, Re, Ta, TI, Sn, Go, Rh, Th, Ru, Os, Pd, Pt, Zn, Au, Ag, and combinations thereof . The ligands to which the metal atom or ion is bound or in complex are not particularly critical, although it is preferred that the ligand be chosen so that the inorganic molecule is labile by exposure to oxidation, hydrolyzation, hydrogenation, chemical or electrochemical environments, as well as labile by exposure to heat or actinic radiation, such as ultraviolet radiation . Suitable ligands include those described above. Specific examples of inorganic molecules that can be used in the practice of the present invention include VOCI3, W (CO) 6, Fe (CO) 5, TiCl4, SiCI4, AICI3. PCI3, SbCI5, As (C2H5) 3, Ba (C3H7) 2, complexes of borane-pyridine and tetrahydrofuran, Cd (BF4) 2, Ca (OOCCH (C2H5) C4H9) 2, cerium (III), 2-ethylhexanoate, 2 - cesium ethylhexoxide, chromium naphthenate (III), Cr02CI2, Co (CO) 3NO, copper (II) dimethylaminoethoxide, triethylgalium, GeCI4, triethylindium, lead naphthenate, C2H5MgCI, (CH3) 2Hg, MoF6, Ni (CO) 4, Nb (OC2H5) 6, HRe04, Ta (OC2H5) 5, Ta (OC2H5) 5, C5H5TI, SnCl4, pi-allyl compounds of Group Illa, IVa, Va, Vlla, or Villa and combinations thereof. Suitable organic molecules are those that can be converted to polymeric materials that are resistant to diffusion, such as macromolecular networks. Suitable organic molecules include compounds such as acetylene, p-phenylene, thiophene, 2,5-thienylene, pyrrole, 2,5-pyrrolylene, 2,5-3-substituted thienylene, 3-substituted pyrrole, aniline, p-phenylenevinylene, 2,5-pyridindiyl, haxadiino and diacetylenes. All these compounds can be diffused to the polymer and then oxidant, chemically or photochemically converted to their corresponding macromolecular complex so that they form a macromolecular network that does not diffuse into the free volume of the polymer. Since the macromolecular networks made of these organic molecules can be electrically or ionically conductive, the infusion of these organic molecules can add varying degrees of electrical and / or ionic properties to the composite material without significantly changing the crystallinity, flexibility or Td of the polymer material. of departure. Organic molecules, such as naphthalenes and pyridines can also be infused to add optical properties to these materials. However, these aromatic materials can not be polymerized to macromolecular networks and, therefore, are not as stable with respect to diffusion out of the polymer, except in cases where they can complex with the functionality of the polymer matrix. As indicated above, the free volume of the polymer is first evacuated. As used herein, evacuation means reducing the pressure in the free volume of the polymer to less than atmospheric pressure (i.e., less than 760 Torr). This can be enhanced by placing the polymer in a chamber, container or other container capable of withstanding the vacuum that is employed and reducing the pressure in the chamber, container or other container to less than about 760 Torr, preferably from about 100 Torr to about 10 Torr. mTorr or less, and most preferably from about 1 Torr to about 10 mTorr or less. Evacuation is typically achieved in approximately 1 minute to several days, depending on temperature and pressure. The free volume, thus evacuated, is then infused with the inorganic or organic molecules. In contrast to the methods of the prior art, the infusion here is performed under non-supercritical conditions (eg, in absence rather than in the presence of supercritical fluids and carriers, under conditions that do not produce the free volume created and the swelling of the polymer , and similar).

The infusion can be carried out through any method. Conveniently, the infusion is carried out with the inorganic or organic molecule in a gaseous state by contacting the evacuated polymer with the inorganic or organic gaseous molecule. The inorganic or organic molecule can be naturally in the gaseous state, as is the case with some metal carbonyls, or the inorganic or organic molecules can be boiled, sublimated, or otherwise vaporized, such as with heat or under reduced pressure, or both In many cases, inorganic or organic molecules will be at least a little reactive with air; in these cases, vaporization, as well as all other manipulations of inorganic or organic molecules, are best conducted in an inert atmosphere, such as under argon or nitrogen, or in a vacuum. The gaseous inorganic or organic molecule is then contacted with the evacuated polymer. This can be done by placing the polymer in a vessel, evacuating the vessel at a pressure of less than 760 Torr, and then flowing the inorganic or organic molecules in the evacuated vessel containing the evacuated polymer. The infusion can be accelerated and, in general, more of the gaseous molecules can be infused by effecting the infusion process in an atmosphere of gaseous inorganic or organic molecules, preferably at elevated temperatures. The temperature and pressure at which the infusion is made is important as they affect the time required for the infusion process. The temperature and pressure are preferably optimized within a scale that allows inorganic or organic materials to have vapor pressures of more than zero and increase the concentration of amorphous regions within the polymer (which provides more free volume). It is believed that, by initially evacuating the container carrying the polymer, the rate of infusion of the inorganic or organic molecules is improved, since inorganic or organic molecules do not need to displace environmental gases residing in the free volume of the polymer. In a preferred embodiment of the present invention, the infusion is carried out at temperatures greater than about 50 ° C below that of the glass transition temperature (Tg) of the polymer and less than the thermal decomposition temperature ("Td. ") of the polymer polymer material (ie, at temperatures greater than about Tg-50 ° C, but less than about Td). The larger the temperature, the higher the rate of incorporation of the inorganic or organic molecules infused into the polymer. Also, the larger the temperature, the greater the resulting concentration of the inorganic or organic material diffused into the polymer due to the thermal rearrangement, which acts to increase the free volume within the polymer. It should be understood that these are only preferred conditions and that the same processes can be performed outside of the preferred temperature ranges. In some cases, it may be preferred to effect the infusion outside this temperature range, such as controlling the concentration of the inorganic or organic molecules in the finished composite. As the skilled artisan will note, in order to practice the present invention at the preferred temperature scale, the inorganic or organic molecule must have a non-zero vapor pressure at temperatures greater than about Tg-50 ° C, but less than about the Td of the polymer and / or the pressure used during the infusion process. In some cases, heating the polymer to temperatures that optimize free space space can result in thermal decomposition of the inorganic or organic molecules that are desired to be infused into the polymer. In such cases, the infusion is best performed at temperatures and pressures at which inorganic or organic molecules can obtain a vapor pressure greater than zero, but thermally they do not decompose. As indicated above, the time required for the infusion varies depending on the temperature, the pressure, the nature of the inorganic or organic molecules, the nature of the polymer, the desired degree of infusion, the desired concentration of the inorganic or organic molecules, and similar. In most cases, the infusion can be carried out from approximately a few minutes to approximately 2 days. After infusion of the inorganic or organic molecules into the polymer, the inorganic or organic molecules can be polymerized under effective conditions to cause the inorganic or organic molecules to assemble into macromolecular networks. Preferably, the polymerization is carried out in the absence of free (ie, non-infused) inorganic or organic molecules. Accordingly, it is preferred that, prior to polymerization, the infused polymer be removed from the atmosphere containing gaseous inorganic or organic molecules or that the atmosphere surrounding the infused polymer be evacuated or replaced with an inert gas. The polymerization can be carried out by exposing the inorganic or organic molecules infused in the free volume of the polymer to any suitable polymerization condition. For example, the infused organic or inorganic material can be oxidized, hydrolyzed, hydrogenated, chemically treated, photoactivated, electrochemically polymerized or thermally polymerized by exposing the infused organic or inorganic material to appropriate conditions, such as by exposing the inorganic or organic material infused to an agent of oxidation, a hydrolyzing agent, a hydrogenation agent, a specific chemical (eg, electrochemical or photochemical), actinic radiation, suitable voltages or appropriate temperatures. Typically, the oxidation, hydrolyzing or hydrogenation agent is gaseous or is contained in the form of vapor in an inert gas. For convenience, oxidation or hydrolysis can be effected by exposing the inorganic molecules to a gas, which includes water, oxygen or combinations thereof, such as ambient air. The oxidation, hydrolysis or hydrogenation can be carried out at any suitable temperature or pressure, preferably at room temperature and at ambient pressure and at temperatures below the Td of the polymer and the decomposition temperature of the inorganic or organic molecules. In the case where the inorganic or organic molecules are sensitive to air or moisture, oxidation or hydrolysis can be conveniently carried out at room temperature and ambient pressure and for about 5 minutes to about 48 hours. Hydrogenation can be carried out by exposing the polymer Nfused to hydrogen gas. For example, a polymer containing a pi-allyl metal compound can be placed in a hydrogen atmosphere at room temperature for about 5 minutes to about 48 hours. The pi-allyl compound is reduced, propane gas is released, and a kind of stabilized metal or a metal network is formed in the free volume of the polymer. In the case where a metal network is formed in the free volume of the polymer, the metal network may or may not interact with functionalities contained within the polymer.

In some cases, the polymerization can be carried out chemically. For example, organic pyrrole molecules can be infused into the free volume of the polymer and then converted to the polypyrrole by contacting the polymer material with a chemical solution containing 50% water and 50% HN03. This solution oxidizes the pyrro to a macromolecular network of polypyrrole, which resides through the free volume of the polymer. Alternatively, the polymer can first be converted to a composite material as described herein, so that the macromolecular network contained in the polymer has oxidizing properties. A suitable macromolecular network having oxidant properties is V205. After formation of this composite material containing V205, organic molecules such as pyrrole can be infused, which are then oxidized by the macromolecular network of V205 to form a network of macromolecular polypyrrole within the free volume of the polymer. Organic monomers that can be electrochemically polymerized, such as acetylene or thiophene, once infused into the free volume of the polymer, can be polymerized by contacting the infused polymer with an electrode and adjusting the potential of the electrode to facilitate the oxidative polymerization of the organic molecules. As a further example, the heat treatment of the organic molecule, C6H-CH2- (R2-S + X ") - CH2-, facilitates the polymerization to the macromolecular polymer, polyphenylenevinylene (See, for example, Yamamoto, which is incorporated here by reference.) Once polymerized, the inorganic or organic molecules self-assemble to macromolecular networks for a period ranging from simultaneous assembly after exposure to polymerization conditions to a few hours to a few days.The assembled macromolecular network can optionally, be infused with dopants, such as Na, 12, Br 2, FeCl 3, AsF 5, and those described in Yamamoto, which is incorporated herein by reference, to improve the conductive properties of the macromolecular network contained within the free volume of the polymer An additional description of these processes and their utility to make, for example, polymer batteries, electrolytic capacitors, electrochromic devices , diodes, solar cells, and non-linear optical materials, can be found in Yamamoto, which is incorporated herein by reference. It is believed that, since the inorganic or organic molecules that are diffused in the polymer, are confined to the free volume of the polymer, the resultant self-assembled macromolecular networks are mainly limited to extending longitudinally (i.e., only a monolayer to a few layers of polymer). the network can be formed in two dimensions and the growth of the network is mainly through a dimensional extension of an individual monolayer chain through the free interconnected volumes contained within the polymer). It is further believed that this results in a material whose polymer phase is relatively unchanged with respect to flexibility, crystallinity, Td and other physical properties. In essence, it is believed that the polymer acts only as a molecular template in which the inorganic network is formed along the space of the free volume associated with these materials. However, since the inorganic or organic macromolecular network is contained in the free volumes, which are homogeneously incorporated through the polymer, imparts its own properties to the composite material as a whole. Such imparted properties include controlled and variable optical densities, catalytic properties and electrical and ionic conductivities, as well as improved thermal-mechanical properties. Alternatively, particularly in cases where the polymer contains adequate functionality, the infused inorganic or organic molecules can be treated under effective conditions to cause the inorganic or organic molecules to interact with the functionality of the polymer. As described above, suitable polymer functionalities include halogens (such as fluorides or chlorides), amines, alkenes, alkynes, carbonyls (such as keto groups, aldehyde groups, carboxylic acid groups, ester groups, amide groups, and the like), alcohols, and thiols. Inorganic molecules that interact with functionalities in the polymer may have the formula MyXj, wherein X is a functionality contained within the polymer (e.g., halogen, such as F or Cl, NH2, NH, 0-C = 0, C- OH, C = C, C = C, or C = 0), and it is the oxidation state of the metal, which can vary from zero to the highest oxidation state of the particular metal, and j is the number of ligands to which the particular metal can be bound within a given polymer. For example, when M is Pd, and X is Cl, j can be 2. In cases where the inorganic or organic molecules contain metal atoms or ions, the metal and polymer functionality interacted can generally be characterized as an inorganic complex, although other types of interactions are also contemplated, such as covalent interactions, ionic interactions, pi-pi electronic interactions, and the like. The interaction between the inorganic or organic material can be spontaneous, that is, it can occur immediately or for a period simply by virtue of the inorganic or organic material that is very close to the functionality of the polymer. In this case, the treatment simply means allowing the inorganic or organic molecules to interact with the functionality of the polymer. In other cases, the interaction between the inorganic or organic material is not spontaneous and requires that inorganic or organic molecules be actively treated, such as by oxidizing, hydrolyzing, hydrogenation, chemically treating or photoactivating, electrochemically activating, the inorganic or organic molecules infused. The inorganic or organic molecules oxidized, hydrolyzed, hydrogenated, chemically treated, photoactivated, electrochemically activated then interact with the functionality of the polymer. In practicing this aspect of the present invention, oxidation, hydrolyzation, hydrogenation, chemical treatment or photoactivation, chemical activation of the infused inorganic or organic molecules can be carried out through the methods described with respect to the polymerization of inorganic or organic molecules. In some cases, very notably in cases where the inorganic molecules contain metal atom and ligands attached thereto, where the binding strength of the metal ligand is large, the oxidation, hydrolysis or hydrogenation of the ligands may be slow or incomplete. For comparisons of the binding strength of the metal ligand and the tendency of the metals to hydrolyze, see Huheey, Inorganic Chemistrv, 3 °. Edition, Principles of Structure and Reactivity- New York: Harper and Row, Chapters 7 and 11, which is incorporated herein by reference. In such cases, it is advantageous to expose the inorganic molecules to actinic radiation, such as ultraviolet ("UV") radiation, preferably a broadband source of about 190 nm to about 400 nm, (or, in some cases, high energy UV). (for example, wavelengths less than 190 nm or X radiation), under effective conditions for splitting the ligands of the metal atoms, typically during a period related to the resistance of the metal ligand binding and the energy output (ie, energy density) of the radiation source. The metal atoms having the split ligands thereof can be treated photochemically, chemically, electrochemically or thermally under effective conditions to cause the metal atoms to interact with the functionality of the polymer. Alternatively, the metal atoms having the ligands split therefrom can then be exposed to a gas containing oxygen or water under effective conditions to cause the metal atoms to assemble into macromolecular networks. A gas or atmosphere containing oxygen or water is preferably present while exposing the inorganic molecules (diffused in the polymer) to actinic radiation, so that oxidation or hydrolysis can occur immediately after the cleavage of the metal ligand. Gases containing oxygen or water suitable for use in this process include: substantially pure oxygen; oxygen mixed with water and / or an inert gas, such as Ar or N2; or environmental air. For example, W (CO) 6 is a complex of tungsten metal, which contains 6 carbonyl ligands. Carbonyl ligands are labile to heat or UV radiation. However, its lability is reduced with the loss of each carbonyl ligand. In other words, after the loss of the first carbonyl, the second carbonyl becomes more difficult to remove; after the loss of the second carbonyl, the third carbonyl becomes more difficult to remove; and so on. Thus, after the infusion of W (CO) 6 into a polymer, the loss of the carbonyl ligands is preferably carried out by activating the tungsten-carbonyl bond through the exposure of a broadband ultraviolet source (e.g. radiation between 190 nm and 400 nm) to facilitate the total decomposition of W (CO) 6. The decomposed tungsten complex is then free to interact with the functionality of the polymer or reacts with surrounding decomposed tungsten complexes to form a macromolecular tungsten oxide network. It is believed that the above polymerization of the inorganic or organic molecules and the assembly to macromolecule networks and / or the prior treatment of the inorganic or organic molecules to cause their interaction with the functionality of the polymer results in improved stability of the complex, such as , for example, by reducing the migration of inorganic or organic molecules out of the free volume of the polymer. The composite materials of the present invention are useful, for example, in the construction of lightweight, flexible, electromagnetic UV and X radiation protections; flexible components for use in the construction of electrochromic or liquid crystal displays; and electrode materials and separators used in the construction of high-energy, lightweight density batteries. The composite materials of the present invention and the composite materials produced according to the method of the present invention, particularly those containing vanadium and oxygen, such as vanadium pentoxide, can be used as an electrically conductive imaging layer of a electroconductive image forming element, such as those that are employed in high speed laser printing processes. The electroconductive imaging element typically includes an insulating support, an electrically conductive layer overlaying the support, and a dielectric imaging layer overlapping the electrically conductive layer. Further details regarding the construction and use of these electroconductive image forming elements can be found in, for example, Anderson I, which is incorporated herein by reference. The composite materials of the present invention and the composite materials made through the processes of the present invention, particularly those containing a macromolecular network of vanadium oxide, can be used as antistatic materials in photographic elements, such as films and photo papers . These photographic elements include a substrate, one or more light sensitive layers, and one or more antistatic layers containing the composite material of the present invention. Other component layers, such as auxiliary layers, barrier layers, filter layers and the like, can also be employed. A detailed description of photographic elements and their various layers and additions can be found in, for example, James, The Theory of the Photographic Process, 4th edition (1977), which is incorporated herein by reference. The present invention is also directed to a fuel cell, such as a battery. The fuel cell includes a composite material of the present invention or a composite material produced in accordance with the method of the present invention, particularly those that are electrically or ionically conductive. The fuel cell also includes an anode and a cathode, which are in contact with the composite material. The present invention is also directed to a method for protecting a material from electromagnetic radiation emitted from a source of electromagnetic radiation. The method includes arranging a composite material of the present invention or a composite material produced according to the method of the present invention between the material to be protected and the source of electromagnetic radiation. Composite materials whose inorganic or organic molecules include a metal complex, such as iron, titanium and vanadium complexes, are particularly well suited to protect visible and ultraviolet radiation. Composite materials whose inorganic or organic molecules include a metal having a high Z number, such as tungsten, lead, and gold, also protect against high-energy ultraviolet light and X-rays. As used herein, protection means filtering, such as when the intensity of the electromagnetic radiation is partially reduced (for example, by 50% or more), as well as blocking, such as when the electromagnetic radiation is completely absorbed or reflected by the composite material. The composite materials of the present invention can also be used as a flame or heat retardant material. More particularly, composite materials containing a zinc oxide, a zinc / molybdenum oxide, a zinc / chromium oxide, a zinc / silicon oxide, a zinc / titanium oxide, a bismuth / boron oxide, an oxide of molybdenum / tin, a molybdenum oxide, an antimony oxide, alumina, or a macromolecular network of silica or combinations thereof, may be used in place of the fluoropolymer composition described in the US patent No. 4,957,961 issued to Chandrasekaren et al., Which is incorporated herein by reference, to thermally insulate wires and cables and to protect them from flames and smoke. Accordingly, the present invention is also directed to a method for protecting a material from heat or flame. The method includes arranging a composite material of the present invention or a composite material produced according to the method of the present invention between the material to be protected and the source of heat or flame. As used herein, the heat source or the flames can be a source of heat or actual flame or a potential source of heat or flames. In addition, the composites of the present invention, which contain inorganic metallic networks known to be conventionally useful as catalysts for carrying out molecular transformations, can be used for heterogeneous catalysis of, for example, combustion gases, car emissions, precursors for industrial grade chemicals and commercially valuable fines, and the like. The composite materials of the present invention are also useful in continuous as well as intermittent flow processes. The catalysis of a reaction of a reagent using the composite material of the present invention involves first providing a composite material of the present invention, wherein the inorganic material is suitable for catalyzing the reaction of the reagent and then contacting the composite with the reagent. Suitable inorganic materials for the catalytic reaction of particular reagents can be identified simply on the basis of conventional catalysts for the particular reagent. For example, vanadium-containing compounds, such as vanadium pentoxide, a well-known catalyst for the reaction of S02 to S03 with molecular oxygen, can be used as the inorganic material in the composite material of the present invention to catalyze that reaction. Optimal reaction conditions for the use of the composite materials of the present invention can be processed for each reagent and individual inorganic material by methods well known in the art. Some reactions wherein the composite materials of the present invention can serve as catalysts and effective process and apparatus, suitable for performing the catalysis using the composites of the present invention include those described in Patchornick et al., J. Chem. Soc. Chem. Commun., 1990: 1090 (1990) ("Patchornick"), U.S. Pat. No. 5,534,472 issued to Winslow et al. ("Winslow"), and patent of E.U.A. No. 5,420,313 issued to Cunnington ("Cunnington") and others, which are incorporated herein by reference. Illustrative reactions that can be catalyzed with the appropriate choice of inorganic or organic macromolecular networks include: the conversion of alkenes to epoxides using subsequent transition metal complexes; the conversion of alkenes to aldehydes using early transition metals such as titanium; selective oxidation of alcohols to aldehydes using subsequent transition metals. Again, the efficiency of these and other reactions can be tuned by own choice of metal and coordination environment, for example, the surrounding ligands and spherical charge of the surrounding polymer. As indicated above, transition metals are particularly useful metals to be incorporated into the composite materials of the present invention when the composite materials are to be used as catalysts. The only characteristics of each transition metal to catalyze different types of reactions should be considered. For example, the synthesis of Fischer-Tropsch ("FTS") of hydrocarbons was stimulated in 1974, when the crisis of oil supply was based mainly on the hydrogenation of CO to CH4. The pattern of transition metals within the transition metal periods of the Periodic Table shows variable activities of these metals. A description of the various transition metals and their usefulness for FTS is given in, for example, "Studies in Surface Science and Catalysis," volume 79 in Moulijn and others, editions, Catalysis, An Integrated Approach to Homogeneous. Heterogeneous and Industrial Catalysts, Elsevier Science Publishers B.V. (1993) ("Moulijn"), which is incorporated herein by reference. As a further example, the catalytic oxidation of sulfur dioxide and ammonia to produce sulfuric acid and nitric acid, respectively, is an extremely important industrial base process. Oxidative catalysis of ethylene and propylene epoxies and italic anhydrides among others are also examples of industrial-base catalytic conversions of alkenes through oxidative catalysis. An illustrative list of catalyst-based synthesis oxidants of important industrial materials, which can be synthesized with the composite materials of the present invention is provided by Moulijn on page 187, which is incorporated herein by reference. For example, the present invention can be used to catalyze the oxidation of an oxidizable substrate. Oxidizable substrates include substituted or unsubstituted alkyl or aryl alkyl alcohols, such as methanol (in which case, the product resulting from the oxidation is formaldehyde or formic acid or both), or a substituted or unsubstituted alkyl or arylalkyl, such as o-xylene (in which case, the oxidation product is phthalic anhydride, a useful precursor in the preparation of many polymers). The reaction is carried out by contacting the oxidizable substrate with the oxidizing agent in the presence of a composite material of the present invention or a composite material prepared according to the method of the present invention. Any suitable oxidation agent can be used. Preferably, the oxidizing agent is a gas, such as oxygen gas (02), optionally mixed with an inert gas, such as helium, nitrogen or argon. In many cases, environmental air can be used as the oxidation agent. The composite material can be in any suitable form, for example, sheets, beads, fibers, powders, and the like. Preferably, the polymer of the composite material is a fluoropolymer (e.g., MFA, PFA, PVDF, PTFE, ECTFE or FEP). Composite materials that include an inorganic material containing titanium or vanadium disposed in the natural free volume of the polymer are particularly useful for catalyzing the oxidation reactions of the present invention. In some cases, the oxidation reactions can be advantageously carried out in the presence of a co-reductant. Examples of suitable co-reductants include iodoisobenzene, which is commonly used in the epoxidation of olefins in the presence of metalloporphyrins and peroxides (e.g., hydrogen peroxide or benzoyl peroxide). In many cases, it is desirable to inflate the composite material of the present invention during or before use as a catalyst to increase the diffusion rate of the reagent in the composite. This can be done by exposing the composite material to standard supercritical conditions. For example, the composite material can be placed in a container capable of withstanding high pressures, such as the pressures commonly encountered in supercritical catalytic processes. The container is then charged with a supercritical fluid under supercritical conditions, such as carbon dioxide at 175.75 kg / cm 2, and the pressure is maintained for a period ranging from 1 to 100 hours. As a result of being exposed to these supercritical conditions, the composite material swells. However, in contrast to prior art materials where impregnation is performed under supercritical conditions, the inorganic or organic materials infused according to the methods of the present invention do not diffuse out of the polymer after subsequent exposure of the material composed to supercritical conditions. The effectiveness of the composite materials of the present invention as heterogeneous catalysts is due to the residence of the inorganic material along the polymer structure which is on the surface of the free volume and which is accessible to the gas phase molecules which they will be catalytically transformed.

