US20050202241A1 - High surface area ceramic coated fibers - Google Patents

High surface area ceramic coated fibers Download PDF

Info

Publication number
US20050202241A1
US20050202241A1 US10/797,582 US79758204A US2005202241A1 US 20050202241 A1 US20050202241 A1 US 20050202241A1 US 79758204 A US79758204 A US 79758204A US 2005202241 A1 US2005202241 A1 US 2005202241A1
Authority
US
United States
Prior art keywords
ceramic
fiber
fibers
coated fiber
tio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/797,582
Inventor
Jian-Ku Shang
Rongcai Xie
Zhongren Yue
James Economy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Illinois
Original Assignee
University of Illinois
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Illinois filed Critical University of Illinois
Priority to US10/797,582 priority Critical patent/US20050202241A1/en
Assigned to BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS, THE reassignment BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUSHANG, JIAN, ECONOMY, JAMES, XIE, RONGCAI, YUE, ZHONGREN
Assigned to THE BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS reassignment THE BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS CORRECTIVE ASSIGNMENT TO CORRECT THE <ASSIGNOR&gt; PREVIOUSLY RECORDED ON REEL 015610 FRAME 0328. ASSIGNOR(S) HEREBY CONFIRMS THE FROM <KUSHANG, JIAN&gt; TO <SHANG, JIAN-KU&gt;. Assignors: SHANG, JIAN-KU, ECONOMY, JAMES, XIE, RONGCAI, YUE, ZHONGREN
Priority to MXPA06010223A priority patent/MXPA06010223A/en
Priority to KR1020067020422A priority patent/KR20070004800A/en
Priority to AU2005222413A priority patent/AU2005222413A1/en
Priority to CN2005800149829A priority patent/CN1950308B/en
Priority to CA002558720A priority patent/CA2558720A1/en
Priority to PCT/US2005/008008 priority patent/WO2005087679A1/en
Priority to BRPI0508566-7A priority patent/BRPI0508566A/en
Priority to JP2007503020A priority patent/JP2007528454A/en
Priority to EP05725270A priority patent/EP1732859A1/en
Publication of US20050202241A1 publication Critical patent/US20050202241A1/en
Priority to US12/876,011 priority patent/US8241706B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/42Coatings containing inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/16Disinfection, sterilisation or deodorisation of air using physical phenomena
    • A61L9/18Radiation
    • A61L9/20Ultra-violet radiation
    • A61L9/205Ultra-violet radiation using a photocatalyst or photosensitiser
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • C02F1/32Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/465Coatings containing composite materials
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • C03C2217/71Photocatalytic coatings
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core