This is in contrast to conventional inorganic-organic mixtures, where the mixing and combination procedures fail to control the placement of the inorganic phase and where, in view of the restrictions of free energy at the surface, it is believed that the Mixing and curing procedures could probably lead to materials that may have little or no inorganic material on the surface of the free volume. The present invention also relates to a method for preventing the incrustation of a surface by organisms. In marine (for example, saltwater) or aquatic (for example, freshwater) environments, surfaces that are in continuous or intermittent contact with these environments are frequently subjected to fouling, such as by binding or growth of organisms on the surfaces. In a method of the present invention, the incrustation of the surface is prevented by applying, to the surface, a composite material of the present invention or a composite material made in accordance with the method of the present invention. For example, the incrustation formation of a surface is avoided according to the present invention by applying, to the surface, a composite material comprising a polymer having a free volume therein, and an inorganic or organic material disposed in the free volume of the polymer. Free volume, as explained above, includes natural free volume, free created volume, or both.

The composite material can be applied to the surface through any suitable method. For example, in one embodiment, the composite material may be provided in a sheet (ie, relatively flat) form. The sheet can then be brought into contact with the surface under effective conditions to bond the sheet to the surface. Illustratively, the sheet can be joined mechanically (for example, through nails, screws or rivets) or by adhering the sheet to the surface (for example, through glue or epoxy). In an alternative embodiment, the composite material may be provided in the form of beads or powder dispersed in an uncured resin. Suitable resins include those that can be cured through polymerization or entanglement. The composite material in the form of beads or powder dispersed in the uncured resin is brought into contact with the surface, such as by painting (e.g., by brushing or rolling), spraying, cathodically depositing or immersing. The uncured resin is then cured, such as by exposure to light or heat. The healing process can be completed, but should, to a minimum, be performed to a degree that is effective for bonding beads or powder of the composite material to the surface. Still alternatively, the uncured resin may be applied to the surface, such as by painting (e.g., by brushing or rolling), spraying, dipping or cathodically depositing, and then contacting the bead or powder of composite material with the resin not healed The resin is then cured to a degree that is effective to bond the beads or powder of composite material to the surface. In another embodiment, the composite material may be provided in the form of beads or powder dispersed in a suitable solvent (eg, ketones, ethers, hydrocarbon (eg, unsubstituted hydrocarbons or chlorinated hydrocarbons), and aromatic solvents (eg, benzene) , toluene or xylenes)). As used herein, "dispersed" includes "dissolved." The beads or powder of composite material dispersed in a suitable solvent is then contacted with the surface, such as by painting (e.g., by brushing or rolling), spraying, dipping or cathodically depositing, and the solvent is evaporated, such as by heating the surface or simply allowing the solvent to evaporate at room temperature. In another modality more, the composite material in pearl or powder form can be applied net with a coating method, which directly applies films or coatings of the beads or powders through thermal base spraying, cathodic deposition or immersion or through the use of high temperature plasma spray technology. In some situations, it may be advantageous to separate the surface that is being protected from the composite material, so that the catalytic activity of the composite material does not cause the surface to degrade. For example, when the surface being protected from fouling by organisms is a metal surface, it may be advantageous to first coat a barrier layer before applying the composite material of the present invention. Said barrier layers can be made of a non-reactive metal or, preferably, a polymer. When the surface to be protected from fouling by organisms is the surface of the polymer having a free volume therein, an alternative method of the present invention may be employed. In this method, the free volume of the polymer is evacuated, and the inorganic or organic molecules are infused to the free void volume of the polymer. This method is particularly suitable when the surface is the surface of a polymer object, such as a plastic pipe or a hull of a fiberglass boat or canoe. However, the method can be employed to prevent scale formation by organisms from surfaces made of metal or other non-polymeric objects by first depositing a polymer having a free volume on the surface of the object and then evacuating the free volume of the polymer and infusing the inorganic or organic molecules to the free volume evacuated. By adjusting the duration of the infusion step, one skilled in the art can easily infuse only the portion of the polymer near the exposed surface of the polymer, thereby, in effect, producing a barrier layer, which prevents the catalytic activity of the materials infused to degrade the metal surface of the object or non-metal. Suitable methods for evacuating and infusing polymeric materials include those described above with respect to the manufacture of the composite materials of the present invention. Although the mechanism by which scale formation is prevented in the above methods is not fully understood, it is believed that the inorganic or organic material contained in the free volume of the polymer either directly inhibits the growth of organisms on the composite surface. or indirectly catalyzes an unidentified reagent on the surface of the composite material, which resists formation of scale via binding or growth. For example, when the inorganic or organic material is an inorganic material containing vanadium, titanium or other metal capable of catalytically depositing the dioxygen (ie, 02), it is hypothesized that any organism that is aerobic (ie, requires dioxygen for respiration) will not thrive or proliferate on said surface, since the respiratory cycle of the organism will be interrupted through the consumption of oxygen radical species created when the metal (for example, vanadium or titanium) divides the dioxygen. Therefore, it is contemplated that composite materials containing metals capable of dividing the dioxygen, such as vanadium, particularly could be effective, especially against the formation of scale by aerobic organisms. Using this method, the formation of scale by marine organisms, aquatic organisms, and microorganism (eg, bacteria, protozoa, algae, and the like) is avoided or reduced. Since crustaceans (particularly barnacles) and mussels (particularly zebra) are especially devastating for aquatic and marine surfaces, it is expected that the method of the present invention will find particular utility to prevent the formation of scaling of these surfaces by crustaceans or mussels. The method of the present invention can be used to prevent scale formation by organisms from a variety of surfaces, including those of waterborne vessels (e.g., boats, boats, barges, and canoes), components of said containers carried by water (eg, helmets, propellers, anchors, and anchor chains) and fixed objects that are in contact with aquatic or marine environments (eg, pillars, buoys, underwater bridge components, oil rigs, and drilling platforms) , shut-off gates and associated components, underwater pipes and cables When the composites of the present invention are used to prevent the formation of scale of surfaces by organisms, it is preferred that the polymer be a fluoropolymer, since the surfaces of the fluoropolymer have low friction coefficients and are inherently non-sticky and hydrophobic. previously liquefied, it is believed that the catalytic properties of the composite materials of the present invention are improved when the fluoropolymers constitute the polymer. In this way, the improved catalytic activity provided by the fluoropolymer, coupled with the non-tacky character of the surface of the fluoropolymer, makes a surface having an improved resistance to the proliferation of organisms and is easy to clean. In cases where the composite material of the present invention is used as an anti-fouling coating in water-borne containers, the low coefficient of friction of the fluoropolymer also reduces the drag experienced by said containers. The anti-fouling method of the present invention is particularly advantageous in environments that are sensitive to the toxic effects of heavy metals. Conventional anti-scaling marine coatings generally include toxic materials (eg, copper or tin). These conventional coatings operate mainly when the toxic materials are ingested by marine organisms, which, due to the effect of the toxic material, subsequently die. The ingestion process can take place either by ingestion via direct contact of the organism with the coating or via the ingestion of toxic material, which has been leached from the antifouling coating into the environment. In the antifouling method of the present invention, it is believed that no toxic material is deposited in the environment. In addition, since the composites of the present invention do not operate by releasing the active ingredient (e.g., metal), it is expected that the composite material will have a much greater anti-fouling life. This is especially important in applications that require the surface to be below water for extended periods (for example, underwater components of bridges and oil rigs, pillars, hulls of large ships or pipelines or underwater cables). The present invention also relates to objects having a surface. All or a portion of the surface includes a polymer, which has a free volume therein, and, in the free volume of the polymer, an inorganic or organic material is disposed. Suitable objects include those that are in continuous or intermittent contact with water and, therefore, are particularly susceptible to fouling by organisms. Other suitable objects are those that are exposed to moisture and / or humid environments. For example, the object can be a container that is carried by the water, which comprises a helmet having attached thereto, at least a portion of the outer surface of the helmet, a composite material according to the present invention. As used in this, hull includes all portions of a boat, boat, barge, or other vessel carried by the water below the line of the platform, including those portions that are typically below the water line, as well as those portions that are typically above the water line, but which intermittently come in contact with the water. Also included within the meaning of hull, as used herein, are those portions of the container carried by the water that are in contact with the hull, such as propellers, anchors, anchor chains, pipe, cables and the like.

Another suitable object according to the present invention is a pipe. The pipe includes a pipe wall having an inner surface and an outer surface and, in addition, a composite material according to the present invention, attached to at least a portion of the inner surface, outer surface, or both, of the pipe. pipeline. For example, in cases where the pipeline is to be used for the transmission of fresh or salt water, the pipeline must have its inner surface, or a portion thereof, coated with the composite material. In cases where the pipeline will be used below the water, the composite material will be attached to the outer surface of the pipe. In certain circumstances, such as when the pipeline transmits water to or from an underwater site (for example, inlet or discharge pipes used in power plant cooling operations), a pipeline may be preferred having the composite material attached to its surfaces interior and exterior. Water inlet pipes for domestic or municipal water treatment facilities are often plagued by the buildup of organisms (particularly zebra) in the pipeline. In such situations, a pipe having the composite material of the present invention disposed at the entrance portion thereof could be advantageous. Fixed structures that have supports, the surface of said supports is in continuous or intermittent contact with water, are also considered as suitable objects. A composite material of the present invention is attached to at least a portion of the support surface. Fixed structures, as used herein, include drilling platforms, oil production rigs, bridges, and pillars. The waterborne containers, pipes and structures of the present invention can be prepared using the methods described above to apply the composite material of the present invention to surfaces. In cases where containers carried by water, pipes, or structures have polymer surfaces, which include a polymer having a free volume therein, the container carried by the water, pipes or structures of the present invention can be prepared by evacuating the free volume of the polymer and infusing inorganic or organic molecules into the free volume, as described above. Although the anti-fouling coatings described above have been illustrated in terms of pipes, water-borne vessels and structures, they can be used on all types of surfaces that are exposed to water, such as standing water, moisture or damp conditions, or other environments conducive to marine, aquatic or microorganism growth. Examples of such surfaces include sumps, pool liners, backstops, pond linings, roofing materials, trays, floor and concrete surfaces. Since medical devices and equipment (e.g., catheters or temporary or permanent in vivo mechanical devices) are frequently exposed to environments that promote microbial growth, it is contemplated to apply the composite materials of the present invention to the surfaces of these devices and equipment. . The present invention, in another aspect thereof, relates to oxyhalopolymer composite materials and oxyhalogenated nonhalopolymer composite materials on the surface. As used herein, "oxyhalopolymers" refers to bulk halopolymer materials whose surface is modified with hydrogen atoms and oxygen atoms or oxygen-containing radicals. As used herein, oxyhalopolymer composites refer to oxyhalopolymers in which free volume an inorganic or organic material is disposed. As used herein, halopolymers refers to bulk materials of halopolymer, which have halogen atoms on the surface. As used herein, halopolymer composite materials refer to halopolymers in which free volume an organic or organic material is disposed. As used herein, "non-halopolymers" refers to polymeric bulk materials other than halopolymers. As used herein, non-halopolymer composite materials refer to non-halopolymers in which free volume an inorganic or organic material is disposed. As used herein, non-halogenated halopolymers on the surface refer to non-halopolymers whose surface is modified with molecularly bonded halogen atoms or a halogenated hydrocarbon or halohydrocarbon film. The outer surface of the halogenated non-halopolymers on the surface in this manner has halogen atoms on the surface. As used herein, halogenated non-halo polymeric surface materials refer to non-halogenated halopolymers on the surface in which free volume an inorganic or organic material is disposed. As used herein, non-halohalogenated halopolymers on the surface refer to non-halogenated halo-polymers on the surface whose halogen atoms molecularly bonded at the surface or halogen atoms of halogenated hydrocarbon or halohydrocarbon surface are modified with hydrogen atoms and atoms of oxygen or oxygen-containing radicals. As used herein, non-halohalogen-containing surface-halogenated composite materials refer to non-halohalogenated halo-polymers on the surface in which free volume an inorganic or organic material is deposited. As used herein, "polymers" refers to one or more of the halopolymers, not halopolymers, oxyhalopolymers, non-halogenated halopolymers on the surface, non-halogenated above-surface oxyhalopolymers. As used herein, "polymer composite materials" refers to one or more of the halopolymer composite materials, non-halo polymer materials, oxyhalopolymer composite materials, halogenated non-halogenated surface-based composite materials, and non-halo composite materials. Halopolymer oxyhalogenated on the surface. The present invention relates to an oxyhalopolymer composite material. The oxyhalopolymer composite material includes an oxyhalopolymer having a free volume therein, and an inorganic or organic material disposed in the free volume of the oxyhalopolymer. The present invention also relates to an oxyhalogenated non-halo polymer material on the surface. The composite material includes a non-homopolymer oxyhalogenated on the surface, which has a free volume therein. The non-halohalogenated halo-polymer material on the surface further includes an inorganic or organic material disposed in the free volume of the non-halohalogenated halo-polymer on the surface. The oxyhalopolymer can be an organic-based halopolymer or an inorganic-organic hybrid halopolymer. Suitable organic base halopolymers for use in the composite materials of the present invention can be homopolymers, copolymers, multi-component polymers or combinations thereof, provided at least some of the homopolymers, copolymers, polymers of multiple components or combinations of them contain a halopolymer. Examples of suitable halopolymers, as well as methods for their preparation or manufacture such as halopolymers include those described above with respect to the composites of the present invention. Non-halopolymers suitable for use in the practice of the present invention include non-organic based halopolymers or non-organic, inorganic hybrid halopolymers. The non-halo-polymers of organic base can be homopolymers, copolymers, polymers of multiple components or combinations thereof, provided they do not contain significant amounts of halopolymer. That is, the non-halopolymer can include halopolymers, but only in insufficient amounts to make the chemical and physical properties of the non-halopolymer closer to those of a pure halopolymer than those of a pure non-halopolymer. Suitable non-organic halopolymers as well as methods for obtaining or making these materials include those described above with respect to the composites of the present invention. The halopolymer and non-halopolymer may alternatively be an organic-organic hybrid polymer or a mixture of organic polymer and an inorganic-organic hybrid polymer, such as those described above. These contain a variety of materials, which are known in the art to modify the properties of the polymer, and can be used in any suitable form. Illustrative surface modifying materials and suitable forms include those described above together with the composite materials of the present invention. The materials that make the polymer (ie, the halopolymer, the oxyhalopolymer, the non-halopolymer, the non-halogenated halo-polymer on the surface, or the nonhalo-halogenated halo-polymer on the surface), which are an organic polymer or an inorganic-organic hybrid material , they contain a free volume (for example a natural free volume or a created free volume). In addition to having a free volume therein, the polymer used in the method of the present invention also has a halogenated surface. In the case where the polymer is a halopolymer, the halopolymer will naturally have a halogenated surface (i.e., a surface with halogen atoms of exposed surface). In the case where the polymer is a non-halopolymer, the surface may contain molecularly bonded halogen atoms (i.e., halogen atoms directly bonded to the carbon base structure of the non-halo polymer on the surface of the non-halo polymer), or, alternatively, the surface can be modified with a halogenated hydrocarbon film or haiohydrocarbon. The thickness of the film is not critical to the practice of the present invention and can vary from several microns to several centimeters, depending on the size of the non-halopolymer on which it is coated and the application to be given. Preferred halogenated hydrocarbon or haiohydrocarbon films are those that are polymeric in nature, for example, those made from the halopolymers set forth above. As indicated above, a portion of the surface halogen atoms of the oxyhalopolymer composites and the nonhalopolymer oxyhalogenated composite materials on the surface of the present invention are substituted with hydrogen atoms and oxygen atoms or oxygen-containing radicals . In this regard, the object is to have either oxygen or oxygen containing groups disposed on the halopolymer or on the halogenated surface of non-halopolymer or halogenated hydrocarbon or halohydrocarbon in place of some of the halogen atoms to form a stable intermediate material. Generally, oxygen atoms are not directly bonded to the base structure of the polymer per se (for example, to form a COC base structure), but only substitute existing halogen atoms, which are dependent on the base structure of the carbon. Representative oxygen-containing radicals suitable for use in the composites of the present invention include hydroxyl (-OH), ether (COC), epoxide (-O-), aldehyde (-CHO), ester (-C (O) O -), and carboxylic acid (-COOH). Other suitable oxygen-containing radicals include oxo, alkoxy (e.g., methoxy, ethoxy and propoxy), radicals having the formula R'-CO-, wherein R 'is hydrogen or alkyl (particularly lower alkyl of 1 to 5 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and the like), and combinations thereof. In addition, oxygen-containing radicals can also take the form of POy or SiOy >;, where y and y 'are 2-3. Oxygen mixtures or not more oxygen-containing radicals and mixtures of two or more oxygen-containing radicals may also be present on the surface. In general, the oxygen sites on the surface of a halopolymer or halogenated non-halo polymer on the surface need only have such a concentration that the oxygen functionality and the resulting base structure of the polymer is stable. Typically, from about 1 to about 98%, preferably from about 3 to about 70% of the original surface halogen atoms on the halogenated halopolymer or halogenated non-halo polymer at the surface are replaced with oxygen or oxygen containing groups. Oxyfluoropolymers, when produced through radio frequency luminescent discharge ("RFGD"), exhibit a wide variety of surface-free energy increases where, for example, a fluoropolymer such as PET with? C of approximately 18 dynes / cm at 20 ° C can be increased to about 40 dynes / cm to a depth of between about 10 to about 100 Á for increased wettability and other surface properties relative to the surface free energy of the material. Even with such increases in surface free energy, the hydrophobic properties of the original material are not destroyed. That is, the composite materials of the present invention, which have hydrogen, oxygen and fluoride functionalities that are covalently bonded to the carbon polymer structure, can still inhibit the formation of surface fouling, penetration, and moisture by liquids with high surface tensions (for example, having surface voltages greater than about 50 dynes / cm), such as water and other similar polar solvents, while they can be wetted by liquids having low surface tensions (e.g. surface less than 50 dynes / cm), such as plasma in the blood and other non-polar organic solvents. As indicated above, the oxyhalopolymer composite and the oxyhalogenated non-halo polymeric material on the surface of the present invention further include an inorganic or organic material, which is disposed in the free volume of the polymer, preferably in the natural free volume. of the polymer. Details regarding the amount, physical and chemical characteristics, and the subsequent treatment of the infused inorganic or organic material, as well as other aspects regarding the interaction between the infused materials and the polymer in which it is infused, can be found here above. The oxyhalopolymer composites of the present invention can be prepared, for example, by the methods that follow, to which the present invention also relates. A method for making an oxyhalopolymer composite material according to the present invention includes providing an oxyhalopolymer, which has a free volume therein, and in which at least a portion of the halogen atoms on the surface of the oxyhalopolymer are substituted. with hydrogen atoms and oxygen atoms or radicals that contain oxygen. The free volume of the oxyhalopolymer is evacuated, and the inorganic or organic molecules are infused into the voided free volume of the oxyhalopolymer. The oxyhalopolymer can be prepared by providing a halopolymer and modifying the halogen atoms on the surface of the halopolymer under effective conditions to replace at least a portion, typically from about 1 to about 98%, preferably from about 3 to about 70% of the halogen atoms on the surface of the halopolymer with hydrogen atoms and oxygen atoms or oxygen-containing radicals. In a preferred embodiment, the halogen atoms of the halopolymer surface are modified through radio frequency luminescent discharge of a vapor gas under vacuum by contacting the halopolymer with a gas / vapor plasma mixture., while exposing the halopolymer to at least one radio frequency luminescent discharge under vacuum and under effective conditions to replace at least a portion of the halogen atoms of halopolymer with covalently bonded hydrogen atoms and oxygen atoms or oxygen-containing radicals . In another method for making an oxyhalopolymer composite material according to the present invention, a halopolymer composite material is provided. The halopolymer composite material includes a halopolymer having a free volume therein and an inorganic or organic material disposed in the free volume of the halopolymer. The halogen atoms on the surface of the halopolymer composite material are then modified under effective conditions to replace at least a portion of the halogen atoms on the surface of the halopolymer composite with hydrogen atoms and oxygen atoms or oxygen-containing radicals . In a preferred embodiment, the halogen atoms on the surface of the composite material of the halopolymer are modified through a radio frequency luminescent discharge of a vapor gas under vacuum by contacting the halopolymer composite with a gas / vapor mixture. , while exposing the halopolymer composite material to at least one radio frequency luminescent discharge under vacuum and under effective conditions to replace at least a portion of the halogen atoms of the halopolymer composite with covalently bonded hydrogen atoms and atoms of oxygen or radicals containing oxygen. The halopolymer composite material used in this method can be prepared by providing a halopolymer having a free volume therein, evacuating the free volume of the halopolymer, and infusing inorganic or organic molecules to the free void volume of the halopolymer. The present invention also relates to methods for making oxyhalogenated non-halo polymeric materials on the surface. One of these methods includes providing an oxyhalogenated non-halo polymer on the surface that has a natural free volume therein. The surface of the nonhalopolymer oxyhalogenated on the surface is oxyhalogenated. That is, the surface is modified with molecularly bonded halogen atoms or a halogenated hydrocarbon film or haiohydrocarbon, and at least a portion of the molecularly bonded halogen atoms or the halogen atoms on the surface of the halogenated hydrocarbon film or haiohydrocarbons, are substituted with hydrogen atoms and oxygen atoms or oxygen-containing radicals. The method further includes evacuating the free volume of the oxyhalogenated non-halo polymer on the surface and infusing inorganic or organic molecules into the voided free volume of the non-halogenated halohydrocarbon on the surface. The non-halohalogenated halopolymer on the surface can be prepared by providing a non-halogenated halo-polymer on the surface, which has a free volume therein and which has a surface that is modified with molecularly bonded halogen atoms or a halogenated hydrocarbon or halohydrocarbon film . In a preferred embodiment, the halogen atoms on the surface of the halogenated non-halo polymer on the surface are modified by contacting the halogenated non-halo polymer at the surface with a gas / vapor plasma mixture, while exposing the halogenated non-halo polymer on the surface. surface to at least one radio frequency luminescent discharge and under effective conditions to replace at least a portion of the halogen atoms of the halogenated non-halo polymer surface at the surface with covalently bonded hydrogen atoms and oxygen atoms or radicals that they contain oxygen. The non-halogenated halogenomers on the surface suitable for use in this method can be made by providing a non-halo polymer (which has free volume therein) and contacting the non-halo polymer surface with halogen atoms or a halogenated hydrocarbon or haiohydrocarbon material under conditions effective to molecularly bond halogen atoms or a halogenated hydrocarbon film or haiohydrocarbon to the surface of non-halopolymer. In cases where the non-halohalogenated halopolymer on the surface includes a non-halo polymer having a surface that is modified with a halogenated hydrocarbon film or haiohydrocarbon (opposite, for example, to molecularly bonded halogen atoms) and wherein both the non-halopolymer and the halogenated hydrocarbon film or haiohydrocarbon have free volumes therein, the method can, optionally, also include the evacuation of the free volume of the hydrocarbon film halogenated or haiohydrocarbon and the infusion of inorganic or organic molecules in the free volume evacuated from the halogenated hydrocarbon film or haiohydrocarbon. In this manner, both the non-halopolymer and the halogenated hydrocarbon or halohydrocarbon film disposed therein can be fused with the inorganic or organic molecules. In another method for making an oxyhalogenated non-halo polymer material on the surface according to the present invention, a halogenated non-halo polymer material is provided on the surface. The halogenated non-halopolymer composite material on the surface includes a halopolymer having a free volume therein and an inorganic or organic material disposed in the free volume of the non-halo polymer. The halogenated non-halo polymer material on the surface also has a surface that is modified with molecularly bonded halogen atoms or with a molecularly bonded halogenated hydrocarbon or halohydrocarbon film. The method further includes modifying the halogen atoms on the surface of the halogenated non-halo polymer material on the surface under effective conditions to replace at least a portion of the halogen atoms on the surface of the halogenated non-halo polymer material on the surface with hydrogen and oxygen atoms or radicals containing oxygen. In a preferred embodiment, the halogen atoms on the surface of the halogenated non-halo polymeric material on the surface are modified by contacting the halogenated non-halo polymer material on the surface with a gas / vapor plasma mixture, while exposing the halogenated non-halo polymer material on the surface to at least one radio frequency luminescent discharge under vacuum and under conditions effective to replace at least a portion of the halogen atoms on the surface of the halogenated non-halo polymer material in the surface with covalently bonded hydrogen atoms and oxygen atoms or oxygen-containing radicals. Non-halogenated surface-halogenated composite materials suitable for use in the practice of this method of the present invention can be prepared, for example, by providing a halogenated non-halo polymer on the surface having a free volume therein and having a surface that is modified with molecularly bound halogen atoms or a halogenated hydrocarbon film or haiohydrocarbon. The free volume of the non-halogenated halo-polymer on the surface is then evacuated, and the inorganic or organic molecules are infused into the free volume evacuated from the non-halogenated halo-polymer on the surface. In the case where the non-halogenated halo-polymer on the surface comprises a non-halopolymer having a surface that is modified with a halogenated hydrocarbon film or haiohydrocarbon (as opposed to molecularly bonded halogen atoms) and wherein both the non-halo polymer and the film Halogenated hydrocarbon or haiohydrocarbon have free volumes therein, the method can further include evacuating the free volume of the halogenated hydrocarbon film or haiohydrocarbon and infusing inorganic or organic molecules therein. Alternatively, non-halogenated surface halogenated composite materials can be prepared by providing a non-halopolymer composite material, which includes a non-halo polymer having a natural free volume and an inorganic or organic material disposed in the natural free volume of the non-halo polymer. The surface of the non-halo polymer material is then contacted with halogen atoms or a halogenated hydrocarbon film or haiohydrocarbon under conditions effective to molecularly bond the halogen atoms or a halogenated hydrocarbon film or haiohydrocarbon to the composite material surface. no halopolymer. In this method, the non-halopolymer composite material can be prepared by providing a non-halo polymer having a free volume therein, evacuating the free volume of the non-halo polymer, and infusing inorganic or organic molecules to the free volume evacuated from the non-halo polymer. Previously, methods were described to evacuate the free volumes, infuse the inorganic or organic molecules to the evacuated free volumes, and modify the inorganic or organic molecules infused into the free volume of the oxyhalopolymer, the halopolymer, the non-halogenated halo-polymer on the surface, no halopolymer, or the halogenated hydrocarbon film or haiohydrocarbon (generically referred to herein as "polymer"). Oxihalopolymers and oxyhalopolymer composites and non-halohalogenated halo-polymers on the surface and non-halohalogenated halo-polymer materials on the surface can be prepared, respectively, from halopolymers and halo-polymer and non-halogenated halo-polymer materials on the surface and halogenated non-halopolymer composite materials on the surface through a variety of techniques. A variety of methods for incorporating reactive oxygen functionality into halopolymers is available and is useful for this invention. These methods include plasma and corona discharge treatments, ion beam and electron beam bombardment, X-ray and gamma treatments, as well as a variety of wet chemical processes, including treatments with sodium in liquid ammonia or sodium naphthalene in glycol ether. or reduction in surface area with the benzoin dianion. All methods are described in detail in Lee et al., "Wet-process Surface Modification of Dielectric Polymers: Adhesion Enhancement and Metallization", I BM J. Res. Develop., 38 (4) (July 1994), Vargo et al. , "Adhesive Electroless Metallization of Fluoropolymeric Substrates" Science, 262: 1711-1712 (1993), Rye et al., "Synchrotron Radiation Studies of Poly (tetrafluoroethylene) Photochemistry", Langmuir, 6: 142-146 (1990), and Tan and others, "Investigated of Surface Chemistry of Teflon 1. Effect of Low Energy Argon Ion Irradiation on Surface Structure", Langmuir, 9: 740-748 (1993), which are incorporated herein by reference. For example, a suitable method for introducing the oxygen functionality involves exposing the surface halogen atoms of the halopolymer or halopolymer composite material or halogenated non-halo polymer to the surface or the halogenated non-halo polymer material on the surface to the actinic radiation, for example, ultraviolet, X-ray, or electron beam radiation, in the presence of oxygen-containing organic compounds commonly referred to as "organic modifiers". Examples of suitable organic modifiers include sodium 4-aminothiophenoxide ("SATP"), sodium benzhydroxide ("SBH"), disodium 2-mercapto-3-butoxide ("DDSMB"), and other strong reducing agents that facilitate abstraction of hydrogen or halogen in the presence of actinic radiation. In practice, the halopolymer or halopolymer composite material or halogenated non-halopolymer on the surface or halogenated non-halo polymeric material on the surface is immersed in one or more organic modifiers and simultaneously exposed to actinic radiation, such as UV radiation, during a prescribed period. Other details regarding this method for introducing oxygen functionality are described in, for example, the US patent. No. 5,051,312 issued to Allmer, which is incorporated herein by reference. Preferably, the oxyhalopolymer or oxyhalopolymer composite or the oxyhalogenated nonhalopolymer on the surface or the oxyhalogenated nonhalopolymer composite material on the surface is prepared by introducing the oxygen functionality onto the surface of the halopolymer or halopolymer composite or the halogenated nonhalopolymer into the surface or halogenated non-halopolymer composite material on the corresponding surface through RFGD of a gas-vapor under vacuum. In summary, the halopolymer or halopolymer composite material or the halogenated non-halo polymer on the surface or the halogenated non-halo polymer material on the surface in an atmosphere of a gas / vapor mixture is exposed to a single or a series of radio luminescent discharges frequency ("RFGD") at power loads less than or equal to 100 watts and pressures below 1 Torr, most preferably, about 50 to 200 mTorr. While not wishing to be maintained in any precise mode of action, the main mechanism of the plasma treatment process of the present invention is believed to involve the transfer of energy to the gaseous ions directly to form charged ionized gas species, i.e. , deposition of polymer ions in the adjoining gas-solid surface. Plasma gas ions of radio frequency luminescent discharge are excited through direct energy transfer by bombarding the gas ions with electrons. In this way, exposing the halopolymer or halopolymer composite material or the halogenated non-halo polymer on the surface or the halogenated non-halo polymer material on the surface to either a single or a series of gas / vapor plasmas of radio luminescent discharge frequency, from about 1% to about 98% of the halogen atoms on the surface are permanently removed in a controlled and / or regulated manner and replaced by hydrogen atoms together with oxygen atoms or low molecular weight oxygen containing radicals. Suitable gas-vapor plasmas include those containing mixtures of hydrogen gas, preferably ranging from about 20% to about 99% by volume, and from about 1% to about 80% by volume, of a liquid vapor, such as liquid vapor of water, methanol, formaldehyde, or mixtures thereof. Although hydrogen is required in all cases, by itself, hydrogen is insufficient to introduce both portions of hydrogen and oxygen into the base structure of the carbon polymer. A non-polymerizable vapor / H2 mixture is necessary to introduce the hydrogen and oxygen or functionalized portions required in the halopolymer by interrupting the morphology of the surface. The use of mixtures of pure gas, specifically H2 / 02, gave inferior results. Radio frequency luminescent discharge plasmas and representative operating conditions are provided in Table 1 below.

TABLE 1 Calculated Atomic Relations (ESCA) Composition Material Pressure Time Depth Mixture of (mTorr) (min.) (A) c / o C / F F / O Stoichiometry RFGD PTFE no - oc 0.45 or C2F23 modified PVDF no - oc 1.0 or C1F1 modified PTFE 2% H20 150 20 100 7.5 1.5 5.0 C15F10H18O2 modified 98% H2 PTFE 2% H20 200 10 100 8.6 0.91 9.7 C19F19H13O2 modified 98% H2 PTFE 20% MeOH (g) 150 30 100 3.0 1.5 2.0 Modified C6F4H602 80% H2 PTFE 20% MeOH (g) 200 100 9.3 2.0 4.7 C26F? 4H2902 modified 80% H2 PVDF modified 2% HzO 200 10 100 8.0 16.0 0.48 C16F? H2902 98% H2 Through the specific and controlled addition of the oxygen functionality via the radio frequency luminescent discharge, the oxyhalopolymer composites and oxyhalogenated non-halopolymer composite materials on the surface described here can remain resistant to scale formation and substance adsorption. , a properties that is consistent with the composite materials of unmodified halopolymer. However, unlike the unmodified halopolymer composites, such as PTFE composites, it was found that oxyhalopolymer composites have the unique ability to react cleanly and rapidly with various atoms, molecules or macromolecules throughout the groups. containing oxygen (eg, hydroxyl, carboxylic acid, ester, aldehyde, and the like) on the surface of the oxyhalopolymer composite to form refunctionalized oxyhalopolymer composites. This is especially advantageous since generally the halopolymer composite materials are inert to wet-surface and physical-chemical processes, at least to those which also do not induce a substantial surface morphological damage. In addition, due to the relative inertia of the oxyhalopolymer composite surfaces, the ability to incorporate reactive functionality onto their surfaces creates a material, which is specifically and controllably reactive, while also being inert to other chemical and environmental aspects, for example, adsorption of contaminants on the surface. Other details with respect to this method are described, for example, in the patents of E.U.A. Nos. 4,946,903, 5,266,309 and 5,627,079, all issued to Gardella and others (collectively "Gardella") and the patent application of E.U.A. Applicant Series No. 08 / 689,707 ("the application '707"), which are incorporated herein by reference. The surfaces of non-halopolymers and non-halopolymer composite materials can be halogenated through a variety of techniques. For example, halogenation can be carried out by adding fluorine or fluorocarbon coatings in the form of films. Non-halopolymers, such as polyolefins, for example, may have their halogenated surfaces either through gas phase surface halogenation processes, or, alternatively, they may be coated with a fluorocarbon-based plasma film. Both processes are well known and well documented in the prior art. Typically, with the fluorination of the gas phase, the non-halopolymers are exposed to a mixture of fluorine and nitrogen, whereby the fluorine atoms are bound to the surface of the polymer at the molecular level. Lagow and others in "Direct Fluorination: A 'New' Approach to Fluorine Chemistry", in Lippard, ed., Progress in Inorganic Chemistry, vol. 26, page 161 ff (1979), which is incorporated herein by reference, disclose gas phase surface fluorination methods to provide low surface energy, anti-reflective films to various commercially available base polymers, such as polyethylene, highly interlaced, polypropylene, poly (methyl) methacrylate, polycarbonate, polyester, polystyrene, and polymethylpentene. Clark et al., "Applications of ESCA to Polymer Chemistry 6. Surface Fluorination of Polyethylene - Application of ESCA to Examination of Structure as a Function of Depth", J. Polvm. Sci. Polvmer Chem. Ed., 13: 857-890 (1975), which is incorporated herein by reference, also describes the surface fluorination of polyethylene films. Other suitable gas phase fluorination methods are described in, for example, U.S. Patents. Nos. 3,988,491 and 4,020,223 issued to Dixon et al., Which are incorporated herein by reference. Methods for preparing films deposited with fluorocarbon plasma are also well documented in the literature. For example, Haque et al., "Preparation and Properties of Plasma-Deposited Films with Surface Energies varying Over a Wide Range", J. App. Polvm. Sci., 32: 4369-4381 (1986), which is incorporated herein by reference, discloses methods suitable for modifying polymer surface with thin films deposited in plasma using a radio frequency (RF) discharge system coupled in the form capacitor Useful and representative fluorinated gaseous materials include hexafluoroethylene, perfluoropropane, and hexafluoropropene. Nakajima et al., "Plasma Polymerization of Tetrafluoroethylene", J. APP. Polvm. Sci .. Vol. 23, 2627-2637 (1979), which is incorporated herein by reference, discloses methods for applying fluorocarbon coatings polymerized with plasma, which can be used to generate surfaces having, for example, low dielectric properties. and not corrosive. The patent of E.U.A. No. 4,718,907 issued to Karwoski et al., Which is incorporated herein by reference, describes useful methods for introducing fluorinated coatings for vascular grafts and other biomedical technologies. Alternatively, thin halopolymer films (from about 0.5 μm to about 50 μm) or thick (from about 50 μm to several mm) (for example, PTFE, PVDF, PFA, MFA, ECTFE, and PCTFE) can be attached to the halopolymers or non-halopolymer composite materials, for example, by methods that are well known in the art. Optionally, the oxyfluoropolymer composite or the oxyhalogenated non-halo polymeric material on the surface of the present invention can be refunctionalized. The types of functionalities by which the surfaces of the oxyfluoropolymer composite material or the non-halogenated oxyhalogenated composite material on the surface that can be re-functionalized include all those that can be reacted with hydroxyl, carboxylic acid, ester and aldehyde groups bonded through the base structure of the halopolymer or the halogen atom of the surface through reactions generally familiar to those skilled in the art. The reactivity of the surface of the oxyhalopolymer composite is determined by the particular type of oxygen functionality. For example, silanes of the organic or inorganic silicon-containing class react vigorously with hydroxyl groups to form a silanol bond or coupled link. However, the reaction rate is further improved due to the close proximity of the reactive oxygen functionality to the electronegative halogen atom (s). This is believed to provide extremely rapid reaction rates through the stabilization of the oxygen anion. Preferred refunctionalized oxyhalopolymer composites or surface oxyhalogenated non-halo polymer compounds can be prepared with a wide variety of organosilane coupling agents having the formula I: Y (CH2) nSi- (R) 3 wherein Y is selected from the group consisting of allyl, alkyl, haloalkyl, amino, mercapto, epoxy, glycidoxy, methacrylate, cyano, and -CH2C02-alkyl; n is from 0 to about 17; and R is independently selected from hydrogen, halogen, alkyl, haloalkyl, alkylamino, alkoxy and triaqylsilyloxy. Silane coupling agents are known materials, which are commercially available, such as from Petrarch Systems, Bristol, Pennsylvania.