Definitions

  • Disinfection by-products are compounds formed in the water treatment process as a result of the disinfection process.
  • a disinfectant such as chlorine is added to source water, where it reacts with a portion of the background organic matter (BOM) present in the source water to produce disinfection by-products.
  • BOM background organic matter
  • AOPs Advanced oxidation processes
  • OH. hydroxyl radical
  • AOPs can be classified into two major groups: AOPs involving homogeneous reactions using hydrogen peroxide (H 2 O 2 ), ozone (O 3 ), chlorine, and ultraviolet (UV) light, alone or in combination; and AOPs employing heterogeneous reactions using photoactive catalysts, such as semiconductors like titanium dioxide (TiO 2 ) and nitrogen-doped titanium dioxide (TiO 2-X N X ).
  • photoactive catalysts such as semiconductors like titanium dioxide (TiO 2 ) and nitrogen-doped titanium dioxide (TiO 2-X N X ).
  • the photocatalytic oxidation processes photoactive semiconductor catalysts are immersed in an oxygenated aqueous solution and illuminated with UV or visible radiation, so that reactive oxygen species are produced, causing the oxidation of organic compounds.
  • the primary oxidant responsible for the photocatalytic oxidation of organic compounds in aqueous solutions is believed to be the highly reactive hydroxyl radical (OH.), although direct reactions of adsorbed organic compounds with surface species, such as holes, have also been reported (Völz et al., 1981; Ceresa et al., Matthews, 1984; and Turchi and Ollis, 1990).
  • OH. hydroxyl radical
  • the anatase form of TiO 2 has a band-gap energy of about 3.2 eV, which is equivalent to the energy of UV light with a wavelength of 387 nm. Consequently, the anatase form of TiO 2 can be activated by radiation with wavelengths less than 387 nm.
  • the excited electrons and the resulting holes may take part in redox processes with adsorbed species, such as H 2 O, OH ⁇ , organic compounds and O 2 at the water-solid interface.
  • the holes may take part in oxidation half reactions with adsorbed H 2 O or OH ⁇ to form hydroxyl radicals.
  • the electrons take part in the reduction half reactions with adsorbed O 2 to produce the superoxide radical O 2 ⁇ , which may also in turn produce H 2 O 2 and OH. (Okamoto et al.,1985).
  • mesoporous TiO 2 with its large surface area is highly desirable, and it was first prepared using a phosphate surfactant through a modified sol-gel process.
  • the product was not pure TiO 2 because of significant amounts of residual phosphorus, and its mesoporous structure underwent partial collapse during template removal by calcination.
  • Another approach produced mesoporous TiO 2 from amphiphilic poly(alkylene) block copolymers as structure-directing agents and organic titanium salts as precursors in a non-aqueous solution. Slight changes in reaction conditions, however, often produced very different results, rendering this method difficult to reproduce.
  • a third method using dodecylamine as a directing agent and titanium isopropoxide as the precursor, and emptying the pores by extractions, yielded a porous structure that was not retained after heat treatment in dry air at 300° C. Thus, it has so far been difficult to produce the highly crystalline TiO 2 that is required for photocatalysis.
  • a further major issue of the current technology is that the powder form of the photocatalyst is difficult to handle, and too fine to be recovered from photoreactors.
  • several films of TiO 2 on various substrates and supports have been developed for photocatalytic applications.
  • particle sintering and agglomeration greatly reduce the surface area of the photocatalyst.
  • the bonding of the TiO 2 to the substrate is also a source of problems.
  • Films of TiO 2 have been assembled on substrates by direct growth and post synthetic crystal attachment. Both methods rely on chemical binders to immobilize TiO 2 to the substrate surface.
  • organic binders are susceptible to decomposition under UV light. Consequently, the TiO 2 films become loose from the substrate, and are easily detached.
  • Powders, fibers and films of TiO 2 have been reported, and a number of photocatalytic TiO 2 powder preparations are commercially available. However, these powders are difficult to apply to water purification, and the surface area of the powders is low, resulting in low catalytic activity and only a small number of catalytic sites.
  • TiO 2 fibers have a very high surface area, high wear and mechanical strength, and high thermal stability. Moreover, when used in chemical reactors, TiO 2 fibers cause only a small pressure drop and can serve as a reinforcement material and as a matrix of various shapes and sizes.
  • TiO 2 fibers may be prepared by various fabrication methods. For example, TiO 2 fibers were prepared by solvothermal reaction of a fibrous K 2 Ti 4 O 9 precursor, by ion-exchange reaction of K 2 O.4TiO 2 fibers and thermal decomposition of H 2 Ti 4 O 9 .
  • Activated carbon fibers are traditionally produced by heating an organic precursor until carbonized, and then activating the carbonized material. Activation is achieved typically by heating the carbonized material in an oxidizing environment. Alternatively, the carbon may be activated chemically. This process involves impregnating the carbon precursor with, for example, phosphoric acid, zinc chloride, or potassium hydroxide, followed by carbonization.
  • U.S. Pat. No. 5,834,114 describes glass or mineral fibers coated with activated carbon. These are prepared by coating the fiber substrate with a resin, cross-linking the resin, heating the coated fiber substrate and resin to carbonize the resin, and exposing the coated fiber substrate to an etchant to activate the coated fiber substrate.
  • U.S. Pat. No. 6,517,906 describes coating the substrate fibers with a mixture containing an organic polymeric material, and a chemical activating agent, for example a Lewis acid or base.
  • a chemical activating agent for example a Lewis acid or base.
  • This mixture carbonizes at temperatures lower than those required by earlier methods, allowing for the formation of activated carbon coatings on low melting point fibers, such as HEPA fibers.
  • the present invention is a method of manufacturing a ceramic coated fiber, comprising heat treating an activated carbon coated fiber containing a ceramic precursor, to form a ceramic coated fiber.
  • the present invention is a ceramic coated fiber, comprising (a) a fiber, and (b) ceramic, coated on the fiber.
  • the ceramic has a BET surface area of at least 60 m 2 /g, and the ceramic comprises crystalline ceramic.
  • the present invention is a method for manufacturing an intermediate for the fabrication of ceramic coated fibers, comprising heating an activated carbon coated fiber containing a ceramic precursor, to cure the precursor.
  • the present invention is a ceramic coated fiber comprising (a) a fiber, and (b) ceramic, coated on the fiber.
  • the ceramic has a BET surface area of at least 50 m 2 /g, and the ceramic comprises at least one member selected from the group consisting of Al 2 O 3 , ZrO 2 , and MgO.
  • FIG. 1 illustrates a surface electron micrograph (SEM) of ceramic fibers produced according to the method of Example 1.
  • FIG. 2 illustrates the photodegradation of stearic acid catalyzed by the fibers of Example 1 ( FIG. 2A ), and by a reference commercial TiO 2 photocatalyst ( FIG. 2B ).
  • FIG. 3 illustrates the photodegradation of stearic acid catalyzed by the fibers of Example 1 ( FIG. 3A ), and by a reference commercial TiO 2 photocatalyst ( FIG. 3B ).
  • FIG. 4 illustrates the photodegradation of humic acid catalyzed by the TiON fibers of Example (3).
  • FIG. 5 illustrates the incubation of an E. coli bacterial culture with the TiON fibers of Example (3) and with the Ag—TiON fibers of Example (5).
  • FIG. 6 illustrates the effect of ACF on surface areas and yield of Al 2 O 3 fibers.
  • FIG. 7 illustrates the effect of the temperature of the second heating on the surface areas and the yield of Al 2 O 3 fibers.
  • FIG. 8 illustrates the effect of the temperature of the second heating on the surface area and the yield of MgO fibers.
  • Activated carbon does not resist temperatures higher than 573 K in an oxidative atmosphere. Therefore, it had been thought to be inapplicable to use activated carbon as a substrate fiber for fabrication processes requiring high temperature calcination, such as the manufacturing of ceramic coated fibers.
  • the present invention is based on the discovery that, despite this instability at high temperatures, activated carbon can be used as a template in the formation of ceramic coated fibers.
  • Activated carbon coated fibers are first prepared by coating substrate fibers with activated carbon or an activated organic coating as described in U.S. Pat. No. 6,517,906.
  • Example substrate fibers include HEPA filters, synthetic fibers used in clothing, polyesters, polyethylene, polyethylene terephthalate, nylon 6, nylon 66, polypropylene, KEVLARTM, TEFLONTM, liquid crystalline polyesters, and syndiotactic polystyrene.
  • Glass fibers such as e-glass fibers; mineral fibers such as asbestos and basalt; ceramic fibers such as TiO 2 , SiC, and BN; metal fibers (or wires) such as iron, nickel, gold, silver, aluminum and platinum; polymer fibers such as TYVEKTM; and combinations thereof.
  • the substrate fibers may be present in any form. Examples include loose fibers, woven and non-woven fabrics, papers, felts and mats.
  • the substrate fibers may be made from substrate fibers already present in a specific form, or the substrate fibers may first be prepared from loose substrate fibers, and made into the specific form.
  • the length of the substrate fibers is not limited, and may be, for example, 0.01 mm to over 100 m in length, but preferably at least 3 micrometers.
  • the substrate fibers may be prepared from longer substrate fibers, then cut or chopped.
  • the diameter of the substrate fibers is also not limited, and may be, for example 100 ⁇ to 1 mm in diameter.
  • the fibers have an aspect ratio of at least 10.
  • the substrate fibers are susceptible to oxidation, it may be advantageous to coat them with an oxidation resistant coating, before forming the activated carbon on the fibers.
  • oxidation resistant coating include water glass and phosphate glass.
  • the activated carbon coated fibers are infiltrated with ceramic precursors by immersion in a solution of one or more ceramic precursors in a volatile solvent.
  • ceramic precursors are compounds of one or more elements present in the ceramic and volatile components, such as halides, nitrates, nitrides, nitrates, hydroxides, organic acid salts and organometallic complexes. When subjected to high temperature treatment, the ceramic elements and any oxygen are left as a ceramic deposit, whereas the remainder of the precursor is volatilized.
  • Ceramic precursors are soluble compounds of the first group, second group, third group, fourth group, the transition metals, the lanthanide and actinide elements, N, O, Se, Te, and Po.
  • Example ceramic precursors include Ti(t-BuO) 4 , Ti(i-Pro) 4 , Si(OEt) 4 , ZnCl 2 , ZrOCl 2 , ZrO(OH)Cl, Zr(COOCH 3 ) 4 , MgCl 2 , Mg(COOCH 3 ) 2 , and MgSO 4 .
  • a mixture of two or more precursors may be used, for instance if a secondary, ternary or quaternary ceramic compound is desired.
  • An oxynitride ceramic coating may be obtained by adding a nitrogen dopant such as a tetraalkylamonium salt.
  • a nitrogen dopant such as a tetraalkylamonium salt.
  • an oxysulfide coating may be made by adding a sulfur dopant such as thiourea.
  • the excess precursor is removed, and the infiltrated precursor may be hydrolyzed by exposure to the moisture in the air, yielding a composite of carbon and the precursor or the hydrolyzed precursor.
  • the ceramic precursor should preferably accumulate in the pores of the template to form an interconnected solid or gel.
  • the system is then subjected to a heat treatment, which may remove residual solvent, cure the precursor, as well as remove the activated carbon, and crystallize the ceramic.
  • the heat treatment may include a first heating at 250° C. to 600° C., or 250° C. to 400° C., optionally in an inert atmosphere, to remove residual solvents and to cure the ceramic precursor.
  • a second heating may follow, for example at 400° C. to 1000° C., in an oxidizing atmosphere, removing the carbon substrate and crystallizing the ceramic, and if necessary, oxidizing the cured precursor.
  • the carbon substrate may also be oxidized by irradiation of the fibers, or by treatment with chemical oxidizers.
  • the resulting fibers may be further modified by adding one or more additional precursors, for example AgNO 3 or Pd(acac) 2 , followed by additional rounds of heating.
  • additional precursors for example AgNO 3 or Pd(acac) 2
  • Such heating may be carried out in a reducing atmosphere, such as an atmosphere containing H 2 .
  • activated carbon coated fibers may be used to prepare Al 2 O 3 coated fibers.
  • ACF may be impregnated in an aqueous solution of AlCl 3 , dried, and heat-treated under N 2 at a temperature of usually 500° C. to 700° C.
  • a second heat treatment this time in an oxidizing atmosphere, removes the carbon.
  • the material is then calcined, yielding thermally stable Al 2 O 3 coated fibers.
  • the temperature of the second heat treatment is about 500° C. or above, air is preferred as an oxidizing atmosphere, as opposed to pure O 2 .
  • air is preferred as an oxidizing atmosphere, as opposed to pure O 2 .
  • pure O 2 is preferable.
  • lower temperatures require longer heating times for the complete removal of the carbon template. For instance, at 500° C., it usually takes more than 24 hours to burn off the template, whereas only a few seconds of heating are needed at 900° C.
  • Lower temperatures also yields Al 2 O 3 coated fibers with a higher Brunauer-Emmett-Teller (BET) surface area and a poorly crystalline structure. By contrast, higher temperature yields fibers with a lower BET surface area and the ceramic is more crystalline.
  • BET Brunauer-Emmett-Teller
  • the ceramic coating may be present on isolated regions on the surface of the substrate fibers, may completely enclose the substrate fibers, or enclose all of the substrate fibers except the ends of the substrate fibers. For example, if the substrate fibers were completely enclosed by the ceramic coating, then chopping would result in the ends of the fibers being exposed.
  • the weight ratio between the ceramic coating and the substrate fibers in the ceramic coated product fibers is not limited, but does affect final properties. For example, if the amount of the ceramic coating is very large compared to the amount of substrate fibers, then the brittleness of the ceramic coating may reduce the flexibility of the product ceramic coated fibers.
  • the product ceramic coated fibers include 10 to 90% by weight of the nanoporous organosilica ceramic coating, more preferably 20 to 80% by weight of the ceramic coating, including 30%, 40%, 50%, 60%, and 70% by weight of the ceramic coating.
  • Ceramic coated fibers may have BET surface areas of at least 50 m 2 /g, preferably more than 50 m 2 /g, more preferably at least 60 m 2 /g, including 60-2000 m 2 /g, and 100-500 m 2 /g.
  • the ceramic of the ceramic coated fibers contains crystalline ceramic, and may also include an amorphous phase.
  • the crystallites (or particles) of ceramic preferably have an average particle diameter of 2 nm to 50 nm. Even though the temperatures used to form the ceramic coated fibers may appear insufficient for crystallization of the bulk ceramic, crystalline material is present.
  • the activated carbon catalyzes the crystallization of the ceramic.
  • the coating holds to the fiber without the need for any binders.
  • the ceramic coated fibers of the invention may be used to catalyze photochemical reactions, for example for the photodegradation of unwanted organic and biological compounds or the disinfection of bacteria.
  • the fibers may be used for the purification and sterilization of water and air, or for the disinfection of tools such as medical room utensils.
  • Other uses include substrates for catalytic material (for example, platinum), and abrasive materials.
  • the fibers of the invention may also be manufactured with conductive fibers, such as metal fibers.
  • product fibers with a metal core and a catalytic oxide surface may be formed, and use as sensors, for instance as oxygen sensors to monitor combustion.
  • a carbon template was prepared by coating glass fibers with PAN resin prior to activation. After activation with H 2 O, the surface area of carbon was 1800 m 2 /g and the pore size was from 1 nm to 10 nm.
  • the pore system of the carbon template was then infiltrated with titanium tetraisopropoxide (TTIP) by wet impregnation for 24 hours at room temperature (20-22° C.). After removing the TTIP by washing with ethanol, precursor hydrolysis was initiated by exposure to air moisture.
  • Mesoporous inorganic particles were then obtained by crystallization or polymerization of TiO 2 at 250-400° C. in a nitrogen atmosphere for 4 hours, followed by removal of the carbon in air at the heating rate of 1 C/min.
  • the surface area of the final product fibers was 500 m 2 /g, based on the TiO 2 weight.
  • FIG. 1 illustrates a surface electron micrograph (SEM) of the product fibers.
  • An activated carbon coated fiber was made by coating glass fiber with phenolic resin prior to activation. Following activation with N 2 , the surface area of the carbon was about 1200 m 2 /g, and the pore size was from 1 to 3 nm.
  • the pore system of the activated carbon coated fiber was infiltrated with the titanium n-butoxide by wet impregnation for 24 h at room temperature. After removal of excess n-butoxide by ethanol wash, the hydrolysis of precursor was initiated by exposure to air moisture.
  • Mesoporous inorganic particles, with an average particle diameter from about 2 nm to about 50 nm, were then obtained by crystallization or polymerization of TiO 2 at 300° C. in air for 4 hours, followed by removal of the carbon at 550° C. in air for 2 hours.
  • the surface area was 230 m 2 /g based on the TiO 2 weight.
  • the activated carbon coated fiber was made by coating glass fibers with PAN resin prior to activation. After activation with H 2 O, the surface area of the carbon was about 1800 m 2 /g, and the pore size was about 1 nm.
  • the pore system of activated carbon coated fiber was infiltrated with a 100:2 mixture of titanium tetroisopropoxide and a nitrogen dopant tetramethylammonium salt by wet impregnation for 24 h at room temperature. The surface was washed with ethanol, and the hydrolysis of the precursor was initiated by exposure to air moisture. The mesoporous inorganic spheres were then obtained by crystallization or polymerization of the TiON at 300° C. in air for 1 h, followed by removal of the carbon and of the nitrogen dopant at 500° C. in air for 3 h.
  • the activated carbon coated fiber was made by coating glass fiber with PAN or phenolic resin prior to activation. After activation with H 2 O, the surface area of carbon was about 1800 m 2 /g and the pore size was about 1 nm.
  • the pore system of the activated carbon coated fiber was infiltrated with the above-described solution by wet impregnation for 24 hours at room temperature. The carbon surface was washed with acetone, and the hydrolysis of the precursor was initiated by exposure to air moisture.
  • the mesoporous inorganic spheres were then obtained by crystallization or polymerization of TiOS at 500° C. in air for 3 hours, followed by removal of the carbon and of the sulfur dopant at 500° C. in air for 1 hours.
  • TiON fibers prepared according to the method of Example (3) were immersed in a 10% (wt) silver nitrate solution for 12 hours at room temperature. The fibers were then washed with de-ionized (DI) water and heated at 300° C. for 2 hours.
  • DI de-ionized
  • TiON fibers prepard according to the method of Example (3) were immersed in a 1% (wt) Pd(acac) 2 toluene solution for 12 hours at room temperature. The fibers were then heated at 400° C. for 1 hour and reduced in H 2 at 200° C. for 3 hours.
  • the photodegradation rate of stearic acid is commonly used to assay the photocatalytic activity of semidconductor films. Accordingly, stearic acid was deposited on a 10 mm ⁇ 10 mm fiber sample by dip coating the fiber in a methanolic solution of stearic acid 0.02 M. The photocatalytic activity was compared to that of a reference photocatalyst film obtained by deposition of commercial TiO 2 (Hombikat UV 100) slurry via dip coating followed by washing in distilled water and drying in air for 1 hour at 80° C. The degradation rates of stearic acid were calculated by measuring the integrated absorbance of stearic acid between 2700 and 3000 cm ⁇ 1 in the infrared spectrum.
  • the percentage of degraded stearic acid was 39% for the mesoporous TiO 2 fibers of the invention, as illustrated in FIG. 2A , and 27% for the reference photocatalyst, as illustreated in FIG. 2B .
  • Example (7) The procedure of Example (7) was followed, with a 12 hours-long exposure to a light source of 365 nm wavelength and 2.4 mW/cm 2 intensity.
  • the percentage of degraded stearic acid was 73% for the mesoporous TiO 2 fibers of the invention, as illustrated in FIG. 3A , and 42% for the reference photocatalyst, as illustrated in FIG. 3B .
  • Humic acid was deposited on a 10 mm ⁇ 10 mm sample of the TiON fibers of Example (3) by dip coating in a 0.25% (wt) aqueous humic acid solution.
  • a degradation experiment according to the procedure of Example (7) was then conducted under a visible light source with an intensity of 1.9 mW/cm 2 .
  • the degradation of the humic acid was calculated by monitoring the absorption intensity of the humic acid solution at 400 nm in a UV-Vis spectrophotometer. As illustrated in FIG. 4 , after 8 hours of exposure to the light source, the TiON fiber of the invention had degraded 43% of the humic acid, whereas the reference photocatalyst of Example (7) showed no photocatalytic activity whatsoever.
  • a culture of E. coli bacteria was grown aerobically in a test-tube at 37° C. for 18 hours.
  • the TiON fibers of Example (3) and the Ag—TiON fibers of Example (5) were then tested as disinfectants on this culture by incubation under visible light at room temperature for 5 hours. Following the incubation, the number of viable cells in the disinfected samples and in control samples was determined by serial dilutions followed by incubation at 37° C. for 24 hours. As illustrated in FIG. 5 , The TiON fiber destroyed more than 80% of the bacteria, whereas Ag—TiON destroyed all of the bacteria.
  • activated carbon coated fiber manufactured by Nippon Kynol (Kansai, Japan), with various surface areas, were used as templates.
  • the activated carbon coated fibers used for this example were designated ACF7, ACF10, ACF15, ACF20 and ACF25, with BET surface areas of 690, 738, 1390, 1590 and 1960 m 2 /g, respectively.
  • Activated carbon coated fiber was impregnated with an aqueous solution of AlCl 3 , heat-dried at about 150° C., then heat-treated under N 2 at a temperature of about 600° C. A second heat treatment at 600° C. in air was then applied to remove the carbon template, and calcination of the product yielded thermally stable, white-colored Al 2 O 3 fibers. The removal of the carbon template was confirmed by thermal gravimetric analysis (TGA).
  • the N 2 absorption isotherms, the BET surface area and the pore size distribution of the product Al 2 O 3 fibers were measured with an Autosor-1 (Quantachrome Corp., Boynton Beach, Fla.) volumetric sorption analyzer. As illustrated in FIG. 6 , it appears that the BET surface area and the yield of Al 2 O 3 fiber was directly proportional to the porosity of the ACF template. N 2 absorption isotherms at 77 K showed that the Al 2 O 3 fibers were mesoporous materials, and pore distribution analysis showed peak values of mesopore in the range between 3.5 nm and 3.8 nm.
  • Illustrated in FIG. 2 (7) are the effects of the carbon oxidation temperature on the surface area of the product fibers.
  • the complete removal of the template required usually more than 24 hours.
  • the template was completely removed within seconds.
  • the BET surface area of the Al 2 O 3 fibers was higher for lower template-removal temperatures, and when the temperature was 500° C. and above, heating in air yielded better results than in O 2 .
  • the temperature was as low as 450° C., only O 2 could be used to remove all the carbon template, yielding a product with a very high BET surface area of above 500 m 2 /g.
  • N 2 absorption isotherms showed that Al 2 O 3 fibers obtained at different template-removal temperatures were all mesoporous materials.
  • X-ray diffractometry revealed an amorphous structure for fibers obtained at a template removal temperature of 450° C., and more crystalline structures for higher template removal temperatures.
  • the N 2 absorption isotherms, the BET surface area and the pore size distribution of the product Al 2 O 3 fibers were measured with an Autosor-1 (Quantachrome Corp., Boynton Beach, Fla.) volumetric sorption analyzer.
  • Autosor-1 Quantachrome Corp., Boynton Beach, Fla.
  • the removal of the carbon was confirmed by thermal gravimetric analysis (TGA), and the crystalline phases present in the fibers were identified by powder X-ray diffraction on a Rigaku D/max-VA (Rigaku/MSC, The Woodlands, Tex.).
  • FIG. 3 ( 8 ) Illustrated in FIG. 3 ( 8 ) are the effects of the carbon removal temperature on the surface area and the yield of the MgO fiber products.
  • lower carbon removal temperatures such as 400° C.
  • longer periods of time were required to remove the carbon, and surface areas up to 250 m 2 /g were obtained.
  • Higher carbon removal temperatures yielded fibers with lower surface areas.
  • N 2 absorption isotherms showed that that all the product MgO fibers were mesoporous materials.
  • X-ray diffractometry of the fibers revealed a cubic MgO crystal structure.
  • the N 2 absorption isotherms, the BET surface area and the pore size distribution of the product ZrO 2 fibers were measured with an Autosor-1 (Quantachrome Corp., Boynton Beach, Fla.) volumetric sorption analyzer.
  • the fibers obtained from the first sample has a BET surface area of 50 m 2 /g, and the fibers obtained from the second sample had a BET surface area of 60 m 2 /g.
  • X-ray diffractometry of the fibers revealed a tetragonal ZrO 2 crystalline structure.