The process for preparing the organosilicon-substituted oxyhalopolymer composites or the oxyhalogenated non-halo polymeric materials on the surface can be illustrated by the following reaction: (CH2) nY R-Si-R T ¡> H -CX2-CH-CX2- Y (CH2) nSi- (R) 3 -CXo-Cfi-CX wherein X is halogen (e.g., F or Cl), and R, Y, and n are as in the formula I. in the above reaction scheme, the first reagent represents the surface of the oxyhalopolymer composite material or the surface of the oxyhalogenated non-halo polymer material on the surface, and the second reagent is the organosilane coupling agent set forth above having the formula I. Preferably, the refunctionalized oxyhalopolymer composite materials and the oxyhalogenated nonhalopolymer composite materials on the surface are prepared using organosilane coupling agents, wherein Y is alkylamino, dialkylamino, mercapto, or glycidoxy and wherein R is chlorine, bromine , fluorine, alkyl having 1 to 4 carbon atoms, chloromethyl, monoethylamino, dimethylamino, methoxy, ethoxy, propoxy, butoxy, or trimethyl Isiioxy. Specific representative organosilanes are 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane to name a few. Other particularly useful functionalities that can be covalently linked with the oxyfluoropolymer composites and the oxyhalogenated non-halo polymeric materials on the surface of the present invention through sites containing reactive oxygen include fluorophores. As used herein, fluorophores include organic compounds that can fluoresce. Preferred fluorophores are the isothiocyanate-substituted types, such as fluorescein isothiocyanate ("FITC'Jm malachite green isothiocyanate, rhodamines (eg, tetramethylrhodamine isothiocyanate (" TRITC ")), and the like.Other isothiocyanate-substituted fluorophores are described in Haughland, Handbook of Fluorescent Probes and Research Chemicals, Molecular Probes, Inc. (1989), which is incorporated herein by reference and are available from Molecular Probes, Inc. Oxyhalopolymer composite materials and non-halohalogenated halo-polymer materials in The surface which are functionalized with isothiocyanate-substituted fluorophores are especially useful in a wide variety of probes and sensors, such as for nucleic acids.In addition to the oxyhalopolymer composites refunctionalized with fluorophore and organosilicon and the oxyhalogenated nonhalopolymer composite materials in the surface, other examples Representatives include alkali metal derivatives of the oxyhalopolymer composites and the oxyhalogenated non-halo polymeric materials on the surface, such as those having the formula: MI or -CX2- + CH ~ CX2- wherein M is an alkali metal (eg, Li, Na and K), and X is a halogen, particularly F. These oxyhalopolymer composites and the non-halohalogenated halo-polymer composite materials on the surface they can be prepared, for example, by reacting alkali metal hydroxide solutions (eg, LiOH, NaOH, KOH, and combinations thereof) with the oxygen-containing groups of the oxyhalopolymer composites and the composite materials of non-halohydrocarbon oxy-halogenated on the surface. Alkali metal oxyhalopolymer composite materials and surface oxyhalogenated non-halo polymer compounds are useful as cell separators in electrochemical cells, such as energy production cells (for example, batteries). Other details regarding refunctionalization can be found in, for example, the US patent. No. 5,266,309 issued to Gardella, Jr., et al., Which is incorporated herein by reference. As used herein, oxyhalopolymers, oxyfluoropolymer composites, non-halohalogenated halopolymers on the surface, and oxyhalogenated non-halo polymeric composites on the surface of the present invention include those containing oxygen or oxygen-containing radicals, which they have been refunctionalized as described above. The oxyfluoropolymer composite or the oxyhalogenated non-halo polymer material on the surface of the present invention can optionally be metallized with one or more transition metals. The transition metals are preferably bonded covalently to the oxyfluoropolymer composite or the oxyhalogenated non-halo polymer material on the surface via oxygen or oxygen-containing radicals, which replace the surface halogen atoms of the composite material of oxyfluoropolymer or the composite material of nonhalopolymer oxyhalogenated on the surface. When metallized, as described above, oxygen or oxygen containing radicals are preferably present not only on the immediate surface, but also at a depth of about 10A to about 200A. This will form a molecular layer of the transition metal bound, preferably covalently, to the oxygen sites or a multi-molecular transition metal film from about 10A to more than about one millimeter in thickness stabilized by an initial molecular metal layer. of Transition. The oxyfluoropolymer materials and the oxyhalogenated non-halo polymeric materials on the surface of the present invention include those containing oxygen or oxygen-containing radicals that have been metallized as described above. The metallized oxyhalopolymer materials and the oxyhalogenated non-halo polymer materials on the surface of the present invention can be referred to herein as metallohalopolymers ("MHPs"). Representative MHPs include those that contain, on their surface, one or more non-terminal units of repeating formulas: - where M is a transition metal; Z is a halogen (eg, fluorine, chlorine), hydrogen, - (CH2) and CH3, -CH3 or -OR; R is hydrogen, - (CH2) and CH3 or -CH3; and it is from 1 to 20; X is a methylene group optionally substituted with one or two halogen atoms (eg, CF2, CFCI, CCI2, CFH, CCIH and CH2); n is from 10 to 1000; t is from 2 to 3; and m is from 0 to 1000. The metals are capable of being covalently bound in controlled amounts, and with predetermined valences. The concentration of the transition metal introduced into the polymer can be controlled, for example, through kinetics, wherein the reaction rate depends on a variety of conditions, including (i) the solution chemistry used; (ii) the binding strength of the ligand on the starting material of the organometallic complex, which is dissociated during the reaction to form the MHP, and (iii) the use of the gas phase opposite to the solution phase (e.g. , the solution phase can react to form metallooxo functional groups on the surface of the oxyfluoropolymer, while a chemical vapor deposition can react to form both a metallooxo bond plus a deposit of an additional metal overlay on the metallooxo functionality) . Alternatively, the metal concentration of the MHP can be controlled by the amount of oxygen functionality initially present in the starting oxyfluoropolymer material, which can be controlled through the methods described by Gardella and in the U.S. patent. No. 5,051,312 issued to Allmer, which are incorporated herein by reference. The methods for controlling the oxidation state of the MHP metal are also varied. For example, an Rh + 3 MHP can be constructed according to the invention by depositing rhodium from an aqueous solution containing RhCl 3, wherein the oxidation state of the rhodium in the starting organometallic complex is +3. Alternatively, an Rh ° MHP can be made by depositing RhCl3 from a solution containing ethanol. In this case, the Rh + 3 of the organometallic starting complex is reduced by the presence of alcohol during the reaction to the oxyhalopolymer composite or the non-halohalogenated non-halo polymer material on the surface in order to form the Rh-MHP. In this way, in this case, control of the oxidation state can be achieved by adding an appropriate reducing agent to the reaction solution, which will effectively reduce the oxidation state of the starting metal contained in the organometallic starting material. In general, the oxidation state of the metal contained in the organometallic starting material can be conserved and, in this way, further controlled by selecting an organometallic starting material containing a transition metal in the desired oxidation state. Thus, for example, to make an MHP with Cu + 2, an organometallic starting material CuCI2 can be treated with an oxyhalopolymer composite material or an oxyhalogenated non-halo polymer material on the surface by exposing the oxyfluoropolymer composite or a composite material of non-halohalogenated halo-polymer on the surface to a millimolar solution of CuCl2 in a suitable solvent (eg, dimethylformamide ("DMF"). A Cu + 1 MHP can be prepared by exposing an oxyfluoropolymer to a millimolar solution of CuSCN in NH4OH 0.5 M. Cu MHP can be prepared by adding an effective reducing agent to the reaction solutions or by immersing Cu + 1 or Cu + 2 MHP in a bath containing an appropriate reducing agent for copper, such as NaBH4. the oxidation state of the transition metal of the MHPs of this invention comprises using the resistance of the ligands making a material The starting point of the organometallic complex. For example, Cr (CO) 6 (chromium hexacarbonyl) represents Cr in a zero oxidation state. Carbonyl ligands bind relative and weakly, so that all six of them can be released during the reaction with an oxyhalopolymer composite material or an oxyhalogenated non-halo polymer material on the surface to produce a C + 6 MHP. Alternatively, the chromium tristrialkylphosphine chloride (III) ((PR3) 3 CrCl3) has three labile chlorine ligands and three relatively stable trialkyl phosphine ligands. After reaction with an oxyfluoropolymer, the chromium in the chromium tristrialkylphosphine chloride (III) loses all three chlorine ligands but retains all three trialkyl phosphines. As a result, a Cr + 3 MHP is produced. It will be understood that the above-described refunctionalization or metallization processes can occur at any stage of the above described process of the present invention to make the oxyhalopolymer composite material or the oxyhalogenated non-halo polymer material on the surface once the oxygen functionality has been introduced to the surface of the polymer or halogen or halogenated polymer composite material. For example, metallization or re-functionalization can be performed on the oxyhalopolymer composite material or the oxyhalogenated non-halo polymeric material on the surface. Alternatively, the metallization or re-functionalization may be carried out subsequent to the modification of surface halogens of the halopolymer or non-halogenated halopolymer on the surface, but before evacuation and infusion with the inorganic or organic material. In some cases, depending on the nature of the infused inorganic or organic material, the metallization (or re-functionalization) and infusion can be performed in a single step, simply by contacting the oxyhalopolymer with or without halogenated oxy-polymer on the surface with the inorganic or organic material under conditions that are effective both for infusing inorganic or organic material into the voided free volume and reacting with surface oxygen or oxygen-containing radicals. Other details regarding the metallization of halogenated surfaces containing covalently bound oxygen or oxygen-containing radicals can be found in, for example, Applicant's 707 application, which is incorporated herein by reference. The co-pending application 707 of the applicants, which is incorporated herein by reference, also describes the uses that can be given to the metallized oxyhalopolymer composite material or to the oxyhalogenated non-halo polymer material in the metallized surface of the present invention. The metallizations and refunctionalizations of the oxyhalopolymer composite material or the oxyhalogenated non-halo-polymer composite on the surface can be on the entire exposed surface or in selected regions. For example, the regions selected for metallization or re-functionalization may be in the form of a predetermined pattern. The metallization and refunctionalization in predetermined patterns can be effected using oxyhalopolymers, oxyhalopolymer composites, non-halohalogenated halopolymers on the surface, or surface-free, halohalogenated non-halo polymer materials whose surface halogen atoms are substituted with oxygen or radicals that they contain oxygen in the predetermined pattern desired. These oxyhalopolymers, oxyhalopolymer composites, non-halohalogenated halopolymers on the surface, or oxyhalogenated non-halogenated composite materials on the surface, in pattern, can be produced by masking the halopolymer, halopolymer composite material, non-halogenated halopolymer on the surface, or material composed of non halogenated halopolymer on the surface and introducing oxygen functionalities to the halogen or its halogenated surface, such as by RFGD of a gas vapor. After exposure of the masked halopolymer or halopolymer composite material or the halogenated non-halo polymer material on the surface or non-halogenated halo polymer on the surface, only unmasked portions have oxygen or oxygen-containing radicals on the surface. When the oxyhalopolymer composites or the patterned oxyhalopolymers, or the oxyhalogenated non-halo polymer materials on the surface in patterns or the non-halohalogenated halopolymers on the surface are exposed to metallization or re-functionalization conditions, as described above, the metallization or Refunctionalization takes place only in regions that have oxygen or oxygen-containing radicals on the surface. In cases where a non-halopolymer is used, the metallized or functionalized pattern can also be controlled using a non-halopolymer, which is modified, in the predetermined pattern, with molecularly bonded halogen atoms or a halogenated hydrocarbon film or haiohydrocarbon. When the oxygen functionality is introduced into said non-halogenated halo-polymer on the surface, only those portions of the non-halo polymer surface which have been halogenated on the surface will have oxygen or an oxygen-containing radical, and, therefore, after metallization or refunctionalization, an oxyhalogenated non-halo polymer material is produced in the metallized or pattern functionalized surface or an oxyhalogenated non-halo polymer in the patterned or refunctionalized surface. As implicit in the above discussion, the modification of the surface of the non-halopolymer substrate with molecularly bonded halogen atoms or a halogenated hydrocarbon film or haiohydrocarbon in the predetermined pattern can occur before or after the evacuation or infusion of the materials organic or inorganic. Methods that relate to pattern formation include photoresist based photoresist, where the modified halogenated surface is coated with a photoresist, is exposed to radiation, and is developed to expose a pattern. The exposed standards are then reacted with a preferred material (eg, organometallic species), metals deposited with steam (including oxides, nitrides, etc., organic molecules, biological molecules, or polymers) and the unexposed photoresist is removed. through conventional methods to produce a patterned surface. Other details regarding this document can be found in, for example, Moreau, Semiconductor Lithograph - Principles, Practices and Materials, New York: Plenum Press (988) (particularly Chapters 8 and 9 (pages 365-458)), the which is incorporated herein by reference. In addition, the halogenated surface can be reacted with a photolabile chemical functionality, which, after using conventional masking techniques and exposure to actinic radiation, produces selective sites, which are capable of binding organometallic species, metals deposited with steam ( including oxides, nitrides, catfish, and borides, etc.), organic molecules, biological molecules, or polymer species only to exposed regions, which become active toward re-functionalization. Details regarding this method can be found in, for example, US Patents. Nos. 5,077,085 and 5,079,600 issued to Schnur et al., Which are incorporated herein by reference. The composite materials of the present invention contain polymeric phases, which have physical properties substantially similar to the properties of the native polymer (ie, in the absence of inorganic or organic molecules or macromolecular networks). Consequently, the composites of the present invention, in relation to conventional inorganic-organic hybrid materials, have significantly more predictable mechanical properties. The composite materials of the present invention also have controllable, predictable and reproducible levels of optical densities and electrical conductivities, ionic and charged species, which make them useful in various applications including protections and filters against photo-radiation, protections and filters against electromagnetic radiation and conduction electrodes. These characteristics also make these composite materials useful as components in the construction of electrolytic cells, fuel cells, optoelectronic devices, semiconductors for microelectronic applications, materials that have flame retardant and heat retarding properties, coatings that inhibit the formation of incrustation by organisms, and heterogeneous catalytic substrates. When the composite material of the present invention is used as a catalyst, it is sometimes desirable for the composite material to swell during or before use as a catalyst to increase the rate of diffusion of the reagent to the composite. This can be done by exposing the composite material to standard supercritical conditions. For example, the composite material may be placed in a container capable of withstanding high pressures, such as the pressures commonly encountered in supercritical catalytic processes. The container is then charged with a supercritical fluid under supercritical conditions, such as carbon dioxide at 175.75 kg / cm 2, and the pressure is maintained for a period ranging from 1 to 100 hours. As a result of being exposed to these supercritical conditions, the composite material swells. However, in contrast to prior art materials where impregnation is performed under supercritical conditions, the inorganic or organic materials infused according to the methods of the present invention do not diffuse out of the polymer after subsequent exposure of the material composed to supercritical conditions. The details regarding these uses are set forth in the patent application of E.U.A. applicant's tax code Series No. 08 / 833,290; patent application of E.U.A. Series No. 08 / 955,901; patent application of E.U.A. Series No. 08/997, 102; and provisional patent application of E.U.A. Series No. 60 / 039,258, which are incorporated herein by reference. In addition, the composite materials of the present invention have a surface containing halogen atoms, a portion of which has been replaced with hydrogen atoms and oxygen atoms or oxygen-containing groups. The oxyhalopolymer surface or non-halohalogenated halopolymer on the surface retains many of the positive attributes characteristic of halogenated surfaces, such as the tendency to repel water and other polar solvents, high thermal stability, low adhesion and coefficients of friction. However, unlike halogenated surfaces, the surfaces of the oxyhalopolymer materials and the oxyhalogenated non-halo polymeric materials on the surface of the present invention have reactive chemical sites, which are either bound to or allow attachment with other functionalities chemicals, such as organosilicon, organometallic precursors, transition metal ions and compounds, transition metal films, fluorescent compounds, dyes, biological materials, such as proteins, enzymes, and nucleic acids. The composites of the present invention are particularly useful for producing conductive and semiconducting films (eg, metal oxides, metal nitrides, metal carbides, metal borides, polyacetylenes, polythiophenes and polypyrroles) on the surfaces of halopolymers. More particularly, conductive and semiconductive films are more easily disposed on the surface of the composite materials of the present invention than on the surfaces of halopolymer composite materials. Referring to Figure 1, it has been observed that, when the halopolymer 20 having a free volume therein is evacuated and the inorganic or organic materials are fused to the void free volume of the halopolymer 20 to produce the halopolymer composite material 22, the inorganic or inorganic materials fused reside in the volume of the halopolymer composite material 22. It has also been observed that there is a thin layer 24 (typically about 0.5 nm to about 3 nm thick) of the halopolymer adjacent to the surface 26 of the material composed of halopolymer 22 which does not contain any inorganic or organic infused material. In many applications, it is important that the inorganic or organic layer be present directly on the surface 26 of the halopolymer composite material 22 to provide a more compatible bonding environment to an adjacent conductive or semiconducting material (e.g., metal, metal oxide, metal nitride, metal carbide, metal boride, polyacetylene, polythiophene and polypyrrole). In particular, semiconductor materials, such as metal oxides, metal nitrides, metal carbides, or metal borides, are actually synthesized, mixed, or coated with fluorine or fluoropolymers (e.g., PTFE or PVDF), due to the chemical and physical inertness of fluoropolymers and dielectric properties. See, for example, Kirschner, Chemical and Engineeing News, 75 (47): 25 (November 24, 1997), patent of E.U.A. No. 5,602,491 issued to Vázquez et al., Patent of E.U.A. No. 5,491,377 issued to Janusauskas, patent of E.U.A. No. 5,287,619 issued to Smith et al., Patent of E.U.A. No. 5,440,805 issued to Daigle et al., And the US patent. No. 5,061,548 issued to Arthur and others, which are incorporated herein by reference. However, it is also desirable to adhere layers or films of inorganic or organic materials (e.g. conductive, semiconducting or luminescent materials) adjacent to the fluoropolymer materials to provide a conductive or semiconductive layer on the semiconductor, which has been synthesized, mixed or coated with fluorine, or fluoropolymers. Similarly, when a halopolymer composite material is replaced by semiconducting materials, which have been synthesized, mixed or coated with fluorine or fluoropolymers, it may be desirable to adhere layer or films of inorganic or organic materials (e.g. conductive, semiconductor or conductive materials). luminescent) adjacent to the halopolymer composite material. For example, in some cases, it is desirable to join the halopolymer composite material between conductive or semiconducting materials. However, referring again to Figure 1, since it has been observed that the infused conductive or semiconductor material contained within the halopolymer composite material 22 lies from about 0.5 nm to about 3 nm below the surface 26 of the composite material of halopolymer 22, the infused material does not facilitate the adhesion of the desired conductive or semiconductive material to the surface 26 of the halopolymer composite material 22. The composite materials of the present invention (ie, the oxyhalopolymer composite materials or non-halopolymer composite materials oxyhalogenated on the surface of the present invention) and the composite materials made according to the methods of the present invention are completely infused into the volume and, in some cases, contain a layer (with a thickness of about 1 nm to about 1 mm ) of a pure conductive or semiconductor material (eg metal, oxide) or metal, metal nitride, metal carbide, metal boride, polyacetylenes, polythiophene and polypyrrole) on the surface of the infused matrix. This is illustrated in Figure 2. The oxyhalopolymer composite 30 includes a halopolymer composite material 32 on whose surface 34 oxygen atoms or oxygen-containing groups 36 are covalently bound, which, in Figure 2, are designated with X The thin layer 38 (typically a thickness of about 0.5 nm to about 3 nm) adjacent to the surface 34 is also infused with the inorganic or organic material, and, in some cases, the layer 40 (with a thickness of about 1 nm to about 1 mm) of pure conductive or semiconducting material is disposed on the surface 34 of the oxyhalopolymer composite material 30. In this way, using the methods of the present invention, a composite material having an organic or inorganic material infused can be prepared in the entire volume of the polymer matrix. More particularly, the organic or inorganic material can be extended from the surface of the polymer matrix and, optionally, from 1 nm to several mm above the surface of the polymer matrix. The composites of the present invention serve particularly well as substrates for bonding conductive or semiconducting materials (eg, metals, metal oxides, metal nitrides, metal carbides, metal borides, polyacetylenes, polythiophenes and polypyrroles), other polymers ( for example, polyurethanes, polyimides, polyamides, polyphosphazenes, halopolymers, polyolefins, polyacrylates, and polyesters), biological materials (eg, proteins, enzymes, nucleotides, antibodies, and antigens), and phosphorescent and fluorescent molecules commonly used in sensors and displays electroluminescent or based on liquid crystal. This is illustrated in Figures 3 and 4. For example, in Figure 3, halopolymer 42 is surface treated so that oxygen atoms or oxygen-containing radicals (denoted by X) 43 are bonded to the surface 44 , thus producing the oxyhalopolymer 45. The oxyhalopolymer 45 is then infused with an organic or inorganic material to produce the oxyhalopolymer 46 composite material. During the infusion process, the layer 47 (with a thickness of about 1 nm to about 1 mm) of a pure conductive or semiconductor material (for example, metal, metal oxide, metal nitride, metal carbide, metal boride, polyacetylenes, polythiophene and polypyrrole) is disposed on the surface 44. The layer 47 of the oxyhalopolymer composite 46 is then reacted with the material 48 ( designated with Y) (for example, conductive or semiconducting materials, other polymers, biological materials, and phosphorescent and fluorescent molecules commonly used in sensors and electroluminescent or liquid crystal based displays) so that the material 48 (designated with Y) joins to layer 47 of the oxyhalopolymer 46 composite material. Alternatively, in some cases, it may be desirable to bond materials directly to the oxyhalopolymer composite or oxyhalogenated non-halo polymeric material on the surface of the present invention without having a thick layer of conductive material or pure semiconductor (for example, metal, metal oxide, metal nitride, carbide me such, metal boride, polyacetylenes, polythiophene and polypyrrole) on the surface of the composite material. This can be facilitated, for example, by using the scheme presented in Figure 4. In Figure 4, the halopolymer 50 is infused with an organic or inorganic material to produce the halopolymer composite material 52. The halopolymer composite material 52 is then treated on the surface such that the oxygen atoms or oxygen-containing radicals 56 (designated X) are bonded to the surface 54 of the halopolymer composite material 52, thereby producing the oxyhalopolymer 58 composite. Oxygen atoms or radicals containing oxygen 56 (designated with X) of the surface of the oxyhalopolymer composite material 58 are then reacted with the material 60 (designated Y) (for example, conductive or semiconducting materials, other polymers, biological materials and fluorescent or fluorescent molecules) commonly used in sensors and electroluminescent screens or liquid crystal based) of maner to which the material 60 (designated with Y) is attached to the oxyhalopolymer composite material 58. Using the scheme illustrated in Figure 4, the coarse bond layer made of the pure conductive or semiconductive material can be excluded from the resulting composite material. The oxyhalopolymer composites or oxyhalogenated non-halo polymer materials on the surface of the present invention can be used to make highly suitable electrical substrate materials to form wiring board, printed, rigid, and integrated circuit wafer carriers, such as those described in the US patent No. 4,849,284 issued to Arthur et al. ("Arthur"), which is incorporated herein by reference, for example, by replacing the oxyhalopolymer composites or the oxyhalogenated non-halo polymer materials on the surface of the present invention for the filled fluoropolymer with ceramics established in Arthur. The oxyhalopolymer composites or the oxyhalogenated non-halo polymeric materials on the surface of the present invention can be used to make materials that exhibit low loss, high dielectric constants and which have acceptable thermal coefficients of dielectric constants, such as those described in the US patent No. 5,358,775 issued to Horn III ("Horn"), which is incorporated herein by reference, for example, by replacing the oxyhalopolymer composites or oxyhalogenated non-halo polymer materials on the surface of the present invention for fluoropolymers filled with ceramics established in Horn. The oxyhalopolymer composite materials or the oxyhalogenated non-halo polymeric composite materials on the surface of the present invention can be used to make solid polymer type fuel cells, such as those described in the patent of E.U.A. No. 5,474,857 issued to Uchida et al. ("Uchida"), which is incorporated herein by reference, for example, by replacing the oxyhalopolymer composites or the oxyhalogenated non-halo polymer materials on the surface of the present invention with the electrolyte of solid polymer established in Uchida. The oxyhalopolymer composites or the oxyhalogenated non-halo polymeric materials on the surface of the present invention can be used to make covalently bonded films for use in printed circuit boards, such as those described in the US patent. No. 5,473,118 issued to Fukutake et al. ("Fukutake"), which is incorporated herein by reference, for example, by replacing the oxyhalopolymer composites or the oxyhalogenated non-halo polymer materials on the surface of the present invention with the fluoropolymer (which is subsequently coated with a thermoplastic or heat cured adhesive) established in Fukutake. The oxyhalopolymer composite materials or the oxyhalogenated non-halo polymeric materials on the surface of the present invention can be used to make multi-layer circuit assemblies, such as through the methods described in the U.S.A. No. 5,440,805 issued to Daigle et al. ("Daigle"), which is incorporated herein by reference, for example, by replacing the oxyhalopolymer composite materials or the oxyhalogenated non-halo polymer compounds on the surface of the present invention with the composite materials of fluoropolymer established in Daigle. The oxyhalopolymer composites or the oxyhalogenated non-halo polymeric materials on the surface of the present invention can be used to make multiple wafer module substrates, such as described in US Pat. No. 5,287,619 issued to Smith et al. ("Smith"), which is incorporated herein by reference, for example by replacing the oxyhalopolymer composites or the oxyhalogenated non-halo polymer compounds on the surface of the present invention with the composite materials of fluoropolymer set in Smith. The oxyhalopolymer composite materials or the oxyhalogenated non-halo polymeric materials on the surface of the present invention can be used to make electroluminescent lamps, such as those described in the U.S.A. No. 5,491,377 issued to Janusauskas ("Janusauskas"), which is incorporated herein by reference, for example, by replacing the oxyhalopolymer composites or the oxyhalogenated non-halo polymer materials on the surface of the present invention with the established fluoropolymer binder. in Janusauskas. The composite materials of the present invention may be in a free-standing form (ie, not bound to another material). Examples of composites in free-standing form include composite beads, composite particles, composite films, composite fibers, composite filaments, composite powders and the like. Alternatively, the composite materials of the present invention can be disposed on a base material (for example a halopolymer, a non-halo polymer, a ceramic, a glass, a metal, and a metal oxide). For example, metal oxide substrates that are coated with composite materials (particularly oxyfluoropolymer composites) of the present invention (particularly those having a surface of metal oxide and metal oxides disposed in the free volumes thereof which they are placed as a coating on the pure metal oxide) are particularly useful in the semiconductor industry. The oxyhalopolymer composites of the present invention disposed on a base material can be prepared, for example, by coating, adhering or otherwise arranging a halopolymer on the base material and then modifying the surface with oxygen or oxygen-containing radicals and, before, during, or subsequent to said modification, evacuate the free volume and infuse an inorganic or organic material in it. Alternatively, the oxyhalopolymer composites of the present invention disposed on a base material can be prepared by coating, adhering or otherwise arranging a halopolymer composite material on the base material and then modifying the surface of the halopolymer composite with oxygen or radicals. that contain oxygen. Still alternatively, the oxyhalopolymer composites of the present invention disposed on a base material can be prepared by coating, adhering or otherwise arranging an oxyhalopolymer on the base material and then evacuating the free volume of the oxyhalopolymer and infusing an inorganic or organic material therein. he. Still alternatively, the oxyhalopolymer composites of the present invention disposed on a base material can be prepared by coating, adhering or otherwise arranging an oxyhalopolymer material on the base material. The oxyhalogenated non-halo polymeric composite materials on the surface of the present invention disposed on a base material can be similarly prepared, for example, by any of the methods described above for preparing the oxyhalopolymers disposed on base materials. The present invention is further illustrated by the following examples.