Abstract

A method of manufacturing a ceramic coated fiber comprises heat treating an activated carbon coated fiber containing a ceramic precursor, to form a ceramic coated fiber.

Description

    BACKGROUND
  • More than 700 organic compounds have been identified in sources of drinking water in the United States (Stachka and Pontius, 1984) and elsewhere. Many water utilities, companies and government agencies must remove or destroy organic compounds from polluted groundwater supplies before those groundwater supplies can be used as drinking water. Additionally, many drinking water utilities are faced with the formation of disinfection by-products in finished water. Disinfection by-products are compounds formed in the water treatment process as a result of the disinfection process. In this process, a disinfectant such as chlorine is added to source water, where it reacts with a portion of the background organic matter (BOM) present in the source water to produce disinfection by-products. The reactive portions of the BOM are referred to as disinfection by-product precursors.
  • Considerable research is being directed at effective and economical treatment strategies that minimize the production of disinfection by-products. Advanced oxidation processes (AOPs) are alternative processes which destroy organic compounds and turn them into nontoxic forms, such as carbon dioxide and water. AOPs involve the generation of highly reactive radicals, such as the hydroxyl radical (OH.), which are responsible for the destruction of the organic compounds. AOPs can be classified into two major groups: AOPs involving homogeneous reactions using hydrogen peroxide (H2O2), ozone (O3), chlorine, and ultraviolet (UV) light, alone or in combination; and AOPs employing heterogeneous reactions using photoactive catalysts, such as semiconductors like titanium dioxide (TiO2) and nitrogen-doped titanium dioxide (TiO2-XNX). In the latter case—the photocatalytic oxidation processes—photoactive semiconductor catalysts are immersed in an oxygenated aqueous solution and illuminated with UV or visible radiation, so that reactive oxygen species are produced, causing the oxidation of organic compounds.
  • The primary oxidant responsible for the photocatalytic oxidation of organic compounds in aqueous solutions is believed to be the highly reactive hydroxyl radical (OH.), although direct reactions of adsorbed organic compounds with surface species, such as holes, have also been reported (Völz et al., 1981; Ceresa et al., Matthews, 1984; and Turchi and Ollis, 1990). When a photoactive semiconductor is illuminated with photons of the band gap energy of the semiconductor, or greater, photons excite electrons from the valence band, overcoming the energy of the band gap to the conduction band, and leaves electron vacancies, or holes, in the valence band. For example, the anatase form of TiO2 has a band-gap energy of about 3.2 eV, which is equivalent to the energy of UV light with a wavelength of 387 nm. Consequently, the anatase form of TiO2 can be activated by radiation with wavelengths less than 387 nm. The excited electrons and the resulting holes may take part in redox processes with adsorbed species, such as H2O, OH, organic compounds and O2 at the water-solid interface. The holes may take part in oxidation half reactions with adsorbed H2O or OH to form hydroxyl radicals. The electrons take part in the reduction half reactions with adsorbed O2 to produce the superoxide radical O2 , which may also in turn produce H2O2 and OH. (Okamoto et al.,1985).
  • For high photocatalytic efficiency, mesoporous TiO2 with its large surface area is highly desirable, and it was first prepared using a phosphate surfactant through a modified sol-gel process. The product was not pure TiO2 because of significant amounts of residual phosphorus, and its mesoporous structure underwent partial collapse during template removal by calcination. Another approach produced mesoporous TiO2 from amphiphilic poly(alkylene) block copolymers as structure-directing agents and organic titanium salts as precursors in a non-aqueous solution. Slight changes in reaction conditions, however, often produced very different results, rendering this method difficult to reproduce. A third method, using dodecylamine as a directing agent and titanium isopropoxide as the precursor, and emptying the pores by extractions, yielded a porous structure that was not retained after heat treatment in dry air at 300° C. Thus, it has so far been difficult to produce the highly crystalline TiO2 that is required for photocatalysis.
  • A second issue of current TiO2 photocatalysis technology is the requirement of ultraviolet light for activation. Because of the large energy of the band gap of TiO2 (Eg=3.2 eV in anatase), its use as a photocatalyst is limited to radiation with a wavelength of less than 380 nm. A material catalytically active when exposed to visible light of wavelengths longer than 380 nm would allow for satisfactory photocatalysis in environments where less intense light is available, for instance indoors or in a vehicle.
  • A further major issue of the current technology is that the powder form of the photocatalyst is difficult to handle, and too fine to be recovered from photoreactors. Thus, several films of TiO2 on various substrates and supports have been developed for photocatalytic applications. However, particle sintering and agglomeration greatly reduce the surface area of the photocatalyst.
  • The bonding of the TiO2 to the substrate is also a source of problems. Films of TiO2 have been assembled on substrates by direct growth and post synthetic crystal attachment. Both methods rely on chemical binders to immobilize TiO2 to the substrate surface. Unfortunately, organic binders are susceptible to decomposition under UV light. Consequently, the TiO2 films become loose from the substrate, and are easily detached.
  • Powders, fibers and films of TiO2 have been reported, and a number of photocatalytic TiO2 powder preparations are commercially available. However, these powders are difficult to apply to water purification, and the surface area of the powders is low, resulting in low catalytic activity and only a small number of catalytic sites.
  • In contrast, TiO2 fibers have a very high surface area, high wear and mechanical strength, and high thermal stability. Moreover, when used in chemical reactors, TiO2 fibers cause only a small pressure drop and can serve as a reinforcement material and as a matrix of various shapes and sizes.
  • TiO2 fibers may be prepared by various fabrication methods. For example, TiO2 fibers were prepared by solvothermal reaction of a fibrous K2Ti4O9 precursor, by ion-exchange reaction of K2O.4TiO2 fibers and thermal decomposition of H2Ti4O9.
  • Activated carbon fibers (ACF) are traditionally produced by heating an organic precursor until carbonized, and then activating the carbonized material. Activation is achieved typically by heating the carbonized material in an oxidizing environment. Alternatively, the carbon may be activated chemically. This process involves impregnating the carbon precursor with, for example, phosphoric acid, zinc chloride, or potassium hydroxide, followed by carbonization.
  • The above methods, however, yields brittle and frangible ACF, limiting their use to systems containing some mechanical support. This problem has been mitigated by preparing fibers where activated carbon is formed as a coating on substrate fibers.
  • For example, U.S. Pat. No. 5,834,114 describes glass or mineral fibers coated with activated carbon. These are prepared by coating the fiber substrate with a resin, cross-linking the resin, heating the coated fiber substrate and resin to carbonize the resin, and exposing the coated fiber substrate to an etchant to activate the coated fiber substrate.
  • U.S. Pat. No. 6,517,906 describes coating the substrate fibers with a mixture containing an organic polymeric material, and a chemical activating agent, for example a Lewis acid or base. This mixture carbonizes at temperatures lower than those required by earlier methods, allowing for the formation of activated carbon coatings on low melting point fibers, such as HEPA fibers.
  • SUMMARY
  • In a first aspect, the present invention is a method of manufacturing a ceramic coated fiber, comprising heat treating an activated carbon coated fiber containing a ceramic precursor, to form a ceramic coated fiber.
  • In a second aspect, the present invention is a ceramic coated fiber, comprising (a) a fiber, and (b) ceramic, coated on the fiber. The ceramic has a BET surface area of at least 60 m2/g, and the ceramic comprises crystalline ceramic.
  • In a third aspect, the present invention is a method for manufacturing an intermediate for the fabrication of ceramic coated fibers, comprising heating an activated carbon coated fiber containing a ceramic precursor, to cure the precursor.
  • In a fourth aspect, the present invention is a ceramic coated fiber comprising (a) a fiber, and (b) ceramic, coated on the fiber. The ceramic has a BET surface area of at least 50 m2/g, and the ceramic comprises at least one member selected from the group consisting of Al2O3, ZrO2, and MgO.
  • BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 illustrates a surface electron micrograph (SEM) of ceramic fibers produced according to the method of Example 1.
  • FIG. 2 illustrates the photodegradation of stearic acid catalyzed by the fibers of Example 1 (FIG. 2A), and by a reference commercial TiO2 photocatalyst (FIG. 2B).
  • FIG. 3 illustrates the photodegradation of stearic acid catalyzed by the fibers of Example 1 (FIG. 3A), and by a reference commercial TiO2 photocatalyst (FIG. 3B).
  • FIG. 4 illustrates the photodegradation of humic acid catalyzed by the TiON fibers of Example (3).
  • FIG. 5 illustrates the incubation of an E. coli bacterial culture with the TiON fibers of Example (3) and with the Ag—TiON fibers of Example (5).
  • FIG. 6 illustrates the effect of ACF on surface areas and yield of Al2O3 fibers.
  • FIG. 7 illustrates the effect of the temperature of the second heating on the surface areas and the yield of Al2O3 fibers.
  • FIG. 8 illustrates the effect of the temperature of the second heating on the surface area and the yield of MgO fibers.
  • DETAILED DESCRIPTION
  • Activated carbon does not resist temperatures higher than 573 K in an oxidative atmosphere. Therefore, it had been thought to be inapplicable to use activated carbon as a substrate fiber for fabrication processes requiring high temperature calcination, such as the manufacturing of ceramic coated fibers. The present invention is based on the discovery that, despite this instability at high temperatures, activated carbon can be used as a template in the formation of ceramic coated fibers.
  • Activated carbon coated fibers are first prepared by coating substrate fibers with activated carbon or an activated organic coating as described in U.S. Pat. No. 6,517,906. Example substrate fibers include HEPA filters, synthetic fibers used in clothing, polyesters, polyethylene, polyethylene terephthalate, nylon 6, nylon 66, polypropylene, KEVLAR™, TEFLON™, liquid crystalline polyesters, and syndiotactic polystyrene. Glass fibers such as e-glass fibers; mineral fibers such as asbestos and basalt; ceramic fibers such as TiO2, SiC, and BN; metal fibers (or wires) such as iron, nickel, gold, silver, aluminum and platinum; polymer fibers such as TYVEK™; and combinations thereof. Some preferred substrate fibers are listed in the table below.
    Company Product Line Description
    CRANE & CO. Crane 230 (6.5 μm) Non-woven Fiber Glass
    Mats
    Crane 232 (7.5 μm) Non-woven Fiber Glass
    Mats
    FIBRE GLAST 519 (0.75 oz.) wovens
    573 (9 oz.) wovens
    HOLLINGS- BG05095 glass paper or felts
    WORTH & VOSE HE1021
    JOHNS 7529 (11 μm) non-woven fiber glass mats
    MANVILLE
    LYDALL MANNIGLAS ® non-woven fiber glass mats
    MANNING
    DUPONT TYVEK ® HDPE Spun bonded paper
  • The substrate fibers may be present in any form. Examples include loose fibers, woven and non-woven fabrics, papers, felts and mats. The substrate fibers may be made from substrate fibers already present in a specific form, or the substrate fibers may first be prepared from loose substrate fibers, and made into the specific form. The length of the substrate fibers is not limited, and may be, for example, 0.01 mm to over 100 m in length, but preferably at least 3 micrometers. The substrate fibers may be prepared from longer substrate fibers, then cut or chopped. Furthermore, the diameter of the substrate fibers is also not limited, and may be, for example 100 Å to 1 mm in diameter. Preferably, the fibers have an aspect ratio of at least 10.
  • If the substrate fibers are susceptible to oxidation, it may be advantageous to coat them with an oxidation resistant coating, before forming the activated carbon on the fibers. Examples of oxidation resistant coating include water glass and phosphate glass.
  • The activated carbon coated fibers are infiltrated with ceramic precursors by immersion in a solution of one or more ceramic precursors in a volatile solvent. In general, ceramic precursors are compounds of one or more elements present in the ceramic and volatile components, such as halides, nitrates, nitrides, nitrates, hydroxides, organic acid salts and organometallic complexes. When subjected to high temperature treatment, the ceramic elements and any oxygen are left as a ceramic deposit, whereas the remainder of the precursor is volatilized.
  • Ceramic precursors are soluble compounds of the first group, second group, third group, fourth group, the transition metals, the lanthanide and actinide elements, N, O, Se, Te, and Po. Example ceramic precursors include Ti(t-BuO)4, Ti(i-Pro)4, Si(OEt)4, ZnCl2, ZrOCl2, ZrO(OH)Cl, Zr(COOCH3)4, MgCl2, Mg(COOCH3)2, and MgSO4. A mixture of two or more precursors may be used, for instance if a secondary, ternary or quaternary ceramic compound is desired. An oxynitride ceramic coating may be obtained by adding a nitrogen dopant such as a tetraalkylamonium salt. Likewise, an oxysulfide coating may be made by adding a sulfur dopant such as thiourea.
  • The excess precursor is removed, and the infiltrated precursor may be hydrolyzed by exposure to the moisture in the air, yielding a composite of carbon and the precursor or the hydrolyzed precursor.
  • The ceramic precursor should preferably accumulate in the pores of the template to form an interconnected solid or gel. The system is then subjected to a heat treatment, which may remove residual solvent, cure the precursor, as well as remove the activated carbon, and crystallize the ceramic. For example, the heat treatment may include a first heating at 250° C. to 600° C., or 250° C. to 400° C., optionally in an inert atmosphere, to remove residual solvents and to cure the ceramic precursor. A second heating may follow, for example at 400° C. to 1000° C., in an oxidizing atmosphere, removing the carbon substrate and crystallizing the ceramic, and if necessary, oxidizing the cured precursor. The carbon substrate may also be oxidized by irradiation of the fibers, or by treatment with chemical oxidizers.
  • The resulting fibers may be further modified by adding one or more additional precursors, for example AgNO3 or Pd(acac)2, followed by additional rounds of heating. Such heating may be carried out in a reducing atmosphere, such as an atmosphere containing H2.
  • For example, activated carbon coated fibers may be used to prepare Al2O3 coated fibers. To this end, ACF may be impregnated in an aqueous solution of AlCl3, dried, and heat-treated under N2 at a temperature of usually 500° C. to 700° C. A second heat treatment, this time in an oxidizing atmosphere, removes the carbon. The material is then calcined, yielding thermally stable Al2O3 coated fibers.
  • When the temperature of the second heat treatment is about 500° C. or above, air is preferred as an oxidizing atmosphere, as opposed to pure O2. For lower temperatures, such as 450° C., pure O2 is preferable. In general, lower temperatures require longer heating times for the complete removal of the carbon template. For instance, at 500° C., it usually takes more than 24 hours to burn off the template, whereas only a few seconds of heating are needed at 900° C. Lower temperatures also yields Al2O3 coated fibers with a higher Brunauer-Emmett-Teller (BET) surface area and a poorly crystalline structure. By contrast, higher temperature yields fibers with a lower BET surface area and the ceramic is more crystalline.
  • The ceramic coating may be present on isolated regions on the surface of the substrate fibers, may completely enclose the substrate fibers, or enclose all of the substrate fibers except the ends of the substrate fibers. For example, if the substrate fibers were completely enclosed by the ceramic coating, then chopping would result in the ends of the fibers being exposed.
  • The weight ratio between the ceramic coating and the substrate fibers in the ceramic coated product fibers is not limited, but does affect final properties. For example, if the amount of the ceramic coating is very large compared to the amount of substrate fibers, then the brittleness of the ceramic coating may reduce the flexibility of the product ceramic coated fibers. Preferably, the product ceramic coated fibers include 10 to 90% by weight of the nanoporous organosilica ceramic coating, more preferably 20 to 80% by weight of the ceramic coating, including 30%, 40%, 50%, 60%, and 70% by weight of the ceramic coating.
  • Ceramic coated fibers may have BET surface areas of at least 50 m2/g, preferably more than 50 m2/g, more preferably at least 60 m2/g, including 60-2000 m2/g, and 100-500 m2/g. Preferably, the ceramic of the ceramic coated fibers contains crystalline ceramic, and may also include an amorphous phase. The crystallites (or particles) of ceramic preferably have an average particle diameter of 2 nm to 50 nm. Even though the temperatures used to form the ceramic coated fibers may appear insufficient for crystallization of the bulk ceramic, crystalline material is present. One possible explanation is that the activated carbon catalyzes the crystallization of the ceramic. Furthermore, the coating holds to the fiber without the need for any binders.
  • The ceramic coated fibers of the invention may be used to catalyze photochemical reactions, for example for the photodegradation of unwanted organic and biological compounds or the disinfection of bacteria. Thus, the fibers may be used for the purification and sterilization of water and air, or for the disinfection of tools such as medical room utensils. Other uses include substrates for catalytic material (for example, platinum), and abrasive materials. The fibers of the invention may also be manufactured with conductive fibers, such as metal fibers. Thus, product fibers with a metal core and a catalytic oxide surface may be formed, and use as sensors, for instance as oxygen sensors to monitor combustion.
  • EXAMPLES
  • (1) TiO2 Fibers
  • A carbon template was prepared by coating glass fibers with PAN resin prior to activation. After activation with H2O, the surface area of carbon was 1800 m2/g and the pore size was from 1 nm to 10 nm. The pore system of the carbon template was then infiltrated with titanium tetraisopropoxide (TTIP) by wet impregnation for 24 hours at room temperature (20-22° C.). After removing the TTIP by washing with ethanol, precursor hydrolysis was initiated by exposure to air moisture. Mesoporous inorganic particles were then obtained by crystallization or polymerization of TiO2 at 250-400° C. in a nitrogen atmosphere for 4 hours, followed by removal of the carbon in air at the heating rate of 1 C/min. The surface area of the final product fibers was 500 m2/g, based on the TiO2 weight.
  • FIG. 1 illustrates a surface electron micrograph (SEM) of the product fibers.
  • (2) TiO2 Fibers
  • An activated carbon coated fiber was made by coating glass fiber with phenolic resin prior to activation. Following activation with N2, the surface area of the carbon was about 1200 m2/g, and the pore size was from 1 to 3 nm. The pore system of the activated carbon coated fiber was infiltrated with the titanium n-butoxide by wet impregnation for 24 h at room temperature. After removal of excess n-butoxide by ethanol wash, the hydrolysis of precursor was initiated by exposure to air moisture. Mesoporous inorganic particles, with an average particle diameter from about 2 nm to about 50 nm, were then obtained by crystallization or polymerization of TiO2 at 300° C. in air for 4 hours, followed by removal of the carbon at 550° C. in air for 2 hours. The surface area was 230 m2/g based on the TiO2 weight.
  • (3) TiON Fibers
  • The activated carbon coated fiber was made by coating glass fibers with PAN resin prior to activation. After activation with H2O, the surface area of the carbon was about 1800 m2/g, and the pore size was about 1 nm. The pore system of activated carbon coated fiber was infiltrated with a 100:2 mixture of titanium tetroisopropoxide and a nitrogen dopant tetramethylammonium salt by wet impregnation for 24 h at room temperature. The surface was washed with ethanol, and the hydrolysis of the precursor was initiated by exposure to air moisture. The mesoporous inorganic spheres were then obtained by crystallization or polymerization of the TiON at 300° C. in air for 1 h, followed by removal of the carbon and of the nitrogen dopant at 500° C. in air for 3 h.
  • (4) TiOS Fibers
  • Two grams of thiourea were dissolved in 20 g of N,N-dimethylformamide (DMF) and added to 10 g TTIP, and 2 g of ethanol were added to the mixture to obtain a transparent solution. The activated carbon coated fiber was made by coating glass fiber with PAN or phenolic resin prior to activation. After activation with H2O, the surface area of carbon was about 1800 m2/g and the pore size was about 1 nm. The pore system of the activated carbon coated fiber was infiltrated with the above-described solution by wet impregnation for 24 hours at room temperature. The carbon surface was washed with acetone, and the hydrolysis of the precursor was initiated by exposure to air moisture. The mesoporous inorganic spheres were then obtained by crystallization or polymerization of TiOS at 500° C. in air for 3 hours, followed by removal of the carbon and of the sulfur dopant at 500° C. in air for 1 hours.
  • (5) Ag—TiON Fibers
  • TiON fibers prepared according to the method of Example (3) were immersed in a 10% (wt) silver nitrate solution for 12 hours at room temperature. The fibers were then washed with de-ionized (DI) water and heated at 300° C. for 2 hours.
  • (6) Pd—TiON Fibers
  • TiON fibers prepard according to the method of Example (3) were immersed in a 1% (wt) Pd(acac)2 toluene solution for 12 hours at room temperature. The fibers were then heated at 400° C. for 1 hour and reduced in H2 at 200° C. for 3 hours.
  • (7) Photodegradation with TiO2 Fibers and 254 nm Light
  • The photodegradation rate of stearic acid is commonly used to assay the photocatalytic activity of semidconductor films. Accordingly, stearic acid was deposited on a 10 mm×10 mm fiber sample by dip coating the fiber in a methanolic solution of stearic acid 0.02 M. The photocatalytic activity was compared to that of a reference photocatalyst film obtained by deposition of commercial TiO2 (Hombikat UV 100) slurry via dip coating followed by washing in distilled water and drying in air for 1 hour at 80° C. The degradation rates of stearic acid were calculated by measuring the integrated absorbance of stearic acid between 2700 and 3000 cm−1 in the infrared spectrum. After a 2 hours-long exposure to a light source of 254 nm wavelength and 2.8 mW/cm2 intensity, the percentage of degraded stearic acid was 39% for the mesoporous TiO2 fibers of the invention, as illustrated in FIG. 2A, and 27% for the reference photocatalyst, as illustreated in FIG. 2B.
  • (8) Photodegradation with TiO2 Fibers and 365 nm Light
  • The procedure of Example (7) was followed, with a 12 hours-long exposure to a light source of 365 nm wavelength and 2.4 mW/cm2 intensity. The percentage of degraded stearic acid was 73% for the mesoporous TiO2 fibers of the invention, as illustrated in FIG. 3A, and 42% for the reference photocatalyst, as illustrated in FIG. 3B.
  • (9) Photodegradation of Humic Acid with TiON Fibers
  • Humic acid was deposited on a 10 mm×10 mm sample of the TiON fibers of Example (3) by dip coating in a 0.25% (wt) aqueous humic acid solution. A degradation experiment according to the procedure of Example (7) was then conducted under a visible light source with an intensity of 1.9 mW/cm2. The degradation of the humic acid was calculated by monitoring the absorption intensity of the humic acid solution at 400 nm in a UV-Vis spectrophotometer. As illustrated in FIG. 4, after 8 hours of exposure to the light source, the TiON fiber of the invention had degraded 43% of the humic acid, whereas the reference photocatalyst of Example (7) showed no photocatalytic activity whatsoever.
  • (10) Disinfection of Bacterial Cultures
  • A culture of E. coli bacteria was grown aerobically in a test-tube at 37° C. for 18 hours. The TiON fibers of Example (3) and the Ag—TiON fibers of Example (5) were then tested as disinfectants on this culture by incubation under visible light at room temperature for 5 hours. Following the incubation, the number of viable cells in the disinfected samples and in control samples was determined by serial dilutions followed by incubation at 37° C. for 24 hours. As illustrated in FIG. 5, The TiON fiber destroyed more than 80% of the bacteria, whereas Ag—TiON destroyed all of the bacteria.
  • (11) Al2O3 Fibers.
  • Commercially available activated carbon coated fiber manufactured by Nippon Kynol (Kansai, Japan), with various surface areas, were used as templates. The activated carbon coated fibers used for this example were designated ACF7, ACF10, ACF15, ACF20 and ACF25, with BET surface areas of 690, 738, 1390, 1590 and 1960 m2/g, respectively.
  • Activated carbon coated fiber was impregnated with an aqueous solution of AlCl3, heat-dried at about 150° C., then heat-treated under N2 at a temperature of about 600° C. A second heat treatment at 600° C. in air was then applied to remove the carbon template, and calcination of the product yielded thermally stable, white-colored Al2O3 fibers. The removal of the carbon template was confirmed by thermal gravimetric analysis (TGA).
  • The N2 absorption isotherms, the BET surface area and the pore size distribution of the product Al2O3 fibers were measured with an Autosor-1 (Quantachrome Corp., Boynton Beach, Fla.) volumetric sorption analyzer. As illustrated in FIG. 6, it appears that the BET surface area and the yield of Al2O3 fiber was directly proportional to the porosity of the ACF template. N2 absorption isotherms at 77 K showed that the Al2O3 fibers were mesoporous materials, and pore distribution analysis showed peak values of mesopore in the range between 3.5 nm and 3.8 nm.
  • (12) Effect of Template-Removal Temperature on Product Al2O3 Fibers
  • ACF23 (surface area=1730 m2/g) was impregnated with an aqueous solution of AlCl3, heat-dried at about 150° C., then heat-treated under N2 at a temperature of about 600° C. A second heat-treatment in air, at a temperature chosen from the range between 450° C. to 900° C., was applied to remove the carbon template. A thermally stable, white-colored Al2O3 fiber was then obtained upon calcination. The removal of the carbon template was confirmed by thermal gravimetric analysis (TGA), and the crystalline phases present in the fibers were identified by powder X-ray diffraction on a Rigaku D/max-VA (Rigaku/MSC, The Woodlands, Tex.).
  • Illustrated in FIG. 2 (7) are the effects of the carbon oxidation temperature on the surface area of the product fibers. At lower temperatures, for example 500° C., the complete removal of the template required usually more than 24 hours. At higher temperatures, for example 900° C., the template was completely removed within seconds. The BET surface area of the Al2O3 fibers was higher for lower template-removal temperatures, and when the temperature was 500° C. and above, heating in air yielded better results than in O2. However, when the temperature was as low as 450° C., only O2 could be used to remove all the carbon template, yielding a product with a very high BET surface area of above 500 m2/g.
  • N2 absorption isotherms showed that Al2O3 fibers obtained at different template-removal temperatures were all mesoporous materials. X-ray diffractometry revealed an amorphous structure for fibers obtained at a template removal temperature of 450° C., and more crystalline structures for higher template removal temperatures.
  • (13) MgO Fibers
  • ACF23 (surface area=1730 m2/g) was impregnated in an aqueous solution of Mg(Ac)2 obtained by dissolving 1 g of Mg(Ac)2 in 2 mL of H2O, heat-dried at about 150° C., and then heat-treated in N2 at about 600° C. A second heat-treatment in air, at a temperature chosen from the range between 450° C. to 900° C., was applied to remove the carbon. Calcination of the product yielded thermally stable, white-colored MgO fibers. The N2 absorption isotherms, the BET surface area and the pore size distribution of the product Al2O3 fibers were measured with an Autosor-1 (Quantachrome Corp., Boynton Beach, Fla.) volumetric sorption analyzer. The removal of the carbon was confirmed by thermal gravimetric analysis (TGA), and the crystalline phases present in the fibers were identified by powder X-ray diffraction on a Rigaku D/max-VA (Rigaku/MSC, The Woodlands, Tex.).
  • Illustrated in FIG. 3(8) are the effects of the carbon removal temperature on the surface area and the yield of the MgO fiber products. At lower carbon removal temperatures, such as 400° C., longer periods of time were required to remove the carbon, and surface areas up to 250 m2/g were obtained. Higher carbon removal temperatures yielded fibers with lower surface areas. N2 absorption isotherms showed that that all the product MgO fibers were mesoporous materials. X-ray diffractometry of the fibers revealed a cubic MgO crystal structure.
  • (14) ZrO2 Fibers
  • Two samples of ACF23 (surface area=1730 m2/g) were impregnated with a Zr(NO3)4 aqueous solution obtained by dissolving 1 g of Zr(NO3)4 in 5 mL of water, heat-dried at about 150° C., and then heat-treated in N2 at about 600° C. The first sample was then heat-treated in air at 450° C., and the second sample was heat-treated in air at 600° C. The fibers were then calcinated, yielding thermally stable, white-colored ZrO2 fibers.
  • The N2 absorption isotherms, the BET surface area and the pore size distribution of the product ZrO2 fibers were measured with an Autosor-1 (Quantachrome Corp., Boynton Beach, Fla.) volumetric sorption analyzer. The fibers obtained from the first sample has a BET surface area of 50 m2/g, and the fibers obtained from the second sample had a BET surface area of 60 m2/g. X-ray diffractometry of the fibers revealed a tetragonal ZrO2 crystalline structure.