EXAMPLES Example 1 - Preparation and Characterization of V? Q.- in Politetraf I uoroethylene-c or -hexaf I or gold propylene A 30.48 cm x 5.08 cm piece of polytetrafluoroethylene-co-hexafluoropropylene, ("FEP") (Dupont) was wrapped around itself to form a loose binding coil and then placed in a 100 ml round bottom flask. The flask was connected to a vacuum line and then pumped at a pressure of less than 10 mTorr. Then, about 1 ml of V (0) CI3 (Strem) was transferred in vacuo to a 100 ml round bottom flask. The flask was then closed and heated to about 75 ° C under vacuum so that a gas phase of V (0) CI3 filled the entire volume of the flask for 1 hour. The flask was removed from the heat, and its temperature was reduced to about room temperature. The V (0) CI3 was then transferred under vacuum out of the FEP polymer, and the 100 ml round bottom flask was opened to ambient air. After opening the flask, the FEP polymer was transparent to the eye but, in a few minutes, it started to turn yellow-orange and reached its darkest level after a few hours. X-Ray Photoelectron Spectroscopy ("XPS") indicated the formation of a highly oxidized vanadium complex, and the visible orange color was indicative of a large macromolecular V205 network. This was further confirmed through visible ultraviolet spectroscopy ("UV-vis"). The broad absorbance spectrum had two major peaks around 370 nm (A = 1.8) and 248 nm (A = 3.2) and was similar to but different from that of pure V2Os powder dissolved in acetonitrile. It is believed that the difference in the UV-vis spectra between the V205 formed in the FEP polymer and that in the acetonitrile solution is attributable to some electronic coordination of the vanadium metal center to the adjacent fluorine functionality contained in the FEP. This is supported by the XPS results, which measure an extremely high binding energy of approximately 518.5 eV, a full eV than that for the V205 powder. This increase in binding energy is consistent with vanadium being in a highly electronic removal environment, which further suggests that vanadium is either directly bound to or affected through space by the fluorine functionality contained in the FEP polymer. To support this further, the FEP polymer containing the vanadium was placed in a beaker containing 50% hydrofluoric acid ("HF") in water for 2 hours. After removing the FEP material, it was observed that the material was completely transparent to the eye (ie, no yellow color was observed). Inspection through UV-vis spectroscopy showed that the absorbance band originally at 248 nm was present (although it was blue that changed to a lower wave number) at approximately the same intensity. However, the band at 370 nm disappeared. Since the band at 370 nm is attributed to intermolecular transitions and the band at 248 nm is attributed to intramolecular transitions, the results are consistent with a mechanism which preferentially coordinates the vanadium species to fluorine ions from the HF. This in turn interrupts the coordination of the vanadium to the fluorine atoms in the FEP polymer, which then leads to an interruption of the macromolecular network. This is also consistent with the loss of visible color (ie, the individual or low molecular weight macromolecules of V205 are transparent at the visible point while the large macromolecular networks show colors ranging from light yellow to orange). After removing this material from the HF solution, it was observed that the yellow color returned in a few hours and that the UV-vis spectrum obtained from this material showed the same characteristics observed with the FEP material before it was exposed to HF. . This indicates that not only the macromolecular network was reformed and that the process is reversible, but also other molecules could easily diffuse into and out of these materials and easily interact with the inorganic portion of the composite material. The method described above can also be used to infuse vanadium oxide to other fluoropolymer resins, for example, PVDF, PTFE, ECTFE, PFA, or MFA. In addition, this method is not restricted to any particular form of fluoropolymer resin. Instead of the 30.48 x 5.08 cm FEP sheet, powders (eg having diameters from about 10 nm to about 0.1 mm), beads (eg, having diameters from about 0.1 to about 0.5 mm), films, filaments can be used. and fibers.

Example 2 - Preparation and Characterization of V? Qs in Polyethylene Terephthalate The same experiment described in Example 1 was performed using a piece of polyethylene terephthalate ("PET"), which is a polyester containing only aliphatic carbon and ester functionality. After exposing the PET in the same manner as described in Example 1, the same observations were made. That is, initially the PET film was transparent and in a few hours it became yellow-green. Although the color at first glance was slightly different, the UV-vis results showed a similar spectrum as that observed for FEP. The XPS, on the other hand, showed a binding energy of approximately 517.5 eV, which is consistent with V205. This further supports the results of Example 1, which indicate that the vanadium was complexed to the fluorine functionality thereby increasing its binding energy by XPS. These results suggest that the electronic state of the inorganic material in the free volume of the polymer matrix can be influenced by the functional groups contained in the polymer that forms the polymer matrix.

Example 3 - Preparation and Characterization of Fe? Oa in Politetraf luoroet i leño -co- hexaf I or gold prop i leño A piece of FEP polymer was treated exactly the same as that described in Example 1, except that instead of using V (0) CI3, 1 ml of Fe (CO) 5 was transferred in vacuo to the flask containing the FEP. The temperature and time of treatment were identical to those described in example 1. After the removal, the film became deep orange. The results of XPS and UV-vis indicate the formation of Fe 03. A slight shift towards a higher binding energy in the XPS for Fe203-FEP material indicated that the iron, in a certain way, electronically coupled to the fluorine functionality in the EFF In accordance with this invention, it is contemplated that the materials are useful protections or filters against light and electromagnetic radiation. Examples 1-3 showed that the macromolecular vanadium and iron networks can be formed within FEP and PET. Both FEP and PET are lightweight and flexible. In addition, the FEP material is extremely weather resistant and is chemically inert. Contact angle experiments were performed on the material made in Example 1 and showed a small change in the surface properties of the FEP fluoropolymer (ie, the contact angle of the water was even greater than 90 degrees), indicating that the inherent resistance to weathering and inertia to solvents and chemicals for this fluoropolymer remained intact. In this way, Examples 1-3 show that the methods of the present invention can be used to make flexible, lightweight materials, which have an absorbance of UV radiation and which have surfaces that resist weathering, the formation of incrustation and chemical degradation.

Example 4 - Preparation and Characterization of TiO; in Polytetrafluoroethylene-co-hexafluoro propylene In Examples 1-3, the inorganic vanadium and iron networks imparted a visible hue to the polymeric materials, which may be undesirable in applications that require high transparency in the visible region of the light spectrum. To provide a material that is transparent to visible light but which blocks or absorbs large amounts of UV radiation, other inorganic complexes based on titanium can be used. One piece of the FEP polymer was treated exactly the same as that described in Example 1, except that instead of using V (0) CI3, 1 ml of TlCI4 was transferred in vacuo to the flask containing the FEP. The temperature and time of treatment were identical to those described in Example 1. After the removal, the film was completely transparent to the naked eye and no change was ever observed. The results of XPS and UV-vis indicated the formation of Ti02, and a slight shift to higher binding energy was observed in the XPS, which indicated that the titanium was somehow electronically coupled to the fluorine functionality in the FEP. As in Example 1, the FEP sheet used herein can be replaced with other fluoropolymer resins (eg, PVDF, PTFE, ECTFE, PFA or MFA) or with other forms of polymer, such as powders (eg, having diameters) from about 10 nm to about 0.1 mm) or beads (for example, having diameters of about 0.1 to about 0.5 mm).

Example 5 - Preparation. Characterization, and Use of WO; in Itetrafluoroethylene-co-hexafluoropropy Although titanium, vanadium and iron are good protections against UV radiation, they could be used to form a network of a metal with a high Z number (ie, high density or heavy weight). The high number Z numbers are efficient not only to block UV radiation, but they are used more frequently to protect against high UV energy and X radiation. Tungsten belongs to this class of metals. However, there is no metallic tungsten complex in a liquid form capable of boiling in a gas phase. In view of this, a different method for self-assembly of a heteropolycondensate of tungsten in polymers was developed.

The method described here illustratively uses an FEP sheet. However, the method can be applied equally to other fluoropolymers (e.g., PVDF, PTFE, ECTFE, PFA, or MFA) and to other resin forms, such as powders (e.g. having diameters from about 10 nm to about 0.1 mm. ) or beads (for example, having diameters of about 0.1 to about 0.5 mm). A 5.08 x 5.08 cm piece of FEP polymer was placed in a 100 ml round bottom flask together with 100 mg W (CO) 6. The flask was connected to a vacuum line and then pumped at a pressure of less than 10 mTorr. Then, the flask was heated to 75 ° C, which, at a pressure of 10 mTorr, was high enough to initiate the sublimation of W (CO) 6 and to create a vapor phase of the tungsten complex inside the flask. After 1 hour, the FEP material was removed and placed under ambient air conditions for 2 hours. The UV-vis experiments showed a large absorbance band at 228 nm (A = 3.4) with a smaller absorbance band at 288 nm (A = 0.4), indicating the formation of a complex within the FEP. The sample was slightly transparent in the visible region of the spectrum. Unlike the vanadium, titanium and iron samples used in Examples 1-4, not only this particular tungsten complex needs to be sublimated instead of boiled, it also possessed carbonyl ligands, which are relatively stable compared to those in the metal complexes used in Examples 1-4.

In this way, after obtaining the UV-vis spectra, the FEP sample was placed under a wide-band, high-energy ultraviolet source at 254 nm in the presence of air for 1 hour. The carbonylated ligands associated with this tungsten compound are known to be photoactive under UV radiation. After exposing the sample to the UV lamp, several changes were observed in the UV-vis spectrum. The absorbance at 288 nm was slightly reduced to A = 0.37; the band at 228 nm was reduced from A = 3.4 to 1.1, at 190 nm (which is the limit of the instrument's capacity with respect to the measurement of low wave number absorbance values), the absorbance changed from 0.4 ( before UV irradiation) to 1.5 (after UV irradiation). This is believed to indicate that the complex formed after irradiation was more prone to protection against higher energy radiation (ie, radiation at lower wave numbers) and could be quite useful as a flexible, visibly transparent material. W03 is well known for its ability to X-radiation. It was observed that, after having been infused into the FEP, the tungsten compound absorbed on the UV medium scale, as might be expected to have the tungsten carbonyl, after having been infused in the FEP, it retained either all or a portion of its original carbonyl ligands. The macromolecular tungsten complexes are known for their ability to protect against high energy radiation, which is what was observed after the carbonyls were removed by UV radiation in the presence of water or air containing oxygen. This supports the proposition that treatment with UV radiation in the presence of air produced a hydrolyzed and / or oxidized form of tungsten, which was then self-assembled with surrounding hydrolyzed or oxidized tungsten to form a macromolecular complex.

Example 6 - Stability of Polycondensate Networks Incorporated in FEP via Exposure to CO Environments? Supercritical Pieces of 15.24 x 15.24 cm of FEP were treated in the same way as the FEP was treated in Example 1. After these FEP films were metallised with V205 as described, the films were placed in a stainless steel container at high pressure. The vessel was then loaded with 175.75 kg / cm2 of C02 gas at 40 ° C. these conditions result in the formation of a supercritical C02 environment under which the FEP is known to swell. The swelling of the FEP films under these conditions allows the rapid exchange of C02 with bound molecules contained within the free volume of the polymer. The FEP samples in this example were left under these conditions for 72 hours. UV-vis analysis of the FEP films (after 72 hours) indicated only an insignificant loss of V205 (less than 10%) and suggested that the network formed within the polymer matrix remained either: (1) permanently trapped within of the polymer due to physical interactions between the polymer chains with macromolecules of the formed heteropolycondensate, and / or: (2) permanently traps within the polymer due to chemical or electronic interactions between the functional groups contained within the polymer and the atoms and / or groups of the macromolecular network of the heteropolycondensate. The stability demonstrated in this example makes these materials good candidates for use as heterogeneous catalysts under supercritical process conditions. Also, the experiment was performed using 50 micron small beads of the ethylenechlorotrifluoroethylene copolymer ("ECTFE"), which also contained macromolecular networks of V205. These materials were also prepared using the procedure described in Example 1. Again, no loss of the inorganic material V205 was observed after exposure to supercritical conditions. It is believed that these experiments show that macromolecular inorganic networks can be permanently stabilized in polymer matrices either by coordinating with functional groups (such as the fluorine and / or chlorine groups contained within FEP and ECTFE) or by entangling within chains contained in the Amorphous regions of the polymer, where the inorganic networks are formed. In addition, since these materials are stable under supercritical conditions, they can be used as heterogeneous catalysts in supercritical fluid reactors, such as those described in Patchornick, Winslow and Cunnington, which are incorporated herein by reference.

Example 7 - Stability of Polycondensate Networks Incoporated in PTFE, ECTFE, PVDF. PMMA, PP, PS. and PVDF Via the Exposure to CO Environments? Supercritical .08 x 5.08 cm pieces of PTFE, ECTFE, PVDF, polymethylmethacrylate ("PMMA"), polypropylene ("PP"), Polystyrene ("PS") and polyvinylidene fluoride ("PVDF") were treated in the same manner as the FEP treated as in Example 1. After these films were metallized with V2Os, these were first analyzed through UV-vis spectroscopy, as previously described, the films were then placed in a high-pressure stainless steel vessel . The vessel was then charged with 175.75 kg / cm2 of CO2 gas at room temperature. Samples were left under these conditions for 72 hours. The UV-vis analysis of these films (after 72 hours) indicated only an insignificant loss of V2Os (less than 10%) and suggested that the network formed within the polymer matrices was either: (1) permanently trapped within the polymer due to physical interactions between the polymer chains with heteropolycondensed macromolecules formed, and / or: (2) permanently trapped within the polymer due to chemical or electronic interactions between the functional groups contained within the polymer and the atoms and / or functional groups of the macromolecular network of heteropolycondensed. The stability demonstrated in this example makes these materials good candidates for use as heterogeneous catalysts, which can be used under supercritical conditions.

Example 8 - Heterogeneous Catalysis of SO? to SOa A 7.62 x 45.72 cm piece of an FEP sample with a thickness of 25.4 microns was treated in the same manner as the FEP material of Example 1. The piece was metallized FEP (V205) then placed in a stainless steel reactor. 100 ml, which was then charged with 4 atmospheres of 02 and 1 atmosphere of S02. The vessel was then heated at 70 ° C for 24 hours. After this treatment, the container was opened and the FEP was removed. Next, a balanced amount of deionized H20 was added to the vessel to convert any S03, which formed during the catalytic reaction to H2SO4. Using a pH meter to measure the acidity resulting from the added deionized H20, the pH was determined as 1.8. The calculations involving the initial concentration of S02 and the resulting pH of the known amount of added H20 determined that more than 90% of S02 was catalytically converted to S03. Subsequent analysis (through UV-vis spectroscopy) of the metallized FEP showed no detectable loss of V2Od, thus indicating the stability of the macromolecular network of V205 within the FEP film during the catalytic process.

Molecular transformations that use V205 as an oxidation catalyst to convert S02 to S03 usually require reaction temperatures greater than 500 ° C, which indicates that the material used here may have improved capabilities with respect to its operation as a catalyst heterogeneous. In addition, the results of this example, although only illustrative, demonstrate the utility of V205 and other interpenetrating metal complexes in inorganic-organic materials as oxidation catalysts.

Example 9 - EMI protections. UV Light Filters and Photolithographic Masking Materials Examples 1-8 showed materials that absorb UV and X radiation at levels that may be useful for coatings or films, which inhibit and / or attenuate radiation penetration into these films, while in contact with sensitive materials.

UV, extreme UV, and X-rays. As an example, this is demonstrated by UV-vis absorbances across the entire scale of the UV-vis spectrum (ie 190 nm - 400 nm) of more than 2.0 absorbance units (ie 99% UV absorbency) for films Nfused with vanadium or titanium. Furthermore, these results, when taken together with the results indicating the formation of macromolecular networks of inorganic / metallic complexes in the composite materials of the present invention, suggest that the composite materials are useful both for absorbing electromagnetic radiation, reflecting electromagnetic radiation and transform electromagnetic radiation varies to electric current (ie, acting as a protection against electromagnetic interference ("EMI")). Since conventional photolithographic and image forming processes require polymeric photoresist materials capable of blocking these different types of radiation during the exposure steps, the composite materials of the present invention can be used as masks in said photolithographic and image forming processes , conventional. For example, the patent of E.U.A. No. 5,387,481 issued to Radford et al. ("Radford"), which is incorporated herein by reference, discloses a vanadium oxide, which may act as a protection, but to block electromagnetic radiation. The vanadium oxide compound used by Radford, when heated, is said to exhibit a rapid and marked transition from a dielectric material, which is transparent to electromagnetic radiation, to an electromagnetic radiation shield, which is impervious to electromagnetic radiation. In the Radford patent, the vanadium oxide material is applied as a film delegated to a solid substrate. In the present invention, the vanadium oxide can be initially incorporated into a polymer matrix to produce a composite material according to the present invention. After heating, the vanadium oxide can be transformed from a material, which is transparent to electromagnetic radiation to one that effectively blocks said radiation. This example is only illustrative: other composite materials of the present invention, particularly those containing conductive macromolecular networks (eg, those containing Ti, Fe, Pb, and Au) can act as efficient blockers of electromagnetic radiation, such as UV radiation , Extreme UV and X.

Example 10 - Battery and Fuel Cell Separators Example 1, above, showed that the hydrofluoric acid molecules ("HF") and the ions generated therefrom can penetrate a fluoropolymeric material such as FEP and PET, which contained a vanadium complex. This was demonstrated through UV-vis data, which showed the disappearance of certain molecular absorbances as well as the naked eye that showed that the material was made from yellow-orange to a totally transparent material when placed in the HF solution . In addition, these materials were observed to change back to a yellow-orange color, without any detectable loss of the vanadium complex, after removing the HF solution and exposing the material to the air. This shows that, even after the formation of the composite material, both gas phase and liquid phase molecules and ions can be transported through the material and can react or coordinate with vanadium (or any other metal or inorganic complex) contained within the free volume of the polymer matrix in a reversible manner. In addition, as described above, many of the inorganic materials incorporated within the free volume of the polymer matrix contain catalytically active metals or metals that can act as good redox materials (i.e., metals that can donate or accept ion electrons or molecules). charged). The ability of gases and liquids to diffuse into free volumes containing catalysts or redox materials suggests that the composites of the present invention are useful as electrodes and separation materials, such as in battery and fuel cell applications. For example, the patent of E.U.A. No. 5,470,449 issued to Bachot et al., Which is incorporated herein by reference, describes the preparation of microporous diaphragms adapted for wet consolidation with composite cathodes for use in electrolytic cells. These microporous diaphragms include a fibrous, microporous, fluoropolymer sheet material, concreted containing from 3% to 35% by weight of the fluoropolymer binder and from 0% to 50% by weight of a uniformly distributed gel of an oxohydroxide (i.e. , a heteropolycondensate) prepared from a metal such as Ti or Si. The methods of the present invention can be used to make a composite material of a fluoropolymer matrix material having macromolecular networks of metal oxohydroxides incorporated therein. For example, Ti oxohydroxides can be formed into a network in FEP films as described in Example 4. As a further example, a macromolecular network of Si oxohydroxide was also incorporated into an FEP film by first placing a piece of 30.48 x 5.08 cm of FEP in a 100 ml round-bottomed flask, connecting the flask to a vacuum line, pumping the flask to a pressure of less than 10 mTorr, and transferring under vacuum about 1 ml of SiCl4 to the flask. The flask was then closed and heated to about 75 ° C under vacuum, so that the SiCl 4 gas phase filled the entire volume of the flask for 1 hour. The SiCl 4 was then transferred under vacuum out of the FEP polymer, and the flask was opened to ambient air. After exposure to air, SiCl4, which was incorporated into the FEP film, was hydrolysed, which resulted in the formation of a macromolecular network of Si oxohydroxide, as confirmed by IR spectroscopy, which measured the absorbance of Si-O at approximately 1025 cm "1. The composites of the present invention can also be used in electrolytic cells and fuel cells described in US Patent No. 5,512,389 issued to Dasgupta et al. (" Dasgupta "), which is incorporated herein by reference, Dasgupta describes the use of a solid polymer electrolyte in a rechargeable lithium battery, thin film, non-aqueous. They can also be used in electrochemical cells instead of the halogenated (eg, fluoropolymer) separator material used in the electrochemical cells described in the U.S. patent. No. 5,415,959 issued to Pyszczek et al., Which is incorporated herein by reference. As a further illustration, the composites of the present invention can be used as a solid polymer electrolyte instead of the solid polymer electrolyte (prepared by bonding catalytic metals to solid polymeric materials) used in the U.S.A. No. 5,474,857 issued to Uchida et al., Which is incorporated herein by reference.

Example 11 - Electrically Conductive Flexible Materials for Optoelectronics Many of the heteropolycondensates formed within the polymer matrices using the methods of the present invention have electrical and / or ionic conductivity properties, which makes them useful in technologies that require flexible materials having electrical or ionically conductive characteristics and / or antistatic For example, MacDiarmid et al., Proc. Materials Research Society, Boston, MA (November 1995) and the patent application of E.U.A. No. 08 / 401,912, which are incorporated herein by reference, describe the use of conductive polymers adhered to flexible substrates as flexible electrode materials in the construction of electro-optical devices. Through the proper selection of a flexible polymer matrix, the methods of the present invention can be used to produce conductive composites, which can be used in said electro-optical devices. For example, a 10.16 x 10.16 cm sheet of FEP was placed in a 100 ml bottom flask. The flask was connected to a vacuum line and then pumped at a pressure of less than 10 mTorr. Then, about 1 ml of pyrrole was transferred under vacuum to the flask, and the flask was closed and heated to about 75 ° C under vacuum so that a gas phase of pyrrole molecules filled the entire volume of the flask for 1 hour. The pyrrole was then transferred under vacuum out of the FEP polymer, and the flask was opened to ambient air. The sample was then placed in an oxidation solution of HN03 for 12 hours. After the removal, the film acquired a gray tint. The UV-vis inspection confirmed the formation of a polypyrrole network within the FEP matrix. As a prophetic example, the indium and tin heteropolycondensates, known as indium tin oxide ("ITO"), when evaporated on a variety of substrates, were used commercially as a transparent conductive film. These ITO films were used as electrode materials in the construction of many devices (for example, flat panel screens based on liquid crystal). The methods of the present invention can be used to produce thin conductive films, which can be used in place of the ITO films in said electro-optical devices. To illustrate this aspect of the present invention, a 10.16 x 10.16 cm sheet of FEP can be placed in a 100 ml round bottom flask. The flask was then connected to a vacuum line and pumped at a pressure of less than 10 mTorr. Next, about 1 ml of triethylindium and about 1 ml of SnCl4 was transferred under vacuum to the flask. The flask was then closed and heated to about 75 ° C under vacuum so that a gas phase of both triethylindium and SnCl 4 filled the entire volume of the flask for 1 hour. The triethylindium and SnCl4 were then transferred under vacuum out of the FEP polymer, and the matrix was opened to ambient air. After exposure to air, both triethylindium and SnCl4, which were incorporated into the FEP film underwent hydrolysis, which resulted in the formation of a macromolecular ITO network.

Example 12 - Electronic Image Formation Applications Rajeshwar, which is incorporated herein by reference, discloses the use of polymer films containing nanodispersed catalyst particles of electronically conductive polymers containing polypyrrole, polyaniline, and polythiophene in imaging applications. The polymer films described by Rajeshwar can be replaced by the composites of the present invention to produce materials useful in imaging. For example, composite materials containing polypyrrole can be prepared and treated in the following manner. A polypyrrole deposition solution was prepared by mixing 100 ml of a solution containing 0.6 ml of pyrrole in deionized water together with 100 ml of a solution containing 3.4 g of FeCl3-6H20, 0.98 g of anthraquinone-2-sulfonic acid sodium salt monohydrate, and 5.34 g of 5-sulfosalicylic acid dihydrate in deionized water, The polypyrrole films were then deposited on a polyethylene terephthalate ("PET") film. measuring 5.08 x 5.08 cm by immersing the PET film for 5 minutes in a magnetically stirred polypyrrole deposition solution. PET having a polypyrrole film thereon, then ultrasound was applied in methanol, rinsed with deionized water, and dried under N2. The polypyrrole film on PET was then treated in the same manner as the FEP treated in Example 1 (to incorporate a macromolecular heteropolycondensed network of V205). After the film containing VOCI3 was exposed to the air to facilitate hydrolysis, it was examined through UV-vis spectroscopy, and the spectrum was compared with the UV-vis spectrum initially obtained from the polypyrrole film, which was deposited on the PET material. The comparison of the UV-vis spectra showed differences, which verified the incorporation of V205 in the conductive layer of polipirrol. In an alternative method, a 10.16 x 10.16 cm sheet of FEP was treated as described in Example 1 (ie, incorporated with a macromolecular heteropolycondensed network of V205). The film was then placed in a 100 ml round bottom flask, and the flask was connected to a vacuum line and pumped at a pressure of less than 10 mTorr. Then, approximately 1 ml of pyrrole was transferred under vacuum to the flask, and the flask was then closed and heated to about 75 ° C under vacuum, so that a gas phase of pyrrole molecules filled the entire volume of the flask for 1 hour. hour. The pyrrole was then transferred under vacuum out of the FEP polymer, and the flask was opened to ambient air. It was observed, without any treatment, that the film acquired a gray dye normally associated with polypyrrole. UV-vis spectroscopy confirmed that pyrrole, which was diffused in the FEP material, was oxidized by the V205 contained in the film prior to exposure to pyrrole. UV-vis spectroscopy also confirmed that the pyrrole molecules were oxidatively converted to a polymeric macromolecular network of polypyrrole. The composite materials of the present invention can also be used as electroconductive imaging elements, such as those used in high-speed laser printing processes, which utilize electro-statography. For example, the composite material of the present invention can be used as a replacement for the electroconductive imaging element described by Anderson I, which is incorporated herein by reference. Suitable composites for use as electroconductive imaging elements include the materials described in Examples 1 and 2, which incorporate macromolecular networks of V205 in both PET and FEP. Using the UV-vis measurements obtained in Example 1 and 2, it was calculated that both the PET and FEP materials contained more than 40 milligrams of V2Os per square meter. Using the processes described herein, the concentration of the inorganic and / or organic macromolecular networks formed within the polymer matrix can be reduced to the levels of V205 described in Anderson I, eg, about 3 mg per square meter.

Example 13 - Methods to Control the Concentration of Inorganic and / or Organic Heteropolycondensates in Polymeric or Inorganic-Organic Matrices All the above examples describe methods for making composite materials, which contain polymers and inorganic-organic hybrid materials having macromolecular networks of polymers and / or macromolecular networks of inorganic polycondensates incorporated within their matrices in regions designated and defined in the specifications of this. request as free volume. The methods used and described in the previous examples demonstrate the ability to conveniently diffuse the inorganic and / or organic molecules in the free volume spaces inherent in any polymeric or inorganic-organic hybrid material, and then convert these molecules to macromolecular networks large or polycondensed macromolecular. These free volumes can be thermally controlled such that the concentration or total amount of organic or polycondensed inorganic networks, which are incorporated in the total volume of the polymeric template hybrid or inorganic-organic material, can also be controlled. Essentially, as the temperature increases during the initial diffusion step of any inorganic, metallic or organic molecule in a given polymer or inorganic-organic hybrid material, the free volume in which these materials can diffuse can also be increased (providing which temperature is below the thermal decomposition temperature of the polymer or inorganic-organic hybrid material and the decomposition temperature of the starting inorganic, metallic or organic molecule). To illustrate this phenomenon, a series of FEP materials was exposed to VOCI3 and subsequently hydrolyzed to V205 in the same manner as that described in Example 1, except that it was initially exposed to VOCI3 vapor at different temperatures. When measuring the absorbance of UV-vis at 225 nm, it was observed that at 27 ° C, A = 0.14; at 40 ° C, A = 0.31; at 60 ° C, A01.05, at 70 ° C, A = 1.63; at 80 ° C, A = 2.5 and at 90 ° C, A = 3.14. These results demonstrate that control over the concentration of the macromolecular material introduced can be facilitated by the methods described herein.

Example 14 - Location of the Macromolecular network This example establishes that macromolecular networks are formed mainly in the free volume of the polymer matrix. As described above, conventional methods for making inorganic-organic hybrids involve either (1) solubilizing an inorganic precursor capable of forming a macromolecular network within a polymeric material with an appropriate solvent to solubilize both the bound polymer and the inorganic molecule starting, adding a hydrolyzing agent and drying and / or curing the mixture to form a composite material, (2) adding an inorganic precursor, which is capable of forming a macromolecular network together with a hydrolyzing agent to a molten polymeric material and drying and / or curing the mixture to form a composite material, or (3) using supercritical fluids. In the first two cases, the resulting material contains both the starting polymeric material and an inorganic heteropolycondensate. Due to mixing and curing, the resulting material is dried and / or cured simultaneously to form a material dependent on the presence of both the initial polymeric starting material and the heteropolycondensate formed. In other words, the final physical (ie, morphological), electrical and chemical properties of the polymer are substantially changed from those of the starting polymer material. In addition, fine control over the resulting properties of the composite material is difficult and requires extensive trial and error, which can show that the desired property is not allowed by the technique used. In the third case, the use of supercritical conditions gives rise to a variety of disadvantages, such as those discussed above. In the composite materials of the present invention, the polymeric or inorganic-organic hybrid materials act only as a template to support the formation of macromolecular networks of organic or inorganic polycondensate within their free volume. Not only can this preserve many of the physical, electrical and chemical properties of both materials, but it also allows to controllably improve the desired properties of either the polymeric matrix material or the incorporated macromolecular network (eg, catalytic activity). For example, the preparation of a porous, hybrid, inorganic-organic filter material, using the methods described in the prior art, requires that the material first be melted or dissolved and then mixed with at least one inorganic precursor. This mixture must then be dried and / or cured, so that it has a porosity similar to that of the starting polymer. This is difficult, if not impossible, due to the new nature of the melted hybrid material or solvated material. In contrast, through the treatment of the same porous filter material used the methods of the present invention, the desired characteristics can be imparted to the pre-formed filter material without changing the physical pore size or the surface morphology of the filter material. . Example 13 shows that the composites of the present invention contain organic macromolecules and heteropolycondensate networks within the free volume of the polymeric and inorganic-organic hybrid materials. To further characterize the composite materials of the present invention, thermal analyzes were conducted in a variety of materials prepared by the methods of the present invention. More particularly, studies of thermal decomposition ("Td") and differential scanning calorimetry ("DSC") were performed on two separate films of heteropolycondensate networks containing titanium and vanadium ECTFE, respectively. The films were prepared using the procedures described in Examples 1, 2 and 4. The results showed only a negligible change in the decomposition temperature of the material and no change in their degree of crystallinity (ie, no change in the morphology of the polymer. original). Also, using the procedures described in Examples 1-3, two perfluorinated alkoxy resin films were treated, such that one contained a heteropolycondensate network of titanium and the other of vanadium. These samples also showed no change in the decomposition temperature or degree of crystallinity. Finally, in the same way two FEP films were treated and also showed insignificant changes with respect to the Td and DSC measurements. These results indicate that macromolecular networks are formed along the free volume spaces of the polymer matrix materials and retain the inherent structure morphology (i.e., the crystallinity and physical morphology) of the polymer matrix.

Example 15 - Increase and / or Stabilization of Mechanical Resistance of Materials Example 8 showed how the chemical functionality and electronic nature of a polymeric matrix can act to improve the catalytic activity of a metal center contained within a macromolecular vanadium polycondensate (ie, a V205 network incorporated in a fluoropolymeric material) . Conversely, the functionality contained in a heteropolycondensate network incorporated in a polymer or inorganic-organic hybrid material can be made to influence the chemical, thermal, and / or mechanical resistance of the matrix material. Many polymers are well known to degrade physically and chemically, either thermally, chemically, or through exposure to actinic radiation. This eventually leads to loss in the mechanical strength of the material. For example, the mechanical thermal analysis ("Tm") of ECTFE shows that, when exposed to temperatures of or about 250 ° C, the mechanical strength is significantly reduced (ie the polymer melts and starts to flow). To demonstrate that the functionality contained in a macromolecular network arranged in the free volumes of a polymer matrix can influence the chemical, thermal, and / or mechanical resistance of the polymeric matrix material, two 5.08 x 5.08 cm pieces of ECTFE were treated. the same way as was done for the FEP samples described in Examples 1, 2 and 4. One piece of the ECTFE contained a macromolecular network consisting of the heteropolycondensate V2C5, and the other contained a heteropolycondensate of Ti02. Both materials were analyzed by mechanical thermal analysis, which measures mechanical resistance as a function of temperature. In the case where the ECTFE film was incorporated with V205, no change in its mechanical strength was observed as a function of the increased temperature, indicating little or no interaction between the incorporated V205 and the ECTFE polymer after heating. In contrast, the measurements of Tm in the Ti02 incorporated with ECTFE showed an interaction of the polycondensate network of Ti02 with the ECTFE after thermally treating the composite material, which resulted in no observable loss of the mechanical strength of the ECTFE up to temperatures of or around 400 ° C. This was an increase of more than 125 ° C compared to the untreated ECTFE, which indicates that the Ti02 network interacts during the warm-up (but not after the initial formation of the composite material) with the ECTFE and acts to stabilize the structure that in turn, it preserves and extends the mechanical strength of the ECTFE at temperatures of 125 ° C above its normal utility.

Example 16 - Antistatic Materials Used as Photographic Elements and Support Layers The composite materials of the present invention can be used as antistatic materials to be used as photographic elements and support layers. The patent of E.U.A. 5,284,714 issued to Anderson et al. ("Anderson M"), which is incorporated herein by reference, discloses photographic support materials comprising an antistatic layer and a heat thickening barrier layer. The antistatic layer comprises a V205 film applied to a material that is coated with a layer of heat thickening polyacrylamide. The composite materials of the present invention can be used in place of the antistatic layer used in Anderson II. For example, instead of applying a thin layer of polyacrylamide on top of an antistatic V2Od film, the antistatic V205 layer can be simply incorporated directly into the polyacrylamide using the methods of the present invention. Similarly, the patent of E.U.A. 5,366,544 issued to Jones et al. ("Jones"), which is incorporated herein by reference, discloses the use of an antistatic layer used as a photographic imaging element prepared by mixing V205 in a polymeric cellulose acetate binder. Using the methods of the present invention, V205 can be incorporated directly into a cellulose acetate binder. This material can then be used in place of the antistatic layer described in Jones. Finally, the patent of E.U.A. 5,439,785 issued to Boston et al. ("Boston"), which is incorporated herein by reference, discloses photographic elements comprising antistatic layers of V205, epoxy silanes and sulfopolyesters. Using the methods of the present invention, V205 can be easily incorporated into the sulfopolyesters as well as epoxy silanes, and these materials can be used as antistatic layers in the photographic elements described in Boston.

Example 17 - Infusion of Metal Species Stabilized to a Preformed Polymer Material A 5.08 x 5.08 cm piece of FEP polymer film was placed in a glass tube with 100 mg of ferrocene, and the tube was connected to a vacuum line and pumped at a pressure less than 10 mTorr. Then, the glass tube containing the FEP film and ferrocene was sealed under vacuum and immersed in an oil bath at 80 ° C, which, at a pressure of 10 mTorr, is high enough to sublimate and produce a phase of ferrocene gas inside the reaction tube. After 1 hour, the FEP was removed from the reaction vessel and thoroughly rinsed in toluene for 30 minutes. In this Example, the ferrocene molecules infused do not form macromolecular networks and the stability of the ferrocene molecules depends on their ability to form a complex or interact with the fluorine functionality contained within the FEP polymer. The incorporation of ferrocene was confirmed through analysis by UV-vis spectroscopy.

Example 18 - Infusion of Pi-alyl Metal Complexes into Preformed Polymer Materials First a polymer film was placed together with 10 mg of pi-allyl complex to a reaction vessel, which subsequently was attached to a vacuum line. The vessel was pumped at a pressure less than 10 mTorr at -196 ° C. the evacuated vessel was then heated at 80 ° C for 1 hour. The polymer film was removed from the reaction vessel and then exposed to an atmosphere of H2 gas, which was converted to the allyl complex contained within the polymer to a reduced metal form, which was stabilized within the polymeric material with the release Concurrent propane gas outside the polymer film.

Example 19 - Catalytic Oxidation of Methanol and o-Xylene 100 mg of MFA resin (beads having diameters of about 0.5 mm) were infused with vanadium (about 1% -2% vanadium, by weight) using the method set forth in Example 1. The infused MFA resin was then placed in a stainless steel container. After sealing the vessel, gas ports were used to fill the vessel with a mixture of 20% oxygen and 80% helium at atmospheric pressure. Then, 5-10 microliters of methanol were introduced and the vessel was heated at 60 ° C for 2 hours. The product was analyzed using gas chromatography, and the conversion of methanol to both formaldehyde and formic acid was indicated. The same experiment was performed using o-xylene instead of methanol. Analysis by both gas chromatography and infrared spectroscopy indicated that o-xylene was selectively oxidized to phthalic anhydride. The infusion of titanium to fluoropolymer resins should also produce a good heterogeneous catalyst, particularly well suited to catalyze selective oxidation reactions as well as to promote the polymerization of alkenes to respective olefinic polymers. In some cases, oxidation reactions may require a co-reductant, such as peroxides (for example, hydrogen peroxide or benzoyl peroxide) or, as another example of many co-reductants, iodoisobenzene, which is commonly used in the epoxidation of olefins in the presence of metalloporphyrins.

Example 20 - Anti-fouling compositions Vanadium was infused into both fluoropolymers of MFA and FEP using the method described in Example 1. The MFA and FEP infused were films with a thickness of 76.2 microns and a geometry of 20.32 x 25.4 cm. These films plus two reference MFA and FEP films (without vanadium) were then epoxidized to a 10.16 x 7.62 cm sheet of plywood, which was subsequently placed in a seawater conduit between the coast in the Gulf of Mexico at the Florida side near Sarasota for two months. When, after two months, the sheet of plywood was removed from the water, all the board was embedded with limpets or other marine crustaceans. After exposure of the board to an asp, moderate ersión of water, however, almost all crustaceans were removed from the films of MFA and FEP, which were infused with vanadium. The removal of the crustacean from the MFA and reference FEP was only about 50%, and the crustaceans attached to the plywood were 100% intact after the water spray test. To establish if vanadium was leached from sheets of MFA and FEP, the sheets of MFA and FEP infused with vanadium were subjected to hot nitric acid solutions for more than 72 hours. The analysis of the solutions through inductively coupled plasma atomic absorption spectroscopy ("ICP") and visible UV spectroscopy showed the absence of any vanadium complex. In this way, no leaching of vanadium was observed at the detection limits of 1 ppb, suggesting that the vanadium complex within the MFA and FEP remained intact. These results demonstrate that the coatings against scale formation of the present invention are not deposited in the environment, in contrast to conventional marine anti-fouling coatings, which mainly operate by releasing heavy metals or other toxic materials from the surface onto the surface. which are placed as coatings. Therefore, the coatings against scale formation of the present invention are particularly advantageous in environments that are sensitive to the toxic effects of heavy metals. In addition, since the composites of the present invention do not operate by releasing the active ingredient (e.g., metal), it is expected that the composite material will have a much greater anti-fouling life.

Example 21 - Modification of FEP Before and After Infusion of FEP with SiCl.? FEP Modified. The FEP was modified using an H2 / MeOH plasma as described here above. For this experiment, the FEP was modified using a 90-second exposure, which results in a nominally modified material (ie, only 2.8% oxygen and approximately a 3: 1 ratio between C-F2 and C functionality). -OH modified measured and observed in the 1S region of ESCA carbon). Infusion of FEP + SiCI4 Modified. This sample was produced using a 90-second radio frequency luminescent discharge composed of H2 and MeOH as described hereinabove, as the preferred method of modification. The infusion was carried out by placing a film with a thickness of 50.8 microns, and 4 x 6 cm, of the thick film of the modified FEP in an evacuated container containing approximately 1.0 g of SiCl4 evacuated to less than 10 mTorr and reacting for 1 hour. hour at room temperature. After removing the FEP sample from the infusion container, the FEP was ultrasonically cleaned in H20 for 30 minutes both to hydrolyze SiCI4 to the polycondensate (e.g., - (SiOx-0-SiOx) and to remove any of the non-covalently formed silicate. Attached to the surface or not permanently infused to the material Subsequent to the analysis through ESCA it was shown that the surface had 1.8% silicon and that the% oxygen was increased from 2.8% (measured in the modified non-infused FEP) to 7.2 These results indicate that the silicate formed not only within the volume, but also, unexpectedly, on the surface Table 2 lists the results of ESCA for the unmodified PEF infused with SiCI 4. When the infusion was carried out in unmodified FEP only 0.3% Si and 2.2% oxygen were measured on the FEP surface, thus, by first modifying the FEP, one can obtain not only a fluoropolymer that has to a global infused metal oxide but also a material having a silicate (metal oxide) coating on the abutting surface of the FEP material. This FEP coating is useful for joining metals, metal oxides, polymers, biological molecules and phosphorescent and / or luminescent materials. Inspection through Photo-electron Spectroscopy of X-ray (ESCA or XPS) of the 1s region of the modified FEP oxygen showed two bands: one at approximately 536.5 and the other at approximately 533.5. The band 533.5 corresponds to the silicate residing on the surface. The band observed at approximately 536.5 is unusually high and is indicative of the silicate oxide contained within the highly electronegative FEP volume. This is consistent with the ESCA results of Si2p, which show only one band centered at approximately 102.8 eV, which is consistent with what you might observe for a silicate. The combination of these results indicates that the silicate species formed both within and on the adjacent surface of the fluoropolymer are the same by chemical nature, but in the silicate formed within the fluoropolymer matrix it was influenced by the electronegativity of the surrounding fluoropolymer, which It results in a silicate in bulk and on the surface having different electronic characteristics. Unmodified FEP Infused with SiCI4. The unmodified FEP was infused with SiCI4 using the identical conditions described above for the infusion of SiCI4 in the modified FEP. Subsequent hydrolysis of SiCI4 to the silicate took place, and, as can be seen in Table 2, only a very small concentration of the silicate is observed on the adjoining surface. The only observation made in this material belongs to the 1s region of the oxygen of the ESCA spectrum, which shows the bands at 536.5 and 533.5. The bands at 536.5 and 533.5 are consistent with the previous discussion, which explains these two different ESCA oxygen bands 1s as similar in chemical nature (ie, a silicate oxide) but different in electronic nature (due to the silicate residing in the fluoropolymer volume against the silicate residing in the surface of the EFF). These results are similar to those reported for the modified silicate-infused FEP material as described above, except that the band associated with the oxygen present on the surface is much greater in the case where the infused FEP was first modified. This is consistent with the above results demonstrating the desire to modify the fluoropolymer surface to obtain a silicon oxide coating above the surface of the fluoropolymer.

TABLE 2 Displays% Fluorine% Carbon% Silicon% Oxygen Modified FEP 58.0 39.2 2.8 (90 sec RFGD) Modified FEP + 55.5 35.5 1.8 7.2 Infusion of SiCI4 Unmodified FEP 64 33.4 0.3 2.2 infused with SiCI4 FEP fused with 46.3 46.7 0.1 6.9 S¡CI4 + 2 min. RFGD Example 22 - Infusion to Modified and Unmodified Fluoropolymers The results listed in Table 3 illustrate that the infusion of metals and metal oxides (as demonstrated in this example using SiCl4) into the volume of halopolymers can be effected in such a way that by first modifying the surface of the layer the union can be obtained of the infused metal or the metal oxide material not only within the volume but on the surface of the halopolymer as well. This is further demonstrated through the ESCA (or XPS) results, which show more than two forms of oxygen and silicon on the surface of these materials. Since the sampling depth of the ESCA experiment allows molecular and polymeric species to be observed both on the surface as well as on the volume of adjoining surface of any inspected material, differences in the material that lies within the volume can be discerned. and on the adjoining surface of the air. Accordingly, the above experiments show multiple spectroscopic bands for both 1s of oxygen and the 2p functionality of silicon as observed in the materials that have been infused. Essentially, the modified materials exhibit only one oxygen band relative to the oxygen uptake due to surface modification achieved using the H2 / MeOH modification RFGD (except in the case of the MFA material, which initially includes an oxygen functionality due to the perfluoroalkoxy functionality included within its polymer structure). After the infusion of SiCI, and its subsequent hydrolysis to a silicate material, at least one other oxygen band by ESCA (in some cases more than one) was observed. These extra bands are thought to be due to the formation of silicon oxides from different polymer structures as well as the silicon oxide formed on the surface. For example, a silicon oxide within the overall material can be directly influenced by the electronegative characteristics of the electron withdrawing halogen functionality, thus giving it a different binding energy in relation to the measurement of silicon oxide species covalently bound to proliferated on the surface of the active oxidized halogenated polymer. This is demonstrated in the following examples as well as the difference between the infusion of surface modified halopolymers against the infusion of halopolymers which have been previously modified to include reactive oxygen functionalities on the surface.

TABLE 3 Sample% Carbon% Oxygen% Fluorine% Silicon% Chlorine Modified PTFE 34.3 2.0 63.7 N / A N / A Modified PTFE 34.2 10.1 52.9 2.8 N / A More infusion SiCI4 Modified MFA 36.0 3.6 60.4 N / A N / A Modified MFA plus infusion SIC 28.2 28.1 34.5 9.2 N / A Modified ECTFE 69.8 9.0 19.3 N / A 1.8 ECTFE plus 43.0 33.1 13.8 9.0 1.1 infusion SiCI4 Example 23 - Modified ECTFE and Unmodified ECTFE Infused with SiCI The results of ESCA infusion of S¡CI4 in both modified and unmodified ECTFE indicate that the atomic percentage of Si residing on the surface (which is related to the concentration of metal oxide on the surface) is higher in the case when The ECTFE material is modified against the unmodified ECTFE material. Specifically,% silicon (strictly due to silicon oxide) is increased from 2.5% to 9.0% in the case where the ECTFE material was modified first. Correspondingly,% oxygen is increased from 8.9% to 33.1% (again the increase was observed in the ECTFE material), indicating a large increase in silicon oxide residing on the surface, which is due to the effect of Initially modify the ECTFE which results in a coating of the silicon oxide covalently bound to the surface of modified ECTFE. This coating is not observed to the same degree in the material infused with unmodified ECTFE.

Example 24 - Surface Modified and Unmodified Halopolymers Infused with TiC A variety of surface modified and non-modified halopolymers were infused with TiCl 4 and then hydrolyzed to form networks of titanium oxide material in the volume of the halopolymers as well as on the surface of the modified halopolymers. The infusion process was performed by placing films of the halopolymers in a glass container, evacuating the container to approximately 10 mTorr or less, then introducing the TiCl4 into the evacuated container, and then heating the container to 90 ° C. After 1 hour, the halopolymer films were removed to room air and then first ultrasonically washed in distilled H20 for 30 minutes and then ultrasonically washed in MeOH for 30 minutes. The ESCA analysis was performed on these halopolymer films, and the results were obtained from three different halopolymer films, mainly PTFE, MFA and ECTFE. For each material, the data from the two separate films were collected: one of which was fused without the previous surface modification and the other was infused after surface modification with H2 / MeOH RFGD. Infusion of PTFE Modified and Unmodified. The modified PTFE was prepared using a 4 minute exposure time to an H2G / MeOH RFGD plasma as described hereinabove as the preferred method of surface modification of the halopolymer. The results of ESCA showed that the% of titanium measured on the surface of these materials increased from 0.25% (measured on the modified PTFE without surface) to 0.60% (measured on the modified PTFE on the surface). The oxygen% due to titanium oxide was increased from 4.1% (measured on the modified PTFE without surface) to 7.8% (measured on the modified PTFE on the surface). These results indicate the desire to modify the PTFE surface first in order to extend the development of titanium oxide (formed within the PTFE volume) out of the volume and on the PTFE surface. The ESCA results also revealed the presence of two oxygen bands (one at 536.4 eV due to the oxide contained in the volume and the other at 532.0 eV due to surface-resident oxide) and two bands of titanium (one at 459.9 eV due to titanato in bulk and the other to 456.2 eV due to the resident titanate on the surface). As discussed previously, the observation of two oxygen bands and two titanium bands is indicative of the formation of titanium oxide in the volume, which is heavily influenced by the electronegative functionality of PTFE and the formation of titanium oxide outside the volume , so that it exists as a homogeneous material, which has different electronic characteristics, which give rise to ESCA signals of oxygen and titanium significantly different from those of the titanium oxide material resident in the PTFE volume. Infusion of Modified and Unmodified MFA. The modified MFA was prepared using a 3 minute exposure time to an RFGD H2 / MEOH plasma as described hereinbefore, as the preferred method of halopolymer surface modification. The results of ESCA showed that the% of titanium measured on the surface of these materials was increased by five times, from 0.20% (measured on the modified MFA without surface) to 1.00% (measured on the modified MFA on the surface). The% oxygen due to titanium oxide was increased from 8.9% (measured on the modified MFA without surface) to 10.25% (measured on the modified MFA on the surface). These results indicate the desire to first modify the surface of MFA in order to extend the development of titanium oxide (formed within the volume of the MFA) outside the volume and on the surface of MFA. The ESCA results also reveal the presence of three oxygen bands (one at 536.1 eV due to the titanium oxide contained in the volume, a second at 533.4 eV due to perfluoroalkoxy functionality contained within the MFA material, and a third at 531.4 eV due to titanium oxide residing on the surface) and two titanium bands (one at 459.4 eV due to bulk titanate) and another 455.7 eV due to surface resident titanate). As discussed previously, the observation of two oxygen bands and two titanium bands is indicative of the formation of titanium oxide in the volume, which is greatly influenced by the electronegative functionality of MFA and the formation of titanium oxide outside the volume so that there is a homogeneous material, which has different electronic characteristics, which give rise to ESCA signals of oxygen and titanium significantly different from those of the titanium oxide material resident in the volume of MFA. Infusion of Modified and Unmodified ECTFE. The modified ECTFE was prepared using a 90 second exposure time to an H2G / MeOH RFGD plasma as described hereinbefore as the preferred method of surface modification of the halopolymer. The ESCA results show that the% of the titanium measured on the surface of these materials was increased by twice 0.50% (measured on the modified ECTFE without surface) to 1.00% (modified on the modified ECTFE on the surface). The% oxygen due to titanium oxide was increased from 4.3% (measured on the modified ECTFE without surface) to 10.90% (measured on the modified ECTFE on the surface). These results indicate the desire to modify the ECTFE surface first in order to extend the development of the titanium oxide (formed within the volume of the ECTFE) outside the volume and on the ECTFE surface. The ESCA results also reveal the presence of two oxygen bands (one at 534.7 eV due to titanium oxide contained in the volume and the other at 531.1 eV due to titanium oxide residing on the surface) and two titanium bands ( one at 457.2 eV due to the bulk titanate and the other at 455.2 eV due to the titanate residing on the surface). As previously discussed, the observation of two oxygen bands and two titanium bands is indicative of the formation of titanium oxide in the volume, which is influenced by the electronegative functionality of ECTFE and the formation of titanium oxide outside the volume of way that exists as a homogeneous material, which has different electronic characteristics that give rise to ESCA signals of oxygen and titanium significantly different from those of the titanium oxide material that resides in the volume of ECTFE.

Example 25 - Infusion of Polymers to Reduce the Permeability of Likes and Gases In many cases, it is useful to reduce the penetration of liquids and gases through polymeric materials. For example, the patent of E.U.A. No. 5,298,291 issued to Klinger et al., Which is incorporated herein by reference, discloses an epoxy-functional fluoropolyol polyacrylate coating of optical fibers as being useful as a moisture inhibitor and for inhibiting the penetration of water through the network. polymer, thus avoiding moisture-induced corrosion of the underlying optical fiber material. As another example, the patent of E.U.A. No. 5,320,888 issued to Stevens, which is incorporated herein by reference, discloses sheets of fluoroelastomers, non-elastomeric fluoropolymers, and non-fluorinated elastomers as being both flexible and useful for inhibiting fuel penetration. The composite materials of the present invention and the composite materials made in accordance with the methods of the present invention are believed to be useful for inhibiting the penetration of both gases and liquids. Both the halopolymers (including elastomeric and non-elastomeric halopolymers) and the non-halopolymers can be infused with metals and / or metal oxides, which can act to fill the free volumes of the halopolymers or non-halopolymers, thus increasing the polymer density and blocking the penetration of both gases and liquids. The degree to which the penetration of gases and liquids is inhibited can be controlled through the selection of metal and / or metal oxide and by the degree to which the metal and / or metal oxide is developed within the free volume of the halopolymer and not halopolymer. For example, 0.1 g of TaF5 was placed in a glass container containing an ECTFE halopolymer film, said film had a density of 1.26 g / cm 3. The vessel was evacuated at a pressure of less than 10 mTorr and then heated to about 150 ° C. After 1 hour, the film was removed from the container and ultrasound was applied in distilled H20 for 30 minutes and then ultrasound was applied in MeOH for 30 minutes. After the sample was dried it was weighed and the density was calculated as 1.51 g / cm3. In this way, the formation of tantalum oxide resulted in an increase in density of 16%. Measurements of the amount of TaOx showed that the amount of TaOx added to the ECTFE film was approximately 2% by weight with the corresponding increase in density being 16%. It is expected that this material will show significant reductions in gas and liquid permeability based on the measured increase in film density. Alternatively, several grams of ECTFE powder (having diameters of between 1 miera and 10 microns) were reacted with TaF5 in the same manner as described above for the ECTFE film. After the infusion of TaF5, TaF5 was converted to TaOx through hydrolysis. It is believed that the powder is useful for coating objects either by thermal spraying or plasma spraying. The sprayed coating will have the same properties as those of the infused ECTFE film and will result in a coating having reduced gas and liquid permeability characteristics as compared to a sprayed ECTFE coating, which was not infused with TaOx. In addition, the infused ECTFE powder can be modified on the surface either before or after the infusion using any of the methods described herein (preferably the H2 / MeOH RFGD plasma treatment method) in order to provide good performance characteristics. wettability and / or adhesion to the surface. These surface-modified powders can then be used to coat other materials, for example, through thermal or plasma spray techniques (or as the surface is more wettable and adhesive) through the mixing of the powders to the surface. paints, lacquers, or other resins that can be applied, for example, by roller, brushing, or spraying.

Although the invention has been described in detail for the purpose of illustration, it is understood that said details are for that purpose only, and variations may be made thereto by those skilled in the art without departing from the spirit and scope of the invention, which is defined in the claims that follow.

Claims (117)

1. CLAIMS 1. - A method for making a composite material comprising: providing a polymer having a free volume therein; evacuate the free volume of the polymer; and infusing inorganic or organic molecules into the free void volume of the polymer.
2. 2. A method according to claim 1, wherein the free volume of the polymer is the natural free volume of the polymer.
3. 3. A method according to claim 1, further comprising: polymerizing the inorganic or organic molecules under conditions effective to assemble the inorganic or organic molecules in macromolecular networks.
4. 4. A method according to claim 3, wherein the polymerization is carried out photochemically, chemically or electrochemically.
5. 5. A method according to claim 3, wherein the polymerization is carried out by oxidizing, hydrolyzing or hydrogenating the inorganic or organic molecules.
6. 6. A method according to claim 5, wherein the oxidation, hydrolyzation or hydrogenation comprises: exposing the inorganic or organic molecules to a gas comprising water, oxygen, hydrogen or combinations thereof.
7. 7. A method according to claim 6, wherein the polymerization is carried out by oxidizing or hydrolyzing the inorganic or organic molecules and wherein the gas is ambient air.
8. 8. A method according to claim 3, wherein the inorganic or organic molecules are inorganic molecules comprising metal atoms and ligands attached thereto, which can be split from the metal atoms through the exposure to actinic radiation and wherein the polymerization comprises: exposing the inorganic molecules to actinic radiation under effective conditions to unfold the ligands of the metal atoms, and exposing the metal atoms having ligands split from them to a gas containing oxygen or that It contains water under effective conditions to cause metal atoms to assemble into molecular networks.
9. 9. A method according to claim 3, wherein the inorganic or organic molecules are pi-allyl compounds of metals of Group Illa, IVa, Va, Via, Vlla or Villa and wherein said polymerization comprises: contacting the pi-allyl compounds with hydrogen gas under conditions effective to cause the formation of a macromolecular metal network of zero conductive valence. 10. - A method according to claim 1, wherein the polymer comprises a functionality and wherein said method further comprises treating the inorganic or organic molecules under effective conditions to cause the inorganic or organic molecules to interact with the functionality of the polymer. 11. A method according to claim 10, wherein the functionality is a halogen atom. 12. A method according to claim 10, wherein the functionality is a fluorine atom. 13. A method according to claim 10, wherein said treatment is carried out photochemically, chemically or electrochemically. 14. A method according to claim 10, wherein the treatment is carried out by oxidizing, hydrolyzing or hydrogenation of the inorganic or organic molecules. 15. A method according to claim 14, wherein the oxidation, hydrolyzation or hydrogenation comprises: exposing the inorganic or organic molecules to a gas comprising water, oxygen, hydrogen or combinations thereof. 16. A method according to claim 15, wherein the treatment is performed by oxidizing or hydrolyzing the inorganic or organic molecules and wherein the gas is ambient air. 17. A method according to claim 10, wherein the inorganic or organic molecules are inorganic molecules comprising metal atoms and ligands attached thereto, which can be split from the metal atoms through the exposure to actinic radiation and where the treatment comprises: exposing the inorganic molecules to actinic radiation under effective conditions to unfold the ligands of the metal atoms, and treating the metal atoms having split ligands thereof photochemically, chemically, electrochemically or thermally under effective conditions to cause the metal atoms to interact with the functionality of the polymer. 18. A method according to claim 1, wherein said infusion is performed under non-supercritical conditions. 19. A method according to claim 1, wherein the inorganic or organic molecules are infused into the free volume of the polymer in a gaseous state. 20. A method according to claim 1, wherein said infusion comprises: vaporizing the inorganic or organic molecules to produce a vapor of inorganic or organic molecule; and contacting the polymer with the vapor of inorganic or organic molecule. 21. A method according to claim 1, wherein the polymer comprises halopolymers, polyimides, polyamides, polyalkenes, poly (phenylenediamine terephthalamide) filaments, polyethylene terephthalates, modified cellulose derivatives, starch, polyesters, polymethacrylates, polyacrylates, polyvinyl alcohol, copolymers of vinyl alcohol with ethylenically unsaturated monomers, polyvinyl acetate, poly (alkylene) oxides, homopolymers and copolymers of vinyl chloride, terpolymers of ethylene with carbon monoxide and with acrylic acid ester or vinyl monomer, polysiloxanes , homopolymers and copolymers of halodioxoles and substituted dioxoles, polyvinylpyrrolidone or combinations thereof. 22. A method according to claim 1, wherein the polymer comprises a halopolymer. 23. A method according to claim 22, wherein the polymer comprises a fluoropolymer. 24. A method according to claim 11, wherein the polymer has a crystallinity of less than about 99%. 25. A method according to claim 1, wherein the polymer has a glass transition temperature of Tg and a temperature of thermal decomposition of Td and wherein said infusion is carried out at a temperature of about Tg - 50 ° C at approximately Td and to which the inorganic or organic molecules have a non-zero vapor pressure. 26. A method according to claim 1, wherein the inorganic or organic molecules are selected from the group consisting of VOCI3, W (CO) 6, Fe (CO) 5, TiCl4, SiCl4, AICI3, PCI3, SbCI5, As (C2H5) 3, Ba (C3H7) 2, complexes of borane-pipdin and tetrahydrofuran, Cd (BF4) 2, Ca (OOCCH (C2H5) C4H9) 2, cerium (III), 2-ethylhexanoate, 2-ethylhexoxide of cesium , chromium naphthenate (lll), Cr02CI2, Co (CO) 3NO, copper (II) dimethylaminoethoxide, triethyl iron, GeCI, triethylindium, lead naphthenate, C2H5MgCI, (CH3) 2Hg, MoF6, Ni (CO) 4, Nb (OC2H5) 6, HRe04, Ta (OC2H5) 5, Ta (OC2H5) 5, C5H5TI, SnCl, pi-allyl compounds of Group Illa, IVa, Va, Vlla, or Villa and combinations thereof. 27. A method according to claim 1, wherein the composite material has flexibility, crystallinity, or a temperature of thermal decomposition, which is substantially equal to those of the polymer. 28. A method according to claim 27, further comprising: treating the thermal composite, chemically, photochemically or electrochemically under conditions effective to alter a physical, chemical, optical or electrical properties of the composite material. 29. A composite material comprising: a polymer that has a natural free volume in it; and an inorganic or organic material disposed in the natural free volume of said polymer. 30. A composite material according to claim 29, wherein said composite material has dimensions that are substantially equal to the dimensions of the polymer. 31. - A composite material according to claim 29, wherein said natural free volume does not contain any carrier liquid. 32. A composite material according to claim 29, having flexibility, crystallinity or temperature of thermal decomposition, which is substantially those of the polymer. 33.- A composite material according to the claim 29, wherein the natural free volume is defined by free volume surfaces and wherein the inorganic or organic material is present as a layer on or along free volume surfaces. 34.- A composite material according to claim 29, wherein the polymer comprises a functionality and wherein said inorganic or organic material interacts with the functionality of the polymer. 35.- A composite material according to claim 34, wherein the functionality is a halogen atom. 36.- A composite material according to claim 34, wherein the functionality is a fluorine atom. 37.- A composite material according to claim 29, wherein the inorganic or organic material is an inorganic or organic macromolecular network. 38.- A composite material according to claim 37, wherein the inorganic or organic macromolecular network is an inorganic macromolecular network. 39.- A composite material according to the claim 38, where the inorganic macromolecular network has the formula, [X (0) n-Oy-X (0) n] m, wherein m is an integer from about 1 to about 10,000; X represents a metal ion that has a charge of + s; s is an integer of 1 to the oxidation state that can be obtained higher than the metal; and is an integer from 0 to s; and n is between zero and s / 2. 40.- A composite material according to claim 38, wherein the inorganic macromolecular network is a macromolecular network of zero conductive valence that contains a metal from Group Illa, IVa, Va, Vía, Vlla or Villa. 41.- A composite material according to the claim 37, wherein the inorganic or organic macromolecular network is an organic macromolecular network. 42.- A composite material according to the claim 40, where the organic macromolecular network has the formula. { R-R) n, where n is an integer from about 1 to about 10,000 and R is a monomer radical. 43.- A composite material according to the claim 40, wherein the organic macromolecular network comprises polyacetylene, polypyrrole, polyaniline, polythiophene, or combinations thereof. 44. A composite material according to claim 29, wherein said polymer comprises halopolymers, polyimides, polyamides, polyalkenes, poly (phenylenediamine terephthalamide) filaments, polyethylene terephthalates, modified cellulose derivatives, starch, polyesters, polymethacrylates, polyacrylates , polyvinyl alcohol, copolymers of vinyl alcohol with ethylenically unsaturated monomers, polyvinyl acetate, poly (alkylene) oxides, homopolymers and copolymers of vinyl chloride, terpolymers of ethylene with carbon monoxide and with acrylic acid ester or vinyl monomer, polysiloxanes, homopolymers and copolymers of halodioxoles and substituted dioxoles, polyvinylpyrrolidone or combinations thereof. 45.- A composite material according to claim 29, wherein said polymer comprises a halopolymer. 46.- A composite material according to claim 45, wherein said polymer comprises a fluoropolymer. 47.- A composite material according to the claim 29, wherein said polymer has a crystallinity of less than about 99%. 48. A composite material according to claim 29, having a volume Vc, wherein the natural free volume is greater than about 1 x 10"6 Vc. 49. A composite material according to claim 29, in wherein the inorganic or organic material is an inorganic material comprising a metal selected from the group consisting of V, W, Fe, Ti, Si, Al, P, Sb, As, Ba, B, Cd, Ca, Ce, Cs, Cr, Co, Cu, Ga, Ge, In, Pb, Mg, Hg, Mo, Ni , Nb, Re, Ta, TI, Sn, Ir, Rh, Th, Ru, Os, Pd, Pt, Zn, Au, Ag, and combinations thereof. 50.- A method for catalyzing a reaction of a reagent comprising: providing a composite material according to claim 29, wherein the inorganic or organic material is suitable to catalyze the reaction of the reagent; and contacting the composite material with the reagent under effective conditions to catalyze the reaction. 51. A method according to claim 50, wherein the reagent is a gaseous reagent. 52. A method according to claim 51, wherein the reagent is S02 and the inorganic or organic material is an inorganic macromolecular network comprising vanadium. 53. A method according to claim 51, wherein the step of contacting is performed under supercritical conditions. 54.- A method according to claim 51, wherein the reaction is an oxidation reaction, the reagent is an oxidizable substrate and wherein said step of contacting is carried out in the presence of an oxidizing agent. 55. A method according to claim 54, wherein the oxidizable substrate is methanol and wherein the method produces formaldehyde and formic acid. 56. A method according to claim 54, wherein the oxidizable substrate is o-xylene and wherein the method produces phthalic anhydride. 57.- A method according to claim 54, wherein the oxidation agent is oxygen. 58. A method according to claim 54, wherein said method is carried out in the presence of a co-reductant. 59. A method according to claim 54, wherein said polymer comprises a fluoropolymer. 60.- A method according to claim 54, wherein the inorganic material comprises vanadium or titanium. 61.- An electroconductive image forming element that comprises: an insulating support; an electrically conductive layer overlapping the support, wherein the electrically conductive layer comprises a composite material of claim 29; and a dielectric imaging layer overlaying the electrically conductive layer. 62.- A photographic element that comprises: a substrate; a layer sensitive to light directly or indirectly disposed on the substrate; and an antistatic layer directly or indirectly disposed on the substrate, wherein the antistatic layer comprises a composite material of claim 29. 63. An electrolytic fuel cell comprising: a composite material of claim 29; an anode in electrical contact with the composite material; and a cathode in electrical contact with the composite material. 64.- A method for protecting a material of electromagnetic radiation emitted from an electromagnetic source comprising: arranging between the material and the source of electromagnetic radiation, a composite material according to claim 29, wherein the inorganic or organic material comprises a metal 65.- A method for protecting a material of the heat source or flames comprising: arranging between the material and the source of heat or flames, a composite material according to claim 29, wherein the inorganic or organic material is a metal oxide. 66.- A method to prevent the formation of scaling of a surface by organisms, the method comprises: applying, to the surface, a composite material comprising a polymer having a free volume therein, and an inorganic or organic material disposed therein the free volume of the polymer. 67.- A method according to claim 66, wherein the surface is the surface of a vessel that goes through the water, a propeller, a pillar or a pipe. 68.- A method according to claim 66, wherein the organisms are aerobic. 69. - A method according to claim 66, wherein the organisms are marine organisms, aquatic organisms or microbes. 70. A method according to claim 66, wherein the organisms are crustaceans or mussels. 71. A method according to claim 66, wherein the inorganic material is capable of catalytically depositing the dioxygen. 72. A method according to claim 66, wherein the inorganic material comprises vanadium or titanium. 73.- A method according to claim 66, wherein the surface is in continuous or intermittent contact with water. 74.- A method according to claim 66, wherein the step of applying comprises: providing the composite material in sheet form and contacting the composite material in sheet form with the surface under effective conditions to bond the composite material in the form of foil to the surface. 75.- A method according to claim 66, wherein the step of applying comprises: providing the composite material in the form of a bead or powder dispersed in an uncured resin; contacting the composite material in the form of a bead or powder dispersed in uncured resin with the surface; and curing the uncured resin to an effective degree to bond the composite material in the pearl or powder form to the surface. 76.- A method according to claim 75, wherein the step of contacting comprises spraying, deposition, painting or immersion. 77.- A method according to claim 66, wherein the step of applying comprises: applying an uncured resin to the surface; contacting the composite material in the form of a pearl or powder with the uncured resin; and curing the uncured resin to an effective degree to bond the composite material in the pearl or powder form to the surface. 78. A method according to claim 66, wherein the step of applying comprises: providing the composite material in the form of a bead or powder dispersed in a suitable solvent; contacting the composite material in the form of a pearl or powder dispersed in a suitable solvent with the surface; and evaporate the solvent. 79.- A method according to claim 66, wherein the step of applying comprises: coating the composite material in the form of a pearl or powder directly on the surface through thermal spraying, deposition, or immersion or through the use of technology of plasma spray at high temperature. 80.- A method according to claim 66, wherein the polymer comprises a fluoropolymer. 81.- A method for preventing the formation of scale on the surface of a polymer by organisms, wherein the surface of the polymer comprises a polymer having a free volume therein, the method comprising: evacuating the free volume of the polymer; and infusing inorganic or organic molecules into the free void volume of the polymer. 82. A method according to claim 81, wherein the surface of the polymer is the polymer surface of a vessel carried by the water, a propellant, a pillar or a pipe. 83.- A method according to claim 81, wherein the organisms are aerobic. 84. A method according to claim 81, wherein the organisms are marine organisms, aquatic organisms or microbes. 85.- A method according to claim 81, wherein the organisms are crustaceans or mussels. 86.- A method according to claim 81, wherein the inorganic material is capable of catalytically depositing the dioxygen. 87. A method according to claim 81, wherein the inorganic material comprises vanadium or titanium. 88.- A method according to claim 81, wherein the surface is in continuous or intermittent contact with water. 89. - A method according to claim 81, wherein said polymer comprises a fluoropolymer. 90.- An object that has a surface, wherein all or a portion of said surface comprises a polymer having a free volume therein, and an inorganic or organic material disposed in the free volume of the polymer. 91. An object according to claim 90, wherein the surface is in continuous or intermittent contact with water. 92. An object according to claim 90, wherein the object that is a container carried by the water comprises: a helmet, the helmet having an outer surface; and a composite material comprising a polymer having a free volume therein and an inorganic or organic material disposed in the free volume of the polymer, wherein the composite material is attached to at least a portion of the surface of the exterior of the helmet. An object according to claim 90, wherein the object that is a pipeline comprises: a pipe wall having an inner surface and an outer surface; and a composite material comprising a polymer having a free volume therein, and an inorganic or organic material disposed in the free volume of the polymer, wherein the composite material is attached to at least a portion of the inner surface of the wall of pipe, outer surface, or both. 94. An object according to claim 90, wherein the object that is a fixed structure comprises: a support having a surface, the surface being in continuous or intermittent contact with the water; and a composite material comprising a polymer having a free volume therein and an inorganic or organic material disposed in the free volume of the polymer, wherein the composite material is bonded to at least a portion of the support surface. 95. An object according to claim 94, wherein the fixed structure is selected from the group consisting of drilling platforms, oil production rigs, bridges, and pillars. 96. An object according to claim 90, wherein the inorganic or organic material is an inorganic or organic macromolecular network. 97. An object according to claim 90, wherein the inorganic material comprises vanadium or titanium. 98. A method for making an oxyhalopolymer composite material comprising: providing an oxyhalopolymer having a free volume therein; evacuate the free volume of the oxyhalopolymer; and infusing the inorganic or organic molecules into the voided free volume of the oxyhalopolymer. 99.- A method according to claim 98, wherein the step of providing the oxyhalopolymer comprises: providing a halopolymer; modifying the halogen atoms on the surface of the halopolymer under effective conditions to replace at least a portion of the halogen atoms on the surface of the halopolymer with hydrogen atoms and oxygen atoms or oxygen-containing radicals. 100. A method according to claim 99, wherein the halogen atoms on the surface of the halopolymer are modified through radio frequency luminescent discharge of a vapor gas under vacuum comprising: contacting the halopolymer with a gas / vapor plasma mixture, while exposing the halopolymer to at least one radio frequency luminescent discharge under vacuum and under effective conditions to replace at least a portion of the halogen atoms of the halopolymer with covalently bound hydrogen atoms and Oxygen atoms or radicals that contain oxygen. 101.- A method for making an oxyhalopolymer composite material comprising: providing a halopolymer composite material; and modifying the halogen atoms on the surface of the halopolymer under effective conditions to replace at least a portion of the halogen atoms on the surface of the halopolymer composite with hydrogen atoms and oxygen atoms or oxygen-containing radicals. 102. - A method according to claim 101, wherein the step of providing the halopolymer composite material comprises: providing a halopolymer having a free volume therein; evacuate the free volume of the halopolymer; and infusing the inorganic or organic molecules to the free volume evacuated from the halopolymer. 103. A method according to claim 101, wherein the halogen atoms on the surface of the halopolymer composite material are modified through a radio frequency luminescent discharge of a gas-vapor under vacuum comprising: contacting the halopolymer composite material with a gas / vapor plasma mixture, while exposing the halopolymer composite material to at least one radio frequency luminescent discharge under vacuum and under effective conditions to replace at least a portion of the carbon atoms. halogen of the surface of the halopolymer composite material with covalently bonded hydrogen atoms and oxygen atoms or oxygen-containing radicals. 104. A method for making a non-halohalogenated halo-polymer material on the surface comprising: providing an oxyhalogenated non-halo polymer on the surface having a free volume therein; evacuate the free volume of the non-halohydrocarbon halogenated on the surface; and infusing the inorganic or organic molecules to the free volume evacuated from the nonhalo-halogenated halopolymer on the surface. 105. A method according to claim 104, wherein the step of providing the non-halohalogenated halopolymer on the surface comprises: providing a halogenated non-halo polymer on the surface having a free volume therein; and modifying the halogen atoms of the halogenated non-halopolymer surface on the surface under effective conditions to replace at least a portion of the halogen atoms on the surface of the halogenated non-halo polymer on the surface with the hydrogen atoms and oxygen atoms or radicals that contain oxygen. 106. A method according to claim 107, wherein the step of providing a non halogenated halopolymer on the surface comprises: providing a non-halo polymer having a free volume therein; and contacting the non-halo polymer surface with halogen atoms or a halogenated hydrocarbon film or haiohydrocarbon under conditions effective to molecularly link the halogen atoms or the halogenated hydrocarbon film or haiohydrocarbon to the surface of the non-halo polymer. 107. A method according to claim 105, wherein the halogen atoms on the surface of the halogenated non-halo polymer on the surface are modified through a radio frequency luminescent discharge of a gas-vapor under vacuum comprising: in contact the non-halogenated halopolymer on the surface with a gas / vapor plasma mixture, while exposing the halogenated non-halo polymer on the surface to at least one radio frequency luminescent discharge under vacuum and under effective conditions to replace at least one portion of the halogen atoms of the halogenated non-halo polymer surface at the surface with covalently bonded hydrogen atoms and oxygen atoms or oxygen-containing radicals. 108. A method according to claim 104, wherein the non-halohalogenated halopolymer on the surface comprises a non-halo polymer having a surface that is modified with a halogenated hydrocarbon film or haiohydrocarbon, wherein both the non-halo polymer and the film of halogenated hydrocarbon or haiohydrocarbon have free volumes therein and wherein the method further comprises: evacuating the free volume of the halogenated hydrocarbon film or haiohydrocarbon; and infusing the inorganic or organic molecules with the free volume evacuated from the halogenated hydrocarbon film or haiohydrocarbon. 109. A method for making a composite material of non-halohalogenated halopolymer on the surface comprising: providing a halogenated non-halo polymer material on the surface; and modifying the halogen atoms on the surface of the halogenated non-halo polymer material on the surface under effective conditions to replace at least a portion of the halogen atoms on the surface of the halogenated non-halo polymeric material on the surface with hydrogen atoms and oxygen atoms or oxygen-containing radicals. 110. A method according to claim 109, wherein the step of providing a halogenated non-halogenated composite material on the surface comprises: providing a non-halogenated halo polymer on the surface having a free volume therein; evacuate the free volume of the non-halogenated halopolymer on the surface; and infusing inorganic or organic molecules into the free volume evacuated from the halogenated non-halopoiimer on the surface. 111. A method according to claim 109, wherein the non-halogenated halo-polymer on the surface comprises a non-halo polymer having a surface that is modified with a halogenated hydrocarbon film and haiohydrocarbon, wherein both the non-halo polymer and the film of halogenated hydrocarbon or haiohydrocarbon have free volumes in them and where the method further includes: evacuate the free volume of the halogenated hydrocarbon film or haiohydrocarbon; and infusing inorganic or organic molecules into the free volume of the halogenated hydrocarbon film or haiohydrocarbon. 112. A method according to claim 109, wherein the step of providing a halogenated non-halo- polymeric material on the surface comprises: providing a non-halo polymer material; and contacting the surface of the non-halo polymer material with hydrogen atoms or a halogenated hydrocarbon film or haiohydrocarbon under conditions effective to covalently link the halogen atoms or the halogenated hydrocarbon film or haiohydrocarbon to the surface of the composite of the non-halogenated hydrocarbon film. halopolymer. 113. A method according to claim 112, wherein the step of providing a non-halopolymer composite material comprises: providing a non-halo polymer that has a free volume therein; evacuate the free volume of the non-halopolymer; and infusing inorganic or organic molecules into the free volume evacuated from the non-halopolymer. 114. A method according to claim 109, wherein the halogen atoms of the halogenated non-halo polymeric material on the surface are modified through radio frequency luminescent discharge of a vapor gas under vacuum, comprising: contacting the non-halogenated halo-polymer material on the surface with a gas / vapor plasma mixture, while exposing the halogenated non-halo polymer material on the surface to at least one radio frequency luminescent discharge under vacuum under effective conditions to replace at least a portion of the halogen atoms on the surface of the composite material of the halopolymer with covalently bonded hydrogen atoms and oxygen atoms or oxygen-containing radicals. 115. An oxyhalopolymer composite material comprising: an oxyhalopolymer having a free volume therein; and an inorganic or organic material disposed in the free volume of the oxyhalopolymer. 116. A material composed of non-halogenated halohydride on the surface comprising: a non-halogenated halohydrocarbon on the surface having a free volume therein; and an inorganic or organic material disposed in the free volume of the oxyhalogenated non-halo polymer on the surface. 117. A surface-oxihalogenated non-halo polymer material according to claim 116, wherein the non-halohalogenated halo-polymer on the surface comprises a non-halopolymer having a surface that is modified with a halogenated hydrocarbon film or haiohydrocarbon, wherein both the non-halopolymer and the halogenated hydrocarbon or haiohydrocarbon film have free volumes therein, and wherein the inorganic or organic material is disposed in the free volume of the non-halopolymer and in the free volume of the halogenated hydrocarbon film or haiohydrocarbon. SUMMARY Composite materials are described which include a polymer having a natural free volume therein and an inorganic or organic material disposed in the free volume of the polymer. In addition, methods for making a composite material are described. A polymer is provided having a free volume in it. The free volume is evacuated, and the inorganic or organic molecules are infused in the free void volume of the polymer. The inorganic or organic molecules are then polymerized under effective conditions to cause the inorganic or polymerized organic molecules to assemble into macromolecular networks. Alternatively, when the polymer contains a functionality, the inorganic or organic molecules can be treated under effective conditions to cause the inorganic or organic molecules to interact with the functionality of the polymer. It also describes the use of composite materials as protections or filters against photo-radiation, protections or filters against electromagnetic radiation, antistatic layers, heterogeneous catalysts, conductive electrodes, materials that have flame retardant properties and heat, components in construction of electrolytic cells, fuel cells, and optoelectronic devices and anti-fouling agent. Also disclosed are oxyhalopolymer composites, which include an oxyhalopolymer having a free volume therein and an inorganic or organic material disposed in the free volume of the oxyhalopolymer. Also disclosed is an oxyhalogenated non-halo polymer material on the surface. The composite material includes an oxyhalogenated non-halo polymer on the surface having a free volume and an inorganic or organic material disposed in the free volume of the non-halohalogenated halo polymer on the surface. Methods for making and using these oxyhalopolymer composite materials and non-halohalogenated halo-polymer materials on the surface are also described.