Claims (31)

1. A method of manufacturing a ceramic coated fiber, comprising:
heat treating an activated carbon coated fiber containing a ceramic precursor, to form a ceramic coated fiber.
2. The method of claim 1, wherein the heat treating comprises:
a first heating at a temperature of at least 250° C., to cure the precursor, and
a second heating, in an oxidizing atmosphere, at a temperature of at least 400° C., to remove the carbon.
3. The method of claim 2, wherein the first heating is in an inert atmosphere.
4. The method of claim 2, wherein the ceramic comprises TiO2 and/or TiON having an anatase structure.
5. The method of claim 4, wherein the ceramic precursor further comprises a nitrogen or sulfur dopant.
6. The method of claim 5, wherein the nitrogen source is tetramethylammonium hydroxide.
7. The method of claim 2, further comprising:
contacting the ceramic coated fiber with a compound containing silver; and
a third heating of the ceramic coated fiber.
8. The method of claim 2, further comprising:
contacting the ceramic coated fiber with a compound containing palladium;
a third heating of the ceramic coated fiber; and
a fourth heating of the ceramic coated fiber in an atmosphere comprising H2.
9. The method of claim 2, wherein the ceramic comprises crystalline ceramic and has a BET surface area of at least 50 m2/g.
10. The method of claim 2, wherein the ceramic comprises at least one member selected from the group consisting of TiO2, TiON, TiOS, Al2O3, ZrO2, and MgO.
11. A ceramic coated fiber manufactured according to the method of claim 1.
12. A ceramic coated fiber manufactured according to the method of claim 2.
13. A method for producing radical species, comprising illuminating the fiber of claim 12,
wherein the ceramic comprises TiO2 and/or TiON having an anatase structure.
14. A method for purifying and disinfecting air or water, comprising contacting the air or water with the fiber of claim 12 and illuminating the fiber,
wherein the ceramic comprises TiO2 and/or TiON having an anatase structure.
15. A photochemical reactor comprising the fiber of claim 12,
wherein the ceramic comprises TiO2 and/or TiON having an anatase structure.
16. A ceramic coated fiber, comprising:
(a) a fiber, and
(b) ceramic, coated on the fiber,
wherein the ceramic has a BET surface area of at least 60 m2/g, and
the ceramic comprises crystalline ceramic.
17. The ceramic coated fiber of claim 16, wherein the ceramic comprises TiO2 and/or TiON having an anatase structure.
18. The ceramic coated fiber of claim 16, wherein the ceramic comprises at least one member selected from the group consisting of TiO2, TiON, TiOS, Al2O3, ZrO2, and MgO.
19. The ceramic coated fiber of claim 16, wherein the ceramic has a B.E.T. surface area of 60 m2/g to 300 m2/g.
20. The ceramic coated fiber of claim 16, wherein the ceramic comprises 10 to 90% by weight of the ceramic coated fibers.
21. The ceramic coated fiber of claim 16, further comprising silver and/or palladium.
22. A method for producing radical species, comprising illuminating the fiber of claim 17.
23. A method for purifying and disinfecting air or water, comprising contacting the air or water with the fiber of claim 17, and illuminating the fiber.
24. A photochemical reactor comprising the fiber of claim 17.
25. A method for manufacturing an intermediate for the fabrication of ceramic coated fibers, comprising heating an activated carbon coated fiber containing a ceramic precursor, to cure the precursor.
26. The method of claim 25, wherein the heating is in an inert atmosphere.
27. An intermediate for the fabrication of ceramic coated fibers manufactured according to the method of claim 25.
28. A ceramic coated fiber, comprising:
(a) a fiber, and
(b) ceramic, coated on the fiber,
wherein the ceramic has a BET surface area of at least 50 m2/g, and
the ceramic comprises at least one member selected from the group consisting of Al2O3, ZrO2, and MgO.
29. The ceramic coated fiber of claim 28, wherein the ceramic has a B.E.T. surface area of 60 m2/g to 300 m2/g.
30. The ceramic coated fiber of claim 28, wherein the ceramic comprises 10 to 90% by weight of the ceramic coated fibers.
31. The ceramic coated fiber of claim 28, further comprising silver and/or palladium.
US10/797,582 2004-03-10 2004-03-10 High surface area ceramic coated fibers Abandoned US20050202241A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US10/797,582 US20050202241A1 (en) 2004-03-10 2004-03-10 High surface area ceramic coated fibers
EP05725270A EP1732859A1 (en) 2004-03-10 2005-03-10 High surface area ceramic coated fibers
JP2007503020A JP2007528454A (en) 2004-03-10 2005-03-10 Large surface area ceramic coated fiber
CA002558720A CA2558720A1 (en) 2004-03-10 2005-03-10 High surface area ceramic coated fibers
KR1020067020422A KR20070004800A (en) 2004-03-10 2005-03-10 High surface area ceramic coated fibers
AU2005222413A AU2005222413A1 (en) 2004-03-10 2005-03-10 High surface area ceramic coated fibers
CN2005800149829A CN1950308B (en) 2004-03-10 2005-03-10 High surface area ceramic coated fibers
MXPA06010223A MXPA06010223A (en) 2004-03-10 2005-03-10 High surface area ceramic coated fibers.
PCT/US2005/008008 WO2005087679A1 (en) 2004-03-10 2005-03-10 High surface area ceramic coated fibers
BRPI0508566-7A BRPI0508566A (en) 2004-03-10 2005-03-10 high surface area ceramic coated fibers
US12/876,011 US8241706B2 (en) 2004-03-10 2010-09-03 High surface area ceramic coated fibers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/797,582 US20050202241A1 (en) 2004-03-10 2004-03-10 High surface area ceramic coated fibers

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/876,011 Continuation US8241706B2 (en) 2004-03-10 2010-09-03 High surface area ceramic coated fibers

Publications (1)

Publication Number Publication Date
US20050202241A1 true US20050202241A1 (en) 2005-09-15

Family

ID=34920083

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/797,582 Abandoned US20050202241A1 (en) 2004-03-10 2004-03-10 High surface area ceramic coated fibers
US12/876,011 Expired - Lifetime US8241706B2 (en) 2004-03-10 2010-09-03 High surface area ceramic coated fibers

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/876,011 Expired - Lifetime US8241706B2 (en) 2004-03-10 2010-09-03 High surface area ceramic coated fibers

Country Status (10)

Country Link
US (2) US20050202241A1 (en)
EP (1) EP1732859A1 (en)
JP (1) JP2007528454A (en)
KR (1) KR20070004800A (en)
CN (1) CN1950308B (en)
AU (1) AU2005222413A1 (en)
BR (1) BRPI0508566A (en)
CA (1) CA2558720A1 (en)
MX (1) MXPA06010223A (en)
WO (1) WO2005087679A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040197552A1 (en) * 2001-07-25 2004-10-07 Bertrand Maquin Mineral fibre provided with a microporous or mesoporous coating
US20050221087A1 (en) * 2004-02-13 2005-10-06 James Economy Nanoporous chelating fibers
US20070190765A1 (en) * 2005-12-29 2007-08-16 Rong-Cai Xie Quaternary oxides and catalysts containing quaternary oxides
US20070202334A1 (en) * 2005-12-29 2007-08-30 Rong-Cai Xie Nanoparticles containing titanium oxide
US20070264467A1 (en) * 2006-05-09 2007-11-15 Ruei-Shan Wang Photocatalyst synthesized fiber product
US20070271682A1 (en) * 2004-05-24 2007-11-29 Eastman Robert Ii Scent-Suppressing Fiber, and Articles Incorporating Same
WO2010022394A2 (en) * 2008-08-22 2010-02-25 The Board Of Trustees Of The University Of Illinois Catalytic compositions, composition production methods, and aqueous solution treatment methods
US20100193449A1 (en) * 2009-02-02 2010-08-05 Jian-Ku Shang Materials and methods for removing arsenic from water
US20100213574A1 (en) * 2004-08-31 2010-08-26 Micron Technology, Inc. High dielectric constant transition metal oxide materials
US20110073358A1 (en) * 2009-09-28 2011-03-31 Kyocera Corporation Circuit substrate, laminated board and laminated sheet
US20120058884A1 (en) * 2008-08-27 2012-03-08 Korea University Research And Business Foundation Fiber including silica and metal oxide
US8241706B2 (en) 2004-03-10 2012-08-14 The Board Of Trustees Of The University Of Illinois High surface area ceramic coated fibers

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9079133B2 (en) * 2011-02-10 2015-07-14 Toyota Jidosha Kabushiki Kaisha Air-purifying device for vehicles
CN103771468B (en) * 2012-10-24 2015-07-22 中国石油化工股份有限公司 Preparation method of nano gamma-alumina powder
CN103771475B (en) * 2012-10-24 2016-03-02 中国石油化工股份有限公司 A kind of gama-alumina raw powder's production technology
CN104045110B (en) * 2014-07-04 2016-05-18 西北师范大学 The preparation method of titanium dioxide nanofiber material
TWI726799B (en) * 2020-08-24 2021-05-01 膜旺能源科技有限公司 Wastewater purification system having catalytic membrane tube

Citations (93)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2670334A (en) * 1952-11-06 1954-02-23 Koppers Co Inc Anion-exchange resins from aminated aryl acetylene
US2885366A (en) * 1956-06-28 1959-05-05 Du Pont Product comprising a skin of dense, hydrated amorphous silica bound upon a core of another solid material and process of making same
US3373104A (en) * 1964-12-17 1968-03-12 Union Tank Car Co Method of cleaning filter tank
US3395970A (en) * 1963-10-30 1968-08-06 Deering Milliken Res Corp Method of carbonizing polyacrylonitrile impregnated cellulose, cyanoethylated cellulose and acrylonitrile graft copolymerized cellulose textiles
US3518206A (en) * 1968-05-17 1970-06-30 Du Pont Supported catalysts composed of substrate coated with colloidal silica and catalyst
US3520805A (en) * 1967-05-29 1970-07-21 Union Tank Car Co Method of disposal of radioactive solids
US3723588A (en) * 1968-03-04 1973-03-27 Carborundum Co Method for production of novolac fibers
US3799796A (en) * 1970-10-06 1974-03-26 Matthey Bishop Inc Preparation of structures with a coating of al2o3/sio2 fibers bonded to al2o3 for use as catalyst substrates
US3903220A (en) * 1972-12-04 1975-09-02 Carborundum Co Method for producing carbon fibers
US3956185A (en) * 1972-12-28 1976-05-11 Matsushita Electric Industrial Co., Ltd. Catalyst for exhaust gas purification
US3971669A (en) * 1972-07-21 1976-07-27 Hyfil Limited Carbon fiber composites
US4039716A (en) * 1974-09-20 1977-08-02 Owens-Corning Fiberglas Corporation Resin coated glass fibers and method of producing same through use of an aqueous silane-containing sizing composition whereby hydrolysis and polymerization of the silane is inhibited
US4045336A (en) * 1974-08-23 1977-08-30 Pauli Henrik Isteri Method and device for oxygenating water with vibrations and under pressure strokes
US4100314A (en) * 1977-03-29 1978-07-11 Airco, Inc. Method for increasing the strength and density of carbonaceous products
US4256607A (en) * 1976-10-05 1981-03-17 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4265768A (en) * 1979-12-26 1981-05-05 Rohm And Haas Company Ion exchange material prepared from partially pyrolyzed macroporous polymer particles
US4285831A (en) * 1976-10-05 1981-08-25 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4312956A (en) * 1978-09-19 1982-01-26 Rohm And Haas Company Filtration and deionization prepared from cationic and anionic emulsion ion exchange resins
US4313832A (en) * 1980-06-12 1982-02-02 Rohm And Haas Company Method for treatment of aqueous solutions with ion exchange fibers
US4321154A (en) * 1979-07-19 1982-03-23 Societe Europeene De Propulsion High temperature thermal insulation material and method for making same
US4476191A (en) * 1981-11-16 1984-10-09 Ppg Industries, Inc. Resorcinol-aldehyde resin composition for an adhesive system to be applied to glass fibers
US4513032A (en) * 1981-07-20 1985-04-23 Dorr-Oliver Producing a solid polymeric electrolyte
US4544499A (en) * 1979-08-10 1985-10-01 Pedro B. Macedo Fixation by anion exchange of toxic materials in a glass matrix
US4550015A (en) * 1983-03-21 1985-10-29 Plastics Engineering Company Vitreous carbon and process for preparation thereof
US4589756A (en) * 1983-09-20 1986-05-20 Nippon Kogaku K. K. Method and apparatus for the automatic control of exposure in camera
US4693828A (en) * 1984-09-10 1987-09-15 Toray Industries, Inc. Method of ion-exchanging and/or adsorption
US4732879A (en) * 1985-11-08 1988-03-22 Owens-Corning Fiberglas Corporation Method for applying porous, metal oxide coatings to relatively nonporous fibrous substrates
US4738896A (en) * 1986-09-26 1988-04-19 Advanced Technology Materials, Inc. Sol gel formation of polysilicate, titania, and alumina interlayers for enhanced adhesion of metal films on substrates
US4740540A (en) * 1984-06-08 1988-04-26 Dainippon Ink And Chemicals, Inc. Fiber-reinforced resol-epoxy-amine resin composition molding material and method for producing same
US4760046A (en) * 1985-01-15 1988-07-26 Bayer Aktiengesellschaft Process for the production of activated carbons using phoshoric acid
US4839402A (en) * 1986-09-26 1989-06-13 Advanced Technology Materials, Inc. Sol gel formation of polysilicate, titania, and alumina interlayers for enhanced adhesion of metal films on substrates
US4917835A (en) * 1986-07-22 1990-04-17 The British Petroleum Company P.L.C. Process for the production of porous shaped articles
US4962070A (en) * 1985-10-31 1990-10-09 Sullivan Thomas M Non-porous metal-oxide coated carbonaceous fibers and applications in ceramic matrices
US4983451A (en) * 1987-08-05 1991-01-08 Kabushiki Kaisha Kobe Seiko Sho Carbon fiber-reinforced carbon composite material and process for producing the same
US5026402A (en) * 1989-11-03 1991-06-25 International Fuel Cells Corporation Method of making a final cell electrode assembly substrate
US5039651A (en) * 1988-09-07 1991-08-13 Takeda Chemical Industries, Ltd. Chemically activated shaped carbon, process for producing same and use thereof
US5039635A (en) * 1989-02-23 1991-08-13 Corning Incorporated Carbon-coated reinforcing fibers and composite ceramics made therefrom
US5102855A (en) * 1990-07-20 1992-04-07 Ucar Carbon Technology Corporation Process for producing high surface area activated carbon
US5114887A (en) * 1990-04-27 1992-05-19 Colloid Research Institute Process for preparing oxynitride ceramic fibers
US5143756A (en) * 1990-08-27 1992-09-01 International Business Machines Corporation Fiber reinforced epoxy prepreg and fabrication thereof
US5204310A (en) * 1992-02-21 1993-04-20 Westvaco Corporation High activity, high density activated carbon
US5204376A (en) * 1990-09-25 1993-04-20 Toray Industries, Inc. Anion Exchanger and a method for treating a fluid
US5206207A (en) * 1992-03-18 1993-04-27 Westvaco Corporation Preparation for high activity high density carbon
US5212144A (en) * 1992-06-01 1993-05-18 Westvaco Corporation Process for making chemically activated carbon
US5250491A (en) * 1992-08-11 1993-10-05 Westvaco Corporation Preparation of high activity, high density activated carbon
US5277802A (en) * 1990-04-06 1994-01-11 Healthguard, Incorporated Dual cartridge filter employing pH control
US5304527A (en) * 1992-11-16 1994-04-19 Westvaco Corporation Preparation for high activity, high density carbon
US5318848A (en) * 1990-01-26 1994-06-07 Shiseido Company Ltd. Modified silica gel in chromatography packing material
US5320870A (en) * 1991-08-28 1994-06-14 The United States Of America As Represented By The Secretary Of The Navy Fire protective coating and method for applying same to a structure
US5320089A (en) * 1990-01-30 1994-06-14 Braun Aktiengesellschaft Heatable appliance for personal use
US5328758A (en) * 1991-10-11 1994-07-12 Minnesota Mining And Manufacturing Company Particle-loaded nonwoven fibrous article for separations and purifications
US5350523A (en) * 1990-02-28 1994-09-27 Mitsubishi Kasei Corporation Anion exchange method
US5389325A (en) * 1993-09-24 1995-02-14 Corning Incorporated Activated carbon bodies having phenolic resin binder
US5416056A (en) * 1993-10-25 1995-05-16 Westvaco Corporation Production of highly microporous activated carbon products
US5424042A (en) * 1993-09-13 1995-06-13 Mason; J. Bradley Apparatus and method for processing wastes
US5451444A (en) * 1993-01-29 1995-09-19 Deliso; Evelyn M. Carbon-coated inorganic substrates
US5482915A (en) * 1993-09-20 1996-01-09 Air Products And Chemicals, Inc. Transition metal salt impregnated carbon
US5487917A (en) * 1995-03-16 1996-01-30 Corning Incorporated Carbon coated substrates
US5501801A (en) * 1993-11-30 1996-03-26 Board Of Control Of Michigan Technology University Method and apparatus for destroying organic compounds in fluid
US5512351A (en) * 1993-12-28 1996-04-30 Nikkiso Company Limited Prepreg, process for preparation of prepreg, and products derived therefrom
US5538929A (en) * 1994-08-09 1996-07-23 Westvaco Corporation Phosphorus-treated activated carbon composition
US5547760A (en) * 1994-04-26 1996-08-20 Ibc Advanced Technologies, Inc. Compositions and processes for separating and concentrating certain ions from mixed ion solutions using ion-binding ligands bonded to membranes
US5614459A (en) * 1995-06-07 1997-03-25 Universidad De Antioquia Process for making activated charcoal
US5629251A (en) * 1994-05-23 1997-05-13 Kabushiki Kaisha Kaisui Kagaku Kankyujo Ceramic coating-forming agent and process for the production thereof
US5707471A (en) * 1991-12-20 1998-01-13 Dow Corning Corporation Method for making ceramic matrix composites
US5710092A (en) * 1993-10-25 1998-01-20 Westvaco Corporation Highly microporous carbon
US5759942A (en) * 1994-10-25 1998-06-02 China Petro-Chemical Corporation Ion exchange resin catalyst for the synthesis of bisphenols and the process for preparing the same
US5872070A (en) * 1997-01-03 1999-02-16 Exxon Research And Engineering Company Pyrolysis of ceramic precursors to nanoporous ceramics
US5965483A (en) * 1993-10-25 1999-10-12 Westvaco Corporation Highly microporous carbons and process of manufacture
US6036728A (en) * 1995-11-21 2000-03-14 Eduard Kusters Maschinenfabrik Gmbh & Co. Kg Method of dyeing continuous strips of textile fabric made of polyester fiber or mixtures of polyester with other fibers, and jigger for carrying out the method
US6077605A (en) * 1997-01-31 2000-06-20 Elisha Technologies Co Llc Silicate coatings and uses thereof
US6124114A (en) * 1987-05-16 2000-09-26 Baxter Biotech Technology Sarl Hemoglobins with intersubunit dislufide bonds
US6130175A (en) * 1997-04-29 2000-10-10 Gore Enterprise Holdings, Inc. Integral multi-layered ion-exchange composite membranes
US6177373B1 (en) * 1996-03-14 2001-01-23 Exxon Chemicals Patents Inc Procedure for preparing molecular sieve films
US6283029B1 (en) * 1998-12-17 2001-09-04 Fuji Photo Film Co., Ltd. Direct drawing type lithographic printing plate precursor
US20020006865A1 (en) * 2000-07-17 2002-01-17 Kabushiki Kaisha Toyota Chuo Kenkyusho Photocatalytic substance
US20020074292A1 (en) * 2000-09-26 2002-06-20 Andreas Schlegel Adsorption vessels
US20020151434A1 (en) * 2000-08-28 2002-10-17 Kazunari Domen Photocatalyst mede of metal oxynitride having responsive to visible light
US6508962B1 (en) * 2000-06-21 2003-01-21 Board Of Trustees Of University Of Illinois Carbon fiber ion exchanger
US6517906B1 (en) * 2000-06-21 2003-02-11 Board Of Trustees Of University Of Illinois Activated organic coatings on a fiber substrate
US6638885B1 (en) * 1997-05-22 2003-10-28 The Trustees Of Princeton University Lyotropic liquid crystalline L3 phase silicated nanoporous monolithic composites and their production
US6680279B2 (en) * 2002-01-24 2004-01-20 General Motors Corporation Nanostructured catalyst particle/catalyst carrier particle system
US6706361B1 (en) * 2000-06-21 2004-03-16 Board Of Trustees Of University Of Illinois Polymeric ion exchange fibers
US20040058149A1 (en) * 2002-09-18 2004-03-25 Toshiba Ceramics Co., Ltd. Titanium dioxide fine particles and method for producing the same, and method for producing visible light activatable photocatalyst
US6743749B2 (en) * 2000-01-27 2004-06-01 Kabushiki Kaisha Toyota Chuo Kenkyusho Photocatalyst
US20040197552A1 (en) * 2001-07-25 2004-10-07 Bertrand Maquin Mineral fibre provided with a microporous or mesoporous coating
US6872317B1 (en) * 1998-04-30 2005-03-29 Chelest Corporation And Chubu Chelest Co., Ltd. Chelate-forming filter, process for producing the same, and method of purifying liquid using the filter
US20050164876A1 (en) * 2004-01-28 2005-07-28 The Hong Hong Polytechnic University, A University Of Hong Kong Photocatalyst and methods of making such
US20050221087A1 (en) * 2004-02-13 2005-10-06 James Economy Nanoporous chelating fibers
US20060014050A1 (en) * 2002-04-17 2006-01-19 Lethicia Gueneau Substrate with a self-cleaning coating
US20060078712A1 (en) * 2002-05-29 2006-04-13 Erlus Aktiengesellschaft Ceramic molded body comprising a photocatalytic coating and method for production the same
US7211513B2 (en) * 2003-07-01 2007-05-01 Pilkington North America, Inc. Process for chemical vapor desposition of a nitrogen-doped titanium oxide coating
US7491349B2 (en) * 2004-12-28 2009-02-17 Ishihara Sangyo Kaisha, Ltd. Black titanium oxynitride

Family Cites Families (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2877142A (en) * 1955-02-28 1959-03-10 Du Pont Process for increasing the soil resistance of a solid surface
US3542582A (en) 1968-10-17 1970-11-24 Allied Chem Preparation of carbon cloth
US3946061A (en) * 1969-01-27 1976-03-23 Buckman Laboratories, Inc. Organo-silica polymers
US3592834A (en) * 1969-01-27 1971-07-13 Buckman Labor Inc Organo-silica polymers
US3676173A (en) 1969-04-10 1972-07-11 Scott Paper Co Method for forming pyrolyzed structures
US3853721A (en) 1971-09-09 1974-12-10 Ppg Industries Inc Process for electrolysing brine
GB1415853A (en) 1972-02-12 1975-11-26 Dunlop Ltd Anti-oxidation coatings
US4045338A (en) 1973-05-29 1977-08-30 Mitsubishi Rayon Co., Ltd. Method of removing scale-forming substances from hot water system
JPS534787A (en) 1976-07-05 1978-01-17 Nichibi Kk Cation exchange fibers and its manufacture
US4178413A (en) 1977-10-03 1979-12-11 The Carborundum Company Fiber reinforced carbon and graphite articles and a method of producing said articles
US4476281A (en) * 1978-11-30 1984-10-09 General Electric Company Silicone resin coating composition
JPS5650107A (en) 1979-09-28 1981-05-07 Toho Rayon Co Ltd Manufacture of fibrous activated carbon
DE3011393A1 (en) 1980-03-25 1981-10-01 Riedel-De Haen Ag, 3016 Seelze CHELATE-MAKING ION EXCHANGER BASED ON AN ORGANIC POLYMER AND METHOD FOR THE PRODUCTION THEREOF
EP0045824A1 (en) 1980-08-08 1982-02-17 Tokyo Organic Chemical Industries, Ltd. Ion exchange material, its preparation and use
US4569756A (en) 1981-07-13 1986-02-11 Max Klein Water treatment system
DE3339756A1 (en) 1983-11-03 1985-05-15 Sigri Elektrographit Gmbh, 8901 Meitingen Activated carbon
GB2155458A (en) * 1984-03-05 1985-09-25 Fiber Materials Ceramic coated graphite fiber and method of making same
US4883596A (en) 1987-03-31 1989-11-28 Tokyo Organic Chemical Industries, Ltd. Carbonaceous adsorbent for removal of pyrogen and method of producing pure water using same
US5376407A (en) 1987-05-07 1994-12-27 The Aerospace Corporation Bendable carbon - carbon composite
JPH0819573B2 (en) 1989-02-17 1996-02-28 群栄化学工業株式会社 Activated carbon fiber manufacturing method
GB8923662D0 (en) 1989-10-20 1989-12-06 Norit Uk Ltd A method of producing granular activated carbon
US5580770A (en) 1989-11-02 1996-12-03 Alliedsignal Inc. Support containing particulate adsorbent and microorganisms for removal of pollutants
JPH0764540B2 (en) * 1990-08-02 1995-07-12 出光興産株式会社 Method for producing hydrophobic silica sol
US5616532A (en) * 1990-12-14 1997-04-01 E. Heller & Company Photocatalyst-binder compositions
US5431852A (en) * 1992-01-10 1995-07-11 Idemitsu Kosan Company Limited Water-repellent emulsion composition and process for the production thereof
US5190661A (en) 1992-06-08 1993-03-02 Brigham Young University Process of removing ions from solutions using a complex with sulfur-containing hydrocarbons
FR2708273B1 (en) 1993-06-28 1995-10-20 Inst Textile De France Process for the preparation of a polymeric ion-exchange material with sulfonic functions and material obtained.
JP3204291B2 (en) 1994-07-21 2001-09-04 シャープ株式会社 Carbon body electrode for non-aqueous secondary battery, method for producing the same, and non-aqueous secondary battery using the same
WO1996037288A1 (en) 1995-05-26 1996-11-28 Hitachi Chemical Company, Ltd. Environment purifying material
US5834114A (en) * 1995-05-31 1998-11-10 The Board Of Trustees Of The University Of Illinois Coated absorbent fibers
US6036726A (en) 1995-10-27 2000-03-14 Solutia Inc. Process for separating polyamide from colorant
US5618766A (en) * 1996-07-22 1997-04-08 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Lightweight ceramic composition of carbon silicon oxygen and boron
DE19647368A1 (en) * 1996-11-15 1998-05-20 Inst Neue Mat Gemein Gmbh Composites
US5981425A (en) * 1998-04-14 1999-11-09 Agency Of Industrial Science & Tech. Photocatalyst-containing coating composition
EP1205245A4 (en) 1999-08-05 2005-01-19 Toyoda Chuo Kenkyusho Kk Photocatalytic material and photocatalytic article
US6313045B1 (en) 1999-12-13 2001-11-06 Dow Corning Corporation Nanoporous silicone resins having low dielectric constants and method for preparation
BR0016539B1 (en) * 1999-12-20 2013-06-04 silica-based sols.
CN1153866C (en) * 2000-02-15 2004-06-16 中国人民解放军国防科学技术大学 Technology for continuously coating hetergeneous organic-inorganic sol on surface of inorganic fibres
US6905772B2 (en) * 2000-05-23 2005-06-14 Triton Systems, Inc. Abrasion and impact resistant coating compositions, and articles coated therewith
JP3587178B2 (en) 2001-04-24 2004-11-10 株式会社豊田中央研究所 Surface-modified inorganic oxides and inorganic oxynitrides
MY137042A (en) * 2002-06-14 2008-12-31 Chevron Phillips Chemical Co Hydrogenation palladium-silver catalyst and methods
JPWO2004081130A1 (en) 2003-03-11 2006-06-15 株式会社豊田中央研究所 Composition for photocatalyst coating and coating film
US20050202241A1 (en) 2004-03-10 2005-09-15 Jian-Ku Shang High surface area ceramic coated fibers

Patent Citations (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2670334A (en) * 1952-11-06 1954-02-23 Koppers Co Inc Anion-exchange resins from aminated aryl acetylene
US2885366A (en) * 1956-06-28 1959-05-05 Du Pont Product comprising a skin of dense, hydrated amorphous silica bound upon a core of another solid material and process of making same
US3395970A (en) * 1963-10-30 1968-08-06 Deering Milliken Res Corp Method of carbonizing polyacrylonitrile impregnated cellulose, cyanoethylated cellulose and acrylonitrile graft copolymerized cellulose textiles
US3373104A (en) * 1964-12-17 1968-03-12 Union Tank Car Co Method of cleaning filter tank
US3520805A (en) * 1967-05-29 1970-07-21 Union Tank Car Co Method of disposal of radioactive solids
US3723588A (en) * 1968-03-04 1973-03-27 Carborundum Co Method for production of novolac fibers
US3518206A (en) * 1968-05-17 1970-06-30 Du Pont Supported catalysts composed of substrate coated with colloidal silica and catalyst
US3799796A (en) * 1970-10-06 1974-03-26 Matthey Bishop Inc Preparation of structures with a coating of al2o3/sio2 fibers bonded to al2o3 for use as catalyst substrates
US3971669A (en) * 1972-07-21 1976-07-27 Hyfil Limited Carbon fiber composites
US3903220A (en) * 1972-12-04 1975-09-02 Carborundum Co Method for producing carbon fibers
US3956185A (en) * 1972-12-28 1976-05-11 Matsushita Electric Industrial Co., Ltd. Catalyst for exhaust gas purification
US4045336A (en) * 1974-08-23 1977-08-30 Pauli Henrik Isteri Method and device for oxygenating water with vibrations and under pressure strokes
US4039716A (en) * 1974-09-20 1977-08-02 Owens-Corning Fiberglas Corporation Resin coated glass fibers and method of producing same through use of an aqueous silane-containing sizing composition whereby hydrolysis and polymerization of the silane is inhibited
US4256607A (en) * 1976-10-05 1981-03-17 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4285831A (en) * 1976-10-05 1981-08-25 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4100314A (en) * 1977-03-29 1978-07-11 Airco, Inc. Method for increasing the strength and density of carbonaceous products
US4312956A (en) * 1978-09-19 1982-01-26 Rohm And Haas Company Filtration and deionization prepared from cationic and anionic emulsion ion exchange resins
US4321154A (en) * 1979-07-19 1982-03-23 Societe Europeene De Propulsion High temperature thermal insulation material and method for making same
US4544499A (en) * 1979-08-10 1985-10-01 Pedro B. Macedo Fixation by anion exchange of toxic materials in a glass matrix
US4265768A (en) * 1979-12-26 1981-05-05 Rohm And Haas Company Ion exchange material prepared from partially pyrolyzed macroporous polymer particles
US4313832A (en) * 1980-06-12 1982-02-02 Rohm And Haas Company Method for treatment of aqueous solutions with ion exchange fibers
US4513032A (en) * 1981-07-20 1985-04-23 Dorr-Oliver Producing a solid polymeric electrolyte
US4476191A (en) * 1981-11-16 1984-10-09 Ppg Industries, Inc. Resorcinol-aldehyde resin composition for an adhesive system to be applied to glass fibers
US4550015A (en) * 1983-03-21 1985-10-29 Plastics Engineering Company Vitreous carbon and process for preparation thereof
US4589756A (en) * 1983-09-20 1986-05-20 Nippon Kogaku K. K. Method and apparatus for the automatic control of exposure in camera
US4740540A (en) * 1984-06-08 1988-04-26 Dainippon Ink And Chemicals, Inc. Fiber-reinforced resol-epoxy-amine resin composition molding material and method for producing same
US4693828A (en) * 1984-09-10 1987-09-15 Toray Industries, Inc. Method of ion-exchanging and/or adsorption
US4760046A (en) * 1985-01-15 1988-07-26 Bayer Aktiengesellschaft Process for the production of activated carbons using phoshoric acid
US4962070A (en) * 1985-10-31 1990-10-09 Sullivan Thomas M Non-porous metal-oxide coated carbonaceous fibers and applications in ceramic matrices
US4732879A (en) * 1985-11-08 1988-03-22 Owens-Corning Fiberglas Corporation Method for applying porous, metal oxide coatings to relatively nonporous fibrous substrates
US4917835A (en) * 1986-07-22 1990-04-17 The British Petroleum Company P.L.C. Process for the production of porous shaped articles
US4738896A (en) * 1986-09-26 1988-04-19 Advanced Technology Materials, Inc. Sol gel formation of polysilicate, titania, and alumina interlayers for enhanced adhesion of metal films on substrates
US4839402A (en) * 1986-09-26 1989-06-13 Advanced Technology Materials, Inc. Sol gel formation of polysilicate, titania, and alumina interlayers for enhanced adhesion of metal films on substrates
US6124114A (en) * 1987-05-16 2000-09-26 Baxter Biotech Technology Sarl Hemoglobins with intersubunit dislufide bonds
US4983451A (en) * 1987-08-05 1991-01-08 Kabushiki Kaisha Kobe Seiko Sho Carbon fiber-reinforced carbon composite material and process for producing the same
US5039651A (en) * 1988-09-07 1991-08-13 Takeda Chemical Industries, Ltd. Chemically activated shaped carbon, process for producing same and use thereof
US5039635A (en) * 1989-02-23 1991-08-13 Corning Incorporated Carbon-coated reinforcing fibers and composite ceramics made therefrom
US5026402A (en) * 1989-11-03 1991-06-25 International Fuel Cells Corporation Method of making a final cell electrode assembly substrate
US5318848A (en) * 1990-01-26 1994-06-07 Shiseido Company Ltd. Modified silica gel in chromatography packing material
US5320089A (en) * 1990-01-30 1994-06-14 Braun Aktiengesellschaft Heatable appliance for personal use
US5350523A (en) * 1990-02-28 1994-09-27 Mitsubishi Kasei Corporation Anion exchange method
US5277802A (en) * 1990-04-06 1994-01-11 Healthguard, Incorporated Dual cartridge filter employing pH control
US5114887A (en) * 1990-04-27 1992-05-19 Colloid Research Institute Process for preparing oxynitride ceramic fibers
US5102855A (en) * 1990-07-20 1992-04-07 Ucar Carbon Technology Corporation Process for producing high surface area activated carbon
US5143756A (en) * 1990-08-27 1992-09-01 International Business Machines Corporation Fiber reinforced epoxy prepreg and fabrication thereof
US5204376A (en) * 1990-09-25 1993-04-20 Toray Industries, Inc. Anion Exchanger and a method for treating a fluid
US5320870A (en) * 1991-08-28 1994-06-14 The United States Of America As Represented By The Secretary Of The Navy Fire protective coating and method for applying same to a structure
US5328758A (en) * 1991-10-11 1994-07-12 Minnesota Mining And Manufacturing Company Particle-loaded nonwoven fibrous article for separations and purifications
US5707471A (en) * 1991-12-20 1998-01-13 Dow Corning Corporation Method for making ceramic matrix composites
US5204310A (en) * 1992-02-21 1993-04-20 Westvaco Corporation High activity, high density activated carbon
US5276000A (en) * 1992-03-18 1994-01-04 Westvaco Corporation Preparation for high activity, high density carbon
US5206207A (en) * 1992-03-18 1993-04-27 Westvaco Corporation Preparation for high activity high density carbon
US5212144A (en) * 1992-06-01 1993-05-18 Westvaco Corporation Process for making chemically activated carbon
US5250491A (en) * 1992-08-11 1993-10-05 Westvaco Corporation Preparation of high activity, high density activated carbon
US5304527A (en) * 1992-11-16 1994-04-19 Westvaco Corporation Preparation for high activity, high density carbon
US5451444A (en) * 1993-01-29 1995-09-19 Deliso; Evelyn M. Carbon-coated inorganic substrates
US5424042A (en) * 1993-09-13 1995-06-13 Mason; J. Bradley Apparatus and method for processing wastes
US5482915A (en) * 1993-09-20 1996-01-09 Air Products And Chemicals, Inc. Transition metal salt impregnated carbon
US5540759A (en) * 1993-09-20 1996-07-30 Air Products And Chemicals, Inc. Transition metal salt impregnated carbon
US5389325A (en) * 1993-09-24 1995-02-14 Corning Incorporated Activated carbon bodies having phenolic resin binder
US5965483A (en) * 1993-10-25 1999-10-12 Westvaco Corporation Highly microporous carbons and process of manufacture
US5416056A (en) * 1993-10-25 1995-05-16 Westvaco Corporation Production of highly microporous activated carbon products
US5710092A (en) * 1993-10-25 1998-01-20 Westvaco Corporation Highly microporous carbon
US5501801A (en) * 1993-11-30 1996-03-26 Board Of Control Of Michigan Technology University Method and apparatus for destroying organic compounds in fluid
US5512351A (en) * 1993-12-28 1996-04-30 Nikkiso Company Limited Prepreg, process for preparation of prepreg, and products derived therefrom
US5547760A (en) * 1994-04-26 1996-08-20 Ibc Advanced Technologies, Inc. Compositions and processes for separating and concentrating certain ions from mixed ion solutions using ion-binding ligands bonded to membranes
US5629251A (en) * 1994-05-23 1997-05-13 Kabushiki Kaisha Kaisui Kagaku Kankyujo Ceramic coating-forming agent and process for the production thereof
US5538929A (en) * 1994-08-09 1996-07-23 Westvaco Corporation Phosphorus-treated activated carbon composition
US5759942A (en) * 1994-10-25 1998-06-02 China Petro-Chemical Corporation Ion exchange resin catalyst for the synthesis of bisphenols and the process for preparing the same
US5487917A (en) * 1995-03-16 1996-01-30 Corning Incorporated Carbon coated substrates
US5614459A (en) * 1995-06-07 1997-03-25 Universidad De Antioquia Process for making activated charcoal
US6036728A (en) * 1995-11-21 2000-03-14 Eduard Kusters Maschinenfabrik Gmbh & Co. Kg Method of dyeing continuous strips of textile fabric made of polyester fiber or mixtures of polyester with other fibers, and jigger for carrying out the method
US6177373B1 (en) * 1996-03-14 2001-01-23 Exxon Chemicals Patents Inc Procedure for preparing molecular sieve films
US5872070A (en) * 1997-01-03 1999-02-16 Exxon Research And Engineering Company Pyrolysis of ceramic precursors to nanoporous ceramics
US6077605A (en) * 1997-01-31 2000-06-20 Elisha Technologies Co Llc Silicate coatings and uses thereof
US6130175A (en) * 1997-04-29 2000-10-10 Gore Enterprise Holdings, Inc. Integral multi-layered ion-exchange composite membranes
US6638885B1 (en) * 1997-05-22 2003-10-28 The Trustees Of Princeton University Lyotropic liquid crystalline L3 phase silicated nanoporous monolithic composites and their production
US6872317B1 (en) * 1998-04-30 2005-03-29 Chelest Corporation And Chubu Chelest Co., Ltd. Chelate-forming filter, process for producing the same, and method of purifying liquid using the filter
US6283029B1 (en) * 1998-12-17 2001-09-04 Fuji Photo Film Co., Ltd. Direct drawing type lithographic printing plate precursor
US6743749B2 (en) * 2000-01-27 2004-06-01 Kabushiki Kaisha Toyota Chuo Kenkyusho Photocatalyst
US6508962B1 (en) * 2000-06-21 2003-01-21 Board Of Trustees Of University Of Illinois Carbon fiber ion exchanger
US6517906B1 (en) * 2000-06-21 2003-02-11 Board Of Trustees Of University Of Illinois Activated organic coatings on a fiber substrate
US6706361B1 (en) * 2000-06-21 2004-03-16 Board Of Trustees Of University Of Illinois Polymeric ion exchange fibers
US20020006865A1 (en) * 2000-07-17 2002-01-17 Kabushiki Kaisha Toyota Chuo Kenkyusho Photocatalytic substance
US6680277B2 (en) * 2000-07-17 2004-01-20 Kabushiki Kaisha Toyota Chuo Kenkyusho Photocatalytic susbstance
US20020151434A1 (en) * 2000-08-28 2002-10-17 Kazunari Domen Photocatalyst mede of metal oxynitride having responsive to visible light
US6878666B2 (en) * 2000-08-28 2005-04-12 Japan Science And Technology Agency Photocatalyst made of metal oxynitride having responsibility of visible light
US20020074292A1 (en) * 2000-09-26 2002-06-20 Andreas Schlegel Adsorption vessels
US20040197552A1 (en) * 2001-07-25 2004-10-07 Bertrand Maquin Mineral fibre provided with a microporous or mesoporous coating
US6680279B2 (en) * 2002-01-24 2004-01-20 General Motors Corporation Nanostructured catalyst particle/catalyst carrier particle system
US20060014050A1 (en) * 2002-04-17 2006-01-19 Lethicia Gueneau Substrate with a self-cleaning coating
US20060078712A1 (en) * 2002-05-29 2006-04-13 Erlus Aktiengesellschaft Ceramic molded body comprising a photocatalytic coating and method for production the same
US20060099397A1 (en) * 2002-05-29 2006-05-11 Erlus Aktiengesellschaft Ceramic moulded body comprising a photocatalytic coating and method for producing the same
US20040058149A1 (en) * 2002-09-18 2004-03-25 Toshiba Ceramics Co., Ltd. Titanium dioxide fine particles and method for producing the same, and method for producing visible light activatable photocatalyst
US7211513B2 (en) * 2003-07-01 2007-05-01 Pilkington North America, Inc. Process for chemical vapor desposition of a nitrogen-doped titanium oxide coating
US20050164876A1 (en) * 2004-01-28 2005-07-28 The Hong Hong Polytechnic University, A University Of Hong Kong Photocatalyst and methods of making such
US20050221087A1 (en) * 2004-02-13 2005-10-06 James Economy Nanoporous chelating fibers
US7491349B2 (en) * 2004-12-28 2009-02-17 Ishihara Sangyo Kaisha, Ltd. Black titanium oxynitride

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040197552A1 (en) * 2001-07-25 2004-10-07 Bertrand Maquin Mineral fibre provided with a microporous or mesoporous coating
US20050221087A1 (en) * 2004-02-13 2005-10-06 James Economy Nanoporous chelating fibers
US8241706B2 (en) 2004-03-10 2012-08-14 The Board Of Trustees Of The University Of Illinois High surface area ceramic coated fibers
US20070271682A1 (en) * 2004-05-24 2007-11-29 Eastman Robert Ii Scent-Suppressing Fiber, and Articles Incorporating Same
US20100213574A1 (en) * 2004-08-31 2010-08-26 Micron Technology, Inc. High dielectric constant transition metal oxide materials
US8791519B2 (en) * 2004-08-31 2014-07-29 Micron Technology, Inc. High dielectric constant transition metal oxide materials
US8541337B2 (en) 2005-12-29 2013-09-24 The Board Of Trustees Of The University Of Illinois Quaternary oxides and catalysts containing quaternary oxides
US7521394B2 (en) 2005-12-29 2009-04-21 The Board Of Trustees Of The University Of Illinois Nanoparticles containing titanium oxide
US20070202334A1 (en) * 2005-12-29 2007-08-30 Rong-Cai Xie Nanoparticles containing titanium oxide
US7901660B2 (en) 2005-12-29 2011-03-08 The Board Of Trustees Of The University Of Illinois Quaternary oxides and catalysts containing quaternary oxides
US20110091514A1 (en) * 2005-12-29 2011-04-21 Rong Xie Quaternary oxides and catalysts containing quaternary oxides
US20070190765A1 (en) * 2005-12-29 2007-08-16 Rong-Cai Xie Quaternary oxides and catalysts containing quaternary oxides
US20070264467A1 (en) * 2006-05-09 2007-11-15 Ruei-Shan Wang Photocatalyst synthesized fiber product
WO2010022394A2 (en) * 2008-08-22 2010-02-25 The Board Of Trustees Of The University Of Illinois Catalytic compositions, composition production methods, and aqueous solution treatment methods
WO2010022394A3 (en) * 2008-08-22 2010-04-15 The Board Of Trustees Of The University Of Illinois Catalytic compositions, composition production methods, and aqueous solution treatment methods
US20110147317A1 (en) * 2008-08-22 2011-06-23 Qi Li Catalytic Compositions, Composition Production Methods, and Aqueous Solution Treatment Methods
US20120058884A1 (en) * 2008-08-27 2012-03-08 Korea University Research And Business Foundation Fiber including silica and metal oxide
US20100193449A1 (en) * 2009-02-02 2010-08-05 Jian-Ku Shang Materials and methods for removing arsenic from water
US8461462B2 (en) * 2009-09-28 2013-06-11 Kyocera Corporation Circuit substrate, laminated board and laminated sheet
US20110073358A1 (en) * 2009-09-28 2011-03-31 Kyocera Corporation Circuit substrate, laminated board and laminated sheet
US8975537B2 (en) 2009-09-28 2015-03-10 Kyocera Corporation Circuit substrate, laminated board and laminated sheet

Also Published As

Publication number Publication date
CN1950308B (en) 2010-05-26
EP1732859A1 (en) 2006-12-20
MXPA06010223A (en) 2007-03-07
CN1950308A (en) 2007-04-18
US8241706B2 (en) 2012-08-14
KR20070004800A (en) 2007-01-09
BRPI0508566A (en) 2007-08-14
US20110064609A1 (en) 2011-03-17
AU2005222413A1 (en) 2005-09-22
CA2558720A1 (en) 2005-09-22
WO2005087679A1 (en) 2005-09-22
JP2007528454A (en) 2007-10-11

Similar Documents

Publication Publication Date Title
US8241706B2 (en) High surface area ceramic coated fibers
KR101083060B1 (en) Method for producing carbon composite nano fiber with photocatalytic activity, carbon composite nano fiber with photocatalytic activity produced by the same method, filters comprising the carbon nano fiber and TiO2,SiO2 sol solutions used for thermo stable photo catalyst
Asahi et al. Nitrogen-doped titanium dioxide as visible-light-sensitive photocatalyst: designs, developments, and prospects
US20080131311A1 (en) Fluorescent lamp device capable of cleaning air
US20100239470A1 (en) Photocatalysts Based on Structured Three-Dimensional Carbon or Carbon-Containing Material Forms
US20110091514A1 (en) Quaternary oxides and catalysts containing quaternary oxides
JP2002517628A (en) Substrate with photocatalytic coating
WO2007023558A1 (en) Tungsten oxide photocatalyst, process for producing the same, and fiber cloth having deodorizing/antifouling function
WO2008005055A2 (en) Nanoparticles containing titanium oxide
JP2002285691A (en) Interior material
WO2002038272A1 (en) Preparation of firmly-anchored photocatalitically-active titanium dioxide coating films with non-gelled organic-doped precursors
JP2003275600A (en) Visible ray responsive and adsorptive composite material
Tijani et al. Synthesis and characterization of carbon doped TiO2 photocatalysts supported on stainless steel mesh by sol-gel method
KR101677842B1 (en) Multifunctional Cu-TiO2-PU having both photocatalyst and adsorbent activity and manufacturing method thereof
KR101104168B1 (en) Preparation method of carbon material based photocatalyst with improved photo catalytic activity, the photocatalyst prepared by the former method and the filter containing the former carbon material based photo catalyst
JP4246943B2 (en) Method for producing article having photocatalyst-containing porous thin film
JP3846673B2 (en) Silica gel molded body having photocatalytic function and method for producing the same
KR20090122291A (en) Silica-based composite oxide fiber, catalyst fiber comprising the same, and process for producing the same
JP3505305B2 (en) Catalyst composition and deodorizing method using the same
WO2013099006A1 (en) Photocatalysts and process for preparing photocatalysts
KR101840038B1 (en) Titanium dioxide composition and method for prepairing the same
JP2001096154A (en) Vanadium oxide/titania hybrid photocatalyst and its manufacturing method
KR100426213B1 (en) A solution for coating of leather and coated leather with multifunctional property
JP2000262909A (en) Product having photocatalytic function
JP2005219966A (en) Production method for titanium oxide solution, titanium oxide solution, and photocatalyst coating material

Legal Events

Date Code Title Description
AS Assignment

Owner name: BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS, T

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KUSHANG, JIAN;XIE, RONGCAI;YUE, ZHONGREN;AND OTHERS;REEL/FRAME:015610/0328;SIGNING DATES FROM 20040702 TO 20040703

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION