US20040213918A1 - Functionalization of porous materials by vacuum deposition of polymers - Google Patents

Functionalization of porous materials by vacuum deposition of polymers Download PDF

Info

Publication number
US20040213918A1
US20040213918A1 US10830608 US83060804A US2004213918A1 US 20040213918 A1 US20040213918 A1 US 20040213918A1 US 10830608 US10830608 US 10830608 US 83060804 A US83060804 A US 83060804A US 2004213918 A1 US2004213918 A1 US 2004213918A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
process
monomer
porous substrate
functionality
produced
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.)
Granted
Application number
US10830608
Other versions
US20060257642A9 (en )
US7157117B2 (en )
Inventor
Michael Mikhael
Angelo Yializis
Original Assignee
Mikhael Michael G.
Angelo Yializis
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

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/022Metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/16Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/16Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/18Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being cellulose or derivatives thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/20Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2003Glass or glassy material
    • B01D39/2017Glass or glassy material the material being filamentary or fibrous
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/20Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2055Carbonaceous material
    • B01D39/2065Carbonaceous material the material being fibrous
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039Inorganic membrane formation
    • B01D67/0072Inorganic membrane formation by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081After-treatment of organic or inorganic membranes
    • B01D67/0088Physical treatment with compounds, e.g. swelling, coating or impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081After-treatment of organic or inorganic membranes
    • B01D67/009After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/60Deposition of organic layers from vapour phase
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/20Carburising
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80After-treatment
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025Corona discharge or low temperature plasma
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08Organic compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/0241Types of fibres, filaments or particles, self-supporting or supported materials comprising electrically conductive fibres or particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0414Surface modifiers, e.g. comprising ion exchange groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0414Surface modifiers, e.g. comprising ion exchange groups
    • B01D2239/0421Rendering the filter material hydrophilic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0414Surface modifiers, e.g. comprising ion exchange groups
    • B01D2239/0428Rendering the filter material hydrophobic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/045Deodorising additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0457Specific fire retardant or heat resistant properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0471Surface coating material
    • B01D2239/0478Surface coating material on a layer of the filter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0471Surface coating material
    • B01D2239/0492Surface coating material on fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/065More than one layer present in the filtering material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/10Filtering material manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12Special parameters characterising the filtering material
    • B01D2239/1291Other parameters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/04Characteristic thickness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/26Electrical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/30Chemical resistance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/36Hydrophilic membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/38Hydrophobic membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141Plasma treatment
    • B05D3/142Pretreatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141Plasma treatment
    • B05D3/142Pretreatment
    • B05D3/144Pretreatment of polymeric substrates
    • 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
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • 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
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955Void-containing component partially impregnated with adjacent component
    • Y10T428/249956Void-containing component is inorganic
    • 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
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987With nonvoid component of specified composition
    • 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
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987With nonvoid component of specified composition
    • Y10T428/24999Inorganic

Abstract

A porous substrate is pretreated in a plasma field and a functionalizing monomer is immediately flash-evaporated, deposited and cured over the porous substrate in a vacuum vapor-deposition chamber. By judiciously controlling the process so that the resulting polymer coating adheres to the surface of individual fibers in ultra-thin layers (approximately 0.02-3.0 μm) that do not extend across the pores in the material, the porosity of the porous substrate is essentially unaffected while the fibers and the final product acquire the desired functionality. The resulting polymer layer is also used to improve the adherence and durability of metallic and ceramic coatings.

Description

  • RELATED APPLICATION [0001]
  • This application is based on U.S. Provisional Application Serial No. 60/465,719, filed on Apr. 25, 2003.[0002]
  • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0003]
  • This invention is related in general to the functionalization of the surface of materials for the purpose of improving their properties for particular applications. In particular, it pertains to a combined plasma-treatment/vapor-deposition process for functionalizing paper, membranes, and other woven and non-woven porous materials. [0004]
  • 2. Description of the Related Art [0005]
  • The term “functionalization” and related terminology are used in the art and herein to refer to the process of treating a material to alter its surface properties to meet specific requirements for a particular application. For example, the surface energy of a material may be treated to render it particularly hydrophobic or hydrophilic as may be desirable for a given use. Thus, surface functionalization has become common practice in the manufacture of many materials because it adds value to the end product. In order to achieve such different ultimate results, functionalization may be carried out in a variety of ways ranging from wet chemistry to various forms of vapor deposition, vacuum metallization and sputtering. [0006]
  • Textiles, non-woven products and paper substrates are fiber-based porous materials with inherent properties derived from the nature of the fibers. Synthetic and natural fibers (for example, polypropylene, nylon, polyethylene, polyester, cellulosic fibers, wool, silk, and other polymers and blends) can be shaped into different products with a great range of mechanical and physical properties. In addition, the porosity of these materials usually serves a necessary function, such as gas and/or liquid permeation, particulate filtration, liquid absorption, etc. Therefore, any subsequent treatment designed to further modify the chemical properties of the fibers by appropriately functionalizing them must be carried out, to the extent possible, without affecting the porosity of the material. This has heretofore been virtually impossible when such functionalization results from the deposition of polymers. [0007]
  • A variety of wet chemical processes have been used traditionally to treat with polymers and functionalize fibers that are otherwise inert or have limited surface functionality. These processes involve the immersion of the fibrous material in liquids or fluid foams designed to coat individual fibers and impart specific functionalities while retaining the material's porosity and ability to breathe. In spite of the many claims made in commercial products, though, it is clear that such wet-chemistry processes at best materially reduce the porosity of the substrate or, in the worst cases, essentially plug the interstices between fibers. Therefore, the functionalization of porous materials by wet-chemistry polymer deposition has produced the desired results in terms of surface functionality, but with the attendant serious deterioration of the mechanical characteristics of the underlying porous substrate. [0008]
  • Thus, prior-art processes for functionalizing porous materials by coating the fibers with a polymer film have produced unsatisfactory results because of loss of porosity. In addition, these solvent-based and water-based processes for woven and non-woven fabrics, paper and other porous materials (like open- and closed-cell plastic foams) have been increasingly facing environmental challenges and constraints that result in higher end-product costs. In some cases, producers have actually withdrawn from the market coatings that present potential health hazards, such as the fluoro and chloro monomer materials used to functionalize products for hydrophobic/oleophobic and biocide properties, respectively. [0009]
  • Therefore, there is a pressing need for new coating technologies that are suitable for porous materials, are safe to implement, do not utilize solvents, and do not effect the mechanical and functional properties of the porous substrate. While polymers applied by vacuum deposition have been used successfully in the art to impart particular functional properties to non-porous, non-permeable substrates, no attempt was historically made to so functionalize porous materials because the vacuum deposition process was believed to be likely to exacerbate the pore plugging problem. [0010]
  • For example, the vacuum deposition of a polymer coating by flash evaporation of a monomer and its subsequent polymerization by radiation curing in a vacuum chamber has been used widely with a variety of monomers, such as free-radical polymerizable acrylates, cationic polymerizable epoxies and vinyl monomers, to control the surface energy of the resulting products and introduce desirable characteristics. Without limitation, these include hydrophobicity, oleophobicity, hydrophilicity, oleophilicity, fire resistance, biocidicity, color, anti-stain, antistatic, and sensor properties. In all cases, the substrate is exposed to a dense fog of vaporized monomer under conditions that cause its immediate condensation and curing on the substrate's surface. Therefore, it stood to reason to believe that these conditions would favor the accumulation of monomer droplets in the pores of a porous substrate and cause it to become impermeable. This invention is based on the surprising discovery that, when appropriately controlled, vacuum deposition can be use successfully to functionalize porous materials while retaining their permeability properties. [0011]
  • BRIEF SUMMARY OF THE INVENTION
  • In view of the foregoing, this invention is directed at a process that is suitable for functionalizing a broad range of porous substrates, including synthetic and natural fabrics, fibers and non-woven materials. Because of the fibrous nature of these substrates and their general commercial uses, the invention is directed particularly at maintaining the breathability of the materials, providing durability in the coatings and prolonged resistance to washing and cleaning, and selectively treating one or both sides of the fabric material. The invention also aims at a process that is compatible with the use of existing equipment and with the application of other coating layers, including various additives and catalysts currently utilized in the art. [0012]
  • Therefore, according to one aspect of the invention, a porous substrate is pretreated in a plasma field and a functionalizing monomer is immediately flash-evaporated, deposited and cured over the substrate in a vacuum vapor-deposition chamber. We discovered that it is possible to control the process so that the resulting polymer coating adheres to the surface of individual fibers in ultra-thin layers (approximately 0.02-3.0 μm, depending on the size of the pores) that do not extend across the pores in the material. As a result, the porosity of the substrate is essentially unaffected while the fibers and the final product acquire the desired functionality. [0013]
  • The vapor deposition of metals and/or ceramics has also been used in the art to produce a great variety of functionalized products. For example, metal-coated substrates provide increased reflectivity and indium-titanium-oxide (ITO) coated materials provide electrical conductivity. Metal, ceramic and polymer layers have been deposited on non-porous substrates separately or in combination to produce different effects, as may be desirable for particular applications. [0014]
  • Therefore, according to another aspect of the invention, multiple layers of polymeric and metallic and/or ceramic materials are vapor deposited in a single process to impart additional functional properties to the porous substrate. For example, while it has been known to deposit metal layers directly on fabrics in order to add reflectivity, the resulting coated products have exhibited low durability and poor resistance to abrasion (i.e., the metal particles do not form an even layer over the microscopically rough fiber surfaces and metal flakes tend to separate from the fabric). According to the invention, a polymer layer is first deposited to produce a smooth thin layer over the fibers and a metal layer is then deposited over the resulting improved substrate. This process yields a smoother fiber surface for receiving the metal deposition, which prevents cracking and separation of the outer metal layer. If necessary, depending on the intended use, an additional polymeric protective layer can yet be added over the metallic film without materially affecting the overall permeability of the fabric. [0015]
  • As detailed below, similar advantages are obtained by combining polymers with ceramics, which also tend to break up and separate from the substrate when deposited directly over fibers. Various other purposes and advantages of the invention will become clear from its description in the specification that follows and from the novel features particularly pointed out in the appended claims. Therefore, the invention consists of the features hereinafter illustrated in the drawings, fully described in the detailed description of the preferred embodiments and particularly pointed out in the claims. [0016]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a schematic representation of a modified vacuum chamber according to the invention. [0017]
  • FIG. 2 is a scanning electron microscope (SEM) picture of an uncoated non-woven polypropylene fabric used to produce an oleophobic filter medium. [0018]
  • FIG. 3 is an SEM picture of the same non-woven polypropylene fabric of FIG. 2 after coating by monomer vacuum deposition according to the invention. [0019]
  • FIG. 4 is a schematic representation of a vacuum chamber equipped with plasma pretreatment, a flash evaporation/condensation station, a monomer radiation-curing station, and a metal or ceramic vapor deposition station for the sequential deposition of multiple layers over a porous substrate according to the invention. [0020]
  • FIG. 5 is a schematic representation of the same chamber of FIG. 4 with an additional in-line vacuum deposition station following the metal/ceramic deposition unit. [0021]
  • FIG. 6 illustrates the functionalizing properties of the invention on a porous non-woven polypropylene filter medium. The lower portion shows the oleo-philic (left) and hydrophobic (right) properties of the uncoated material. The middle portion shows the medium's oleophobic property acquired after coating with a TEFLON®-like polymer (a fluorinated acrylate). The top portion shows the hydrophilic property acquired after coating with a wetting polymer (a carboxylic acid functionalized acrylate). [0022]
  • FIG. 7 is a flow chart of the basic steps of the process of the invention. [0023]
  • FIG. 8 is a flow chart of the steps involved in a second embodiment of the invention. [0024]
  • FIG. 9 is a flow chart of the steps involved in a third embodiment of the invention. [0025]
  • DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
  • The invention lies in the discovery that utilizing the process of vacuum deposition to functionalize a porous substrate with a polymeric film makes it possible to control the thickness of the deposited layer and avoid the problem of pore plugging encountered when functionalization is carried out by wet chemistry. The invention also lies in the discovery that coating individual fibers of a porous substrate with a thin polymer layer produces a surface that is better adapted for receiving the subsequent deposition of metal or ceramic layers. Surprisingly, when deposited over an underlying polymer layer already used to coat individual fibers, metals and ceramics are found to be much more resistant to breakage and separation than heretofore possible using prior-art deposition techniques. Without limitation, porous substrates to which this invention applies consist of polypropylene, polyethylene, fluoro-polymers, polyester, nylon, rayon, paper, wool, cotton, glass fibers, carbon fibers, cellulose based fibers, and metals. [0026]
  • For the purposes of this disclosure, the term “porous” is used in a macroscopic sense with reference to any substrate through which fluids can easily permeate under normal conditions. These include, for example, paper, textiles, woven or non-woven fabrics, solid foams, membranes and similar materials exhibiting permeability properties typically associated with these products. “Porous” is not intended to cover materials which, though they exhibit structural porosity, are not used functionally as permeable substrates. The term “condensation” refers to a phase-change process from gas to liquid (and subsequently solid) obtained upon contact with a surface having a temperature lower than the dew point of the gas at a given operating pressure. For the purposes of the invention, such a surface is the substrate subjected to vapor deposition which has been either pre-chilled or is in contact with a cold drum in the vacuum chamber. Finally, the term “monomer” is intended to include also oligomers and blends of monomers or oligomers capable of flash evaporation in a vacuum chamber. [0027]
  • In its preferred embodiment, the invention is practiced by first pretreating the porous substrate in a plasma field and then immediately subjecting it to the deposition of a thin layer of vaporized monomer in a vacuum deposition process under conditions that prevent the formation of condensate blocking the pores of the substrate. The monomer film is subsequently polymerized by exposing it to an electron-beam field or other radiation-curing process. The monomer is flash-evaporated and condensed on the porous substrate in conventional manner but, in order to retain the structural porosity and the related functional properties of the substrate, the residence time of the substrate within the deposition zone of the vacuum chamber is controlled to ensure that a very thin film is deposited relative to the size of the pores in the substrate. Thus, monomer penetration within the porous structure of the substrate produces a coating of individual fibers (or pore walls) without sealing the openings between fibers. This is achieved by controlling the vapor density and the speed of the moving substrate to limit the thickness of the coating to about 0.02 to 3 μm. [0028]
  • Vacuum plasma has been used for some time to pretreat as well as to finish treating products of vapor deposition processes. Pretreatment is used to clean and activate the substrate. These functions are attributed to the plasma ablation of contaminants and the generation of free radical and ionic species, respectively. Plasma finishing treatment has been shown to have chemical and physical effects that are useful in improving the outcome of vapor-deposition processes. For example, plasma for hydrocarbon gases and other functional monomer vapors that polymerize on the vapor-deposited surface may be added (plasma grafting and polymerization) to produce specific results, such as hydrophilic and hydrophobic surfaces. [0029]
  • We found that, when coupled with the vacuum deposition of monomers over fibrous substrates, plasma pretreatment produces the additional unexpected effect of preventing the formation of monomer droplets (an effect referred to as “beading” in the art) over the substrate. This discovery is particularly advantageous to prevent the plugging of pores in fabrics, paper and other porous materials being coated with functionalizing monomers. Therefore, the combination of plasma pretreatment with vapor deposition is much preferred in carrying out the invention. [0030]
  • As illustrated in FIG. 1, in order to practice the invention a conventional vacuum chamber [0031] 10 is modified to enable the serial plasma-field pretreatment, vapor deposition, and radiation curing of a porous substrate in a continuous process. Typically, the porous substrate 12 (like paper or fabric) is processed entirely within the vacuum chamber 10 while being spooled continuously between a feed reel 14 and a product reel 16. The substrate 12 is first passed through a cold compartment 18 to chill it to a temperature sufficiently low to ensure the subsequent cryocondensation of the monomer vapor. The substrate is then passed through a plasma pretreatment unit 20 and immediately thereafter (within no more than a few seconds, preferably within milliseconds) through a flash evaporator 22, where it is exposed to the monomer vapor for the deposition of a thin liquid film over the cold substrate. The monomer film is then polymerized by radiation curing through exposure to an electron beam unit 24 and passed downstream through another (optional) cooled compartment 18. As is well known in the art, instead of pre-chilling the substrate 12 being processed, a rotating cold drum (typically kept at −20° C. to 30° C.) in contact with the substrate past the evaporator 22 may be used to effect the condensation of the monomer vapor.
  • We found that the monomer feed to the evaporator unit [0032] 22 and the speed of the spooling substrate can be judiciously tailored to ensure the three-dimensional coverage of the porous structure of the substrate 12 while limiting the thickness of the film deposited over the substrate fibers. For example, feeding a fluoro-acrylate monomer at a rate of about 40 ml/minute to the flash evaporator 22 and moving the substrate 12 (1.2 meter wide) through the chamber at a speed of about 100 meters per minute produces the formation of a substantially uniform film about 0.5-μm thick over the polypropylene fibers of a typical filter medium with pores about 20-40 μm wide. As a result, the porosity of the medium is not significantly affected, but the material is thoroughly functionalized to exhibit oleophobic properties.
  • FIGS. 2 and 3 illustrate SEM pictures of such a non-woven filter medium before and after coating, respectively, according to the invention. The micrographs show no evidence of polymer obstruction between the fibers and, in fact, air permeation tests showed no significant difference between the two samples. This resulted from the conformal (i.e., shaped to conform to the structure of individual fibers) deposition of the liquid monomer from a vapor phase state over the surface of the fibers, in contrast to conventional liquid-based methods that exhibit very limited levels of conformal deposition. The smooth and pliable nature of the polymer surface covering each fiber after vapor deposition is believed to be the reason for the greater adhesion and resistance to breakage of metallic and/or ceramic layers whey they are further used to cover the fibers. [0033]
  • In general, we found that thin polymer coatings (0.1 μm or less) designed to alter the chemical functionality of a porous substrate have no significant effect on gas permeability. Thicker coatings, designed to provide physical protection against wear and tear, have only a minor effect on breathability. As illustrated in Table 1 below for three different fabrics treated with the process of the invention, air permeability appears to be (and remain after treatment) simply a function of the weight of the material (i.e., the coarseness of the weave), rather than of the polymer coating. Each material in the table (A-cotton, B-polyester, C-wool) consisted of a woven fabric coated with as much as 2-3 μm of vacuum deposited acrylate polymer prior to metallization. This relatively thick polymer coating enhanced the abrasion resistance and washability properties of the metallized fabrics but did not materially affect the permeability of the material. [0034]
    TABLE 1
    Basis weight Air permeability
    Material (OZ/Y2) (CFM/M2)
    A-uncoated cotton 5.83 39.6
    A-coated cotton 6.06 38.9
    B-uncoated polyester 6.76 16.0
    B-coated polyester 6.90 15.5
    C-uncoated wool 3.38 118.7
    C-coated wool 3.54 108.6
  • Based on these results, it is clear that the invention provides an environmentally friendly vacuum-based process that utilizes solvent-free and water-free monomers and produces high-quality polymer coatings that do not effect the functional porosity of the substrate. The coating process can be implemented in conventional vacuum coating plants and can be combined with in-line plasma treatment and metallization to create unique and high value-added products. The common feature of all embodiments of the invention is coating of the fibers or voids in the porous substrate produced by flash evaporation and radiation curing of a monomer to produce a conforming, thin, polymer layer that functionalizes the surface of a porous material with virtually no effect on its permeability or breathability. [0035]
  • Various tests have shown that the process can be used successfully to functionalize surfaces of woven and non-woven fabrics, paper, membranes and foam substrates. Properties such as oil and water repellency and wettability, release, antibacterial and other chemical functionalities are easily achievable with ultra thin polymer coatings (less than 0.2 μm). Thicker polymer layers, of the order of 0.2-3 μm, have been used to provide thermo-mechanical properties such as heat sealing, abrasion resistance and chemical resistance against moisture, acids, bases and organic solvents. Such thin coatings of multifunctional acrylates, monoacrylates, vinyls, epoxies and various other oligomers can be deposited over a substrate traveling at speeds as high as 1000 ft/min. This high productivity, combined with relatively low monomer material costs, results in a very economical and cost effective functionalization process. [0036]
  • When further combined with the vapor deposition of metal and/or ceramic layers, the process of the invention affords improvements in a wide range of multifunctional products. FIG. 4 illustrates schematically a vacuum chamber [0037] 30 that includes a station 32 for depositing metals and ceramics (such as a sputtering unit or a reactive electron-beam evaporation unit). Note that in the process illustrated in this figure the porous substrate 12 is chilled by contact with a cold drum 34 for the condensation step. If desirable, additional layers may be deposited sequentially in line by adding further deposition units. For example, a transparent polymer layer may be further used to coat the metal layer already deposited on the fabric (over the initial thin polymer film of the invention) in order to protect the metal and prevent abrasion while retaining the reflectivity of the fabric. In such a case, as shown in FIG. 5, an additional flash evaporation unit 36, followed by a second radiation curing unit 38, would be utilized after the metallization stage.
  • It is anticipated that such a combination of layers can be used advantageously in the production of a variety of improved products. For example, metallized fabrics are used for decoration and to achieve energy savings in the production of roll, vertical, and horizontal blinds. Similarly, breathable insulation in the form of metallized paper and non-woven polymers is widely used in construction to reflect heat while minimizing the formation of mold and mildew. Metallized fabrics are used to decorate garments and paper for labels. They are also used as clothing liners and in camping gear, such as sleeping bags and tents, to improve insulation without affecting weight and breathability. The same advantages are desirable in blankets and tapes for medical applications, in fire protective suits designed to reflect infrared radiation in a multitude of military applications (jackets, shirts, garments, tents and tarps used to reduce infrared signature), in garments for workers in microwave and radar communication industries, and in clothing for electro-magnetic interference (EMI) testing personnel. [0038]
  • Metallized fabrics are also widely used in the automotive industry to provide engine and exhaust-heat insulation, and filter media (such as functionalized the non-woven polypropylene used to produce electrostatically charged filter systems and air filters with EMI shielding properties). Foams and fabrics are metallized to produce electromagnetic shields for gasket materials, cable shields, covers and liners for motors, avionic boxes, cable junctions, antennas, portable shielded rooms, window drapery, wall coverings and electrostatic dissipating garments. The performance of the porous materials used in all of these applications can be materially improved by the initial deposition of a first thin-film polymer layer according to the present invention. [0039]
  • A great variety of paper, as well as woven and non-woven fabrics, were coated according to the invention with different polymer formulations designed to serve specific applications. The coated materials were subjected to surface microscopic investigation. The data showed in all cases that condensing a flash-evaporated monomer vapor on the plasma pretreated fibers produces a homogeneous thin liquid layer that covers the entire surface of each individual fiber without connecting fiber to fiber and blocking the pores. The following examples illustrate these applications of the invention (all percentages are by weight). [0040]
  • EXAMPLE 1 Hydrophobic/Oleophobic Coating
  • A melt-blown polypropylene nonwoven fabric was functionalized with a hydrophobic/oleophobic fluorinated acrylate polymer coating to create a repellent surface. The monomer was flash evaporated at about 100 Millitorr. The fabric was pretreated in a plasma field and within one second it was exposed to the monomer vapor for condensation while traveling at a speed of about 50 meters/minute. The condensed monomer layer was cured in-line by electron beam radiation within 100 milliseconds. A polymer coating thickness of about 0.1 μm resulted from the run, which was found to provide adequate repellency for water and oil with a surface energy of about 27 dyne/cm. The functionalized fabric repelled both water-based and oil-based fluids while substantially retaining the original permeability of the fabric. The coated materials showed high performance as electrostatic charged filter media. The same coating process with the same fluoro-acrylate monomer was repeated on nonwoven polyethylene, paper, fluoro-polymers, polyester fibers, nylon fibers, rayon fibers, wool fabrics, and cotton fabrics. Similar water/oil repellency results were obtained with all kinds of fabric materials where the functionalizing monomer was deposited in thicknesses ranging from 0.02 to 3.0 μm. In addition to water and oil repellency, the coated materials showed a lower coefficient of friction, which produced a silky feel in the coated fabrics. In a similar experiment at a higher speed (200 meter/minute), the functionalized coating was restricted to the exposed surface of the fabric material. The back side of the coated web retained its original properties. (It is noted that the option of selectively coating only one side of the web is another unique characteristic for the process of the invention.) As illustrated in FIG. 6 (left-center side), these coating formulations produced the desired repellent characteristics in these fabrics without loss oil repellency properties of the treated fabric remained substantially unaltered after 10 wash cycles. [0041]
    TABLE 2
    Durability of Water and Oil Repellent Fluoro-Polymer Coatings
    Water/Alcohol Oil
    Repellency Test* Repellency Test*
    10 Wash 10 Wash
    Fabrics Samples Un-washed cycles Un-washed cycles
    Cotton Uncoated 1 1 1 1
    Coated 6 4 5 3
    Poly- Uncoated 3 3 1 1
    ester Coated 6 5 6 4
    Nylon
    Uncoated 3 3 1 1
    Coated 6 5 6 4
  • EXAMPLE 2 Hydrophilic Coating
  • A melt-blown polypropylene nonwoven fabric was coated with a hydrophilic acrylate polymer film functionalized with hydroxyl, carboxyl, sulfonic, amino, amido and ether groups (in separate tests) to create a water absorbent surface. The monomer was flash evaporated at about 10 Millitorr. The fabric was pretreated in a plasma field and within one second it was exposed to the monomer vapor for condensation while traveling at a speed of about 30 meters/minute. The condensed monomer layer was cured in-line by electron beam radiation within 150 milliseconds. A polymer coating thickness of about 0.1 μm resulted from the run, which was found to provide adequate wettability in all cases by water with a surface energy of about 70-72 dyne/cm. The functionalized fabrics absorbed water while substantially retaining the original permeability of the fabrics. The coated materials showed high performance as water absorbent media. The same coating process with the same hydrophilic acrylate monomers was repeated on nonwoven polyethylene, fluoro-polymers, polyester fibers and fluoropolymer fabrics. Similar results were obtained with all kinds of fabric materials with monomer layers ranging from 0.1 to 3.0 μm. In a similar experiment at a higher speed (200 meter/minute), the functionalized coating was restricted to the exposed surface of the fabric material. The back side of the coated web kept its original properties. FIG. 6 illustrates water tests on the surface of a non-woven polypropylene filter medium used in the examples, before and after coating, as detailed above. Before coating, the material was hydrophobic, as seen at the bottom-right portion of the picture. After functionalization according to the invention, the material became clearly hydrophilic, as illustrated at the top-right portion of the picture by the water drop absorbed into the fabric. Thus, these coated substrates can be used advantageously for diapers, filters, battery separators and ion transport membranes. Table 3 below shows three water-strike tests for non-woven polypropylene coated with two hydrophilic acrylate-based formulations (Sigma 1033 and Sigma 1032 coatings). Filter paper, which is known to be highly absorbing, was used as the reference control material (because untreated diaper material—polypropylene—is known to be hydrophobic). [0042]
    TABLE 3
    Water strike test for non-woven polypropylene (NW PP).
    Time in seconds required for
    complete absorption of a
    ten-gram portion of DI water
    1st 2nd 3rd Average
    Material strike strike strike time
    Uncoated 89.36 64.36 65.92 73.21
    NW PP
    Filter paper 3.15 6.98 7.35 5.83
    control
    1033 coating on 4.71 6.29 5.99 5.66
    PP
    1032 2.7 6.77 7.05 5.51
    coating on PP
  • EXAMPLE 3 Hydrophobic/Oleophobic Colored Coating
  • The same experiment as in Example 1 was repeated with 3-5% organic dyes (e.g., disperse red) mixed in the fluorinated acrylate monomer. The coated substrates showed the same levels of water and oil repellency, measured at about 6 and 5 on the Dupont® Teflon® Repellency Test, respectively, with the color added to the coating. The intensity of the color can be controlled by monitoring either the amount of organic dye or the thickness of the coating. [0043]
  • EXAMPLE 4 Hydrophilic Colored Coating
  • The same experiment as in Example 2 was repeated with 3-5% organic dyes (e.g., Malachite green) mixed in the hydrophilic acrylate monomer. The coated substrates showed a colored surface with comparably high water absorption. [0044]
  • EXAMPLE 5 Hydrophobic/Oleophobic Biocide Coating
  • The same experiment as in Example 1 was repeated with 2-4% organic antibacterial additive (e.g., chlorinated aromatic compound) in the fluorinated acrylate monomer. The coated substrates showed water and oil repellency with antibacterial properties as indicated below. [0045]
    Results (Zone Size)
    Staphylococcus Klebsiella Pneumoniae
    Sample identification (13 mm) (13 mm)
    Control uncoated paper no inhibition to no inhibition to growth
    growth complete inhibition
    Both side Coated paper complete inhibition
  • EXAMPLE 6 Hydrophilic Biocide Coating
  • The same experiment as in Example 2 was repeated with 3-5% organic antibacterial additive (e.g., chlorinated aromatic compound) in the hydrophilic acrylate monomer. The coated substrates showed antibacterial properties and high water absorption. [0046]
  • EXAMPLE 7 Fire Retardant Coatings
  • The same experiments as in Example 1 and 2 were repeated with 5-20% brominated compound in the diacrylate monomer. The coated substrates showed fire resistance properties with hydrophobic/oleophobic and hydrophilic properties comparable to those of Examples 1 and 2. [0047]
  • EXAMPLE 8 Color Changing Sensing Coatings
  • The same experiments as in Example 1 and 2 were repeated with 5-20% of a pH indicator compound, such as phenol phthaleine, in the diacrylate monomer. The resulting coated substrates changed color reversibly with corresponding changes in the environment's pH. The same experiments were repeated using 5-30% heat-sensitive molecules, such as 4-pentyl-4-cyanobiphenyl, which produces a change in color from clear to grey when the temperature reaches about 50 degrees C. The coated materials changed color with changes in the temperature of the environment. [0048]
  • EXAMPLE 9 Flavored Coatings
  • The same experiments as in Example 1 and 2 were repeated with 5-20% artificial fruit-flavor compounds in the diacrylate monomer; for example, an ionone such as 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one is used to confer a strawberry. The coated substrates exhibited a corresponding emission of a fruity scent in addition to hydrophobic/oleophobic and hydrophilic properties comparable to those of Examples 1 and 2. [0049]
  • EXAMPLE 10 Wet Tensile Strength Coatings
  • The same experiments as in Example 1 and 2 were repeated at a slower rate (<100 fpm) to allow the monomer vapor to penetrate all the way through the fibers of paper material and coat the entire available surface of individual fibers (retaining the porosity if the material). The resulting coated paper exhibited a high wet tensile strength in addition to hydrophobic/oleophobic and hydrophilic properties comparable to those of Examples 1 and 2. [0050]
  • EXAMPLE 11 Chemical Resistant Coatings
  • The same experiments as in Example 1 and 2 were repeated with a monomer that contained 5-40% triacrylate monomer in order to increase cross-linking and the density of the coating, thereby increase it chemical resistance. The coated substrates showed that the addition of the triacrylate monomer increased the chemical resistance to organic solvents as well as acid and base solutions while retaining hydrophobic/oleophobic and hydrophilic properties comparable to those of Examples 1 and 2. [0051]
  • EXAMPLE 12 Metal Chelating Coatings
  • The same experiments as in Example 2 were repeated with 10-20% acrylated acetyl acetonate monomer in the diacrylate monomer. The coated substrates showed metal chelating properties by bonding to metal ions (e.g., Cu, Pb, Cr). Accordingly, they were tested successfully as filters for removing metal ions from water. [0052]
  • EXAMPLE 13 Proton Conductor Coatings
  • As in the previous examples, porous polypropylene and fluoropolymer films were coated with a sulfonated compound monomer and then cured with an electron beam. The coated substrates exhibited proton conductivity, thereby showing potential for use as a fuel-cell membrane. [0053]
  • EXAMPLE 14 Ion Conductor Coatings
  • As in the previous examples, porous polypropylene and fluoropolymer films were coated with a sulfonated compound that was co-deposited with metallic lithium to form lithium sulfonate and then cured with an electron beam. The coated substrates exhibited lithium-ion conductivity, thereby showing potential for use as a battery separator and electrolyte. [0054]
  • In addition to the foregoing examples, the ability to deposit a polymer layer followed by metallization in line, as illustrated in FIG. 5, offers some unique opportunities in the production of metallized fabrics and paper. A top thin polymer layer can provide abrasion and corrosion protection which is a basic requirement for most metallized layers. For example, we have shown that the washability of metallized fabrics can be prolonged significantly when coated with a vacuum deposited acrylate layer that has a thickness of about 1.0 μm. Such thin polymer layers have no practical effect on the fabric breathability and “comfort” properties. Similarly, metallized fabrics for heat reflecting applications can be protected with thin polymer layers that have low infrared absorption in order to minimize heat absorption upon exposure to high temperatures (low emissivity). Other functionalizing polymer properties include controlling the surface energy, which may be varied from high surface energy for improved adhesion and wettability of the metallized material to low surface energy for release applications and Teflon®-like performance. [0055]
  • As illustrated by the examples above, coating formulations have also been effectively functionalized with biocide compounds, such as chlorinated molecules. A small amount of biocide is evaporated simultaneously with the acrylate monomer and becomes trapped in the matrix of the radiation cured host polymer. Such coatings have been successfully deposited directly on fabric substrates or over other polymer, metal or ceramic films. Colored decorative coatings were similarly prepared and applied by synthesizing functionalized organic dyes formulated in a binder and applying them to white paper and non-woven webs. [0056]
  • This invention demonstrates that porous materials may be functionalized by monomer vacuum deposition to produce desired surface properties without significant loss of the original characteristics of the substrate. Thus, vacuum deposited polymer coatings on fabric and paper webs provide a real alternative to conventional solvent- and water-based coating processes. Highly functional coatings can be obtained that conformally coat the fibers of these materials with little or no effect on porosity and gas or liquid permeation. Coatings with submicron thickness can be used to replace liquid-based fluoro treatments and wax impregnation processes, which are facing environmental and recycleability challenges. The totally enclosed conditions of a vacuum chamber are environmentally friendly, permitting fluoro, chloro and other hazardous-monomer formulations to be processed safely. [0057]
  • FIGS. 7, 8 and [0058] 9 are flow charts illustrating the basic steps of the preferred embodiments of the invention for single, double and triple layer applications, respectively. Various changes in the details, steps and components that have been described may be made by those skilled in the art within the principles and scope of the invention herein illustrated and defined in the appended claims. For example, while the invention has been described mainly in terms of one-side coating, it is clear that the two sides of a sheet-type substrate may be coated separately or on line to produce different functionalities. For example, diaper material may be functionalized to improve hydrophilicity on one side and produce hydrophobicity on the opposite side, thereby producing a diaper that is highly absorbent in the interior and repellent in the exterior, as desirable for most uses.
  • Thus, while the present invention has been shown and described herein in what is believed to be the most practical and preferred embodiments, it is recognized that departures can be made therefrom within the scope of the invention, which is not to be limited to the details disclosed herein but is to be accorded the full scope of the claims so as to embrace any and all equivalent processes and products. [0059]

Claims (41)

We claim:
1. A process for functionalizing a porous substrate to impart a particular functionality to the substrate while retaining its permeability, comprising the following steps:
(a) flash evaporating a monomer having said functionality in a vacuum chamber to produce a vapor;
(b) condensing the vapor on the porous substrate to produce a film of said monomer on the porous substrate; and
(c) curing the film to produce a functionalized polymeric layer on the porous substrate;
wherein said condensing step is carried out under vapor-density and residence-time conditions that limit said polymeric layer to a maximum thickness of about 3.0 μm.
2. The process of claim 1, further including the step of pretreating said substrate in a plasma field within about one second prior to the condensation step.
3. The process of claim 1, further including the step of vacuum depositing an inorganic layer over said polymeric layer.
4. The process of claim 3, wherein said inorganic layer is selected from the group consisting of metals and ceramics.
5. The process of claim 2, further including the step of vacuum depositing an inorganic layer over said polymeric layer.
6. The process of claim 5, wherein said inorganic layer is selected from the group consisting of metals and ceramics.
7. The process of claim 3, further including the steps of flash evaporating and condensing a second film of monomer on said inorganic layer, and the further step of curing the second film to produce a second polymeric layer on the inorganic layer.
8. The process of claim 4, further including the steps of flash evaporating and condensing a second film of monomer on said inorganic layer, and the further step of curing the second film to produce a second polymeric layer on the inorganic layer.
9. The process of claim 5, further including the steps of flash evaporating and condensing a second film of monomer on said inorganic layer, and the further step of curing the second film to produce a second polymeric layer on the inorganic layer.
10. The process of claim 6, further including the steps of flash evaporating and condensing a second film of monomer on said inorganic layer, and the step of curing the second film to produce a second polymeric layer on the inorganic layer.
11. The process of claim 1, wherein said porous substrate comprises a porous material selected from the group consisting of polypropylene, polyethylene, fluoro-polymers, polyester, nylon, rayon, paper, wool, cotton, glass fibers, carbon fibers, cellulose-based fibers, and metals; and said monomer is a fluorinated monomer to provide a water and oil repellency functionality.
12. The process of claim 11, wherein said monomer comprises a color additive.
13. The process of claim 11, wherein said monomer comprises a biocide additive.
14. The process of claim 11, wherein said monomer comprises a brominated monomer to provide a fire retardant functionality.
15. The process of claim 1, wherein said porous substrate comprises a porous material selected from the group consisting of polypropylene, polyethylene, polyester, nylon, rayon, paper, cotton, wool, glass fibers, carbon fibers, cellulose-based fibers, and metals; and said monomer is functionalized with a functional group selected from the group of hydroxyl, carboxyl, sulfonic, amino, amido, or ether to provide a hydrophilic functionality.
16. The process of claim 15, wherein said monomer comprises a color additive.
17. The process of claim 15, wherein said monomer comprises an biocide additive.
18. The process of claim 15, wherein said monomer comprises a brominated material to provide a fire-retardant functionality.
19. The process of claim 15, wherein said monomer comprises an acrylated acetyl acetonate monomer to provide a metal-chelating functionality.
20. The process of claim 1, wherein said porous substrate comprises a porous material selected from the group consisting of polypropylene, polyethylene, fluoro-polymers, polyester, nylon, rayon, paper, cotton, wool, glass fibers, carbon fibers, cellulose-based fibers and metals; and said monomer includes a sulfonic acid group to provide a proton-conductivity functionality.
21. The process of claim 1, wherein said porous substrate comprises a porous material selected from the group consisting of polypropylene, polyethylene, fluoro-polymers, polyester, nylon, rayon, paper, wool, cotton, glass fibers, carbon fibers, cellulose based fibers, and metals; said monomer includes a sulfonic acid group; and further comprising the step of co-depositing metallic lithium over said monomer prior to the curing step to provide a polymer electrolyte with ion-conductivity functionality.
22. The process of claim 3, wherein said porous substrate comprises a porous material selected from the group consisting of polypropylene, polyethylene, fluoro-polymers, polyester, nylon, rayon, paper, wool, cotton, glass fibers, carbon fibers, cellulose-based fibers and metals; and said metal layer provides a low-emissivity functionality.
23. The process of claim 7, wherein said porous substrate comprises a porous material selected from the group consisting of polypropylene, polyethylene, fluoro-polymers, polyester, nylon, rayon, paper, wool, cotton, glass fibers, carbon fibers, cellulose based fibers and metals; and said metal layer provides a low-emissivity functionality.
24. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a hydrophilic and oleophilic functionality.
25. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a hydrophilic electrostatic dissipation functionality.
26. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a hydrophobic and oleophobic functionality.
27. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a color.
28. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a biocide functionality.
29. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a fire-resistant functionality.
30. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a metal-chelating functionality.
31. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a proton-conductivity functionality.
32. A porous substrate produced by the process of claim 1, wherein said monomer incorporates an ion-conductivity functionality.
33. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a pH-sensing functionality.
34. A porous substrate produced by the process of claim 1, wherein said monomer incorporates a scent-emission functionality.
35. A porous substrate with increased wet tensile strength produced by the process of claim 1.
36. A porous substrate with increased chemical resistance produced by the process of claim 1.
37. A porous substrate with increased abrasion resistance produced by the process of claim 1.
38. A porous substrate with a reduced friction coefficient produced by the process of claim 1.
39. A porous substrate with two sides and corresponding opposite functionalities produced by the process of claim 1.
40. A porous substrate produced by the process of claim 3, wherein said inorganic layer is metallic to provide electrical conductivity, low-emissivity and electrostatic dissipation functionalities.
41. A porous substrate produced by the process of claim 5, wherein said inorganic layer is metallic to provide electrical conductivity, low-emissivity and electrostatic dissipation functionalities.
US10830608 2002-06-26 2004-04-23 Functionalization of porous materials by vacuum deposition of polymers Active US7157117B2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US39186402 true 2002-06-26 2002-06-26
US46571903 true 2003-04-25 2003-04-25
US10465399 US20040028931A1 (en) 2002-06-26 2003-06-19 Coated sheet materials and packages made therewith
US10830608 US7157117B2 (en) 2002-06-26 2004-04-23 Functionalization of porous materials by vacuum deposition of polymers

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10830608 US7157117B2 (en) 2002-06-26 2004-04-23 Functionalization of porous materials by vacuum deposition of polymers
US11589564 US20070048512A1 (en) 2002-06-26 2006-10-30 Functionalization of porous materials by vacuum deposition of polymers
US12250083 US20090041936A1 (en) 2002-06-26 2008-10-13 Composite reflective barrier

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US10465399 Continuation-In-Part US20040028931A1 (en) 2002-06-26 2003-06-19 Coated sheet materials and packages made therewith

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11589564 Division US20070048512A1 (en) 2002-06-26 2006-10-30 Functionalization of porous materials by vacuum deposition of polymers

Publications (3)

Publication Number Publication Date
US20040213918A1 true true US20040213918A1 (en) 2004-10-28
US20060257642A9 true US20060257642A9 (en) 2006-11-16
US7157117B2 US7157117B2 (en) 2007-01-02

Family

ID=33303278

Family Applications (2)

Application Number Title Priority Date Filing Date
US10830608 Active US7157117B2 (en) 2002-06-26 2004-04-23 Functionalization of porous materials by vacuum deposition of polymers
US11589564 Abandoned US20070048512A1 (en) 2002-06-26 2006-10-30 Functionalization of porous materials by vacuum deposition of polymers

Family Applications After (1)

Application Number Title Priority Date Filing Date
US11589564 Abandoned US20070048512A1 (en) 2002-06-26 2006-10-30 Functionalization of porous materials by vacuum deposition of polymers

Country Status (1)

Country Link
US (2) US7157117B2 (en)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040028931A1 (en) * 2002-06-26 2004-02-12 Bletsos Ioannis V. Coated sheet materials and packages made therewith
US20060040091A1 (en) * 2004-08-23 2006-02-23 Bletsos Ioannis V Breathable low-emissivity metalized sheets
US20060240312A1 (en) * 2005-04-25 2006-10-26 Tao Xie Diffusion media, fuel cells, and fuel cell powered systems
WO2006127946A2 (en) * 2005-05-25 2006-11-30 Gore Enterprise Holdings, Inc. Multi-functional coatings on microporous substrates
WO2006130122A1 (en) * 2005-06-02 2006-12-07 Institut 'jozef Stefan' Method and device for local functionalization of polymer materials
US20070037465A1 (en) * 2005-08-11 2007-02-15 Michel Nutz Porous metallized sheets coated with an inorganic layer having low emissivity and high moisture vapor permeability
US20070125700A1 (en) * 2005-12-05 2007-06-07 Jiang Ding Nanoweb composite material and gelling method for preparing same
US20070125703A1 (en) * 2005-12-05 2007-06-07 Chapman John S Method for providing resistance to biofouling in a porous support
US20070272606A1 (en) * 2006-05-25 2007-11-29 Freese Donald T Multi-functional coatings on microporous substrates
US20080107822A1 (en) * 2006-11-02 2008-05-08 Apjet, Inc. Treatment of fibrous materials using atmospheric pressure plasma polymerization
US20080113573A1 (en) * 2006-11-13 2008-05-15 Erick Jose Acosta Partially fluorinated amino acid derivatives as gelling and surface active agents
US20090047498A1 (en) * 2007-08-13 2009-02-19 E. I. Dupont De Nemours And Company Method for providing nanoweb composite material
US20090075033A1 (en) * 2007-09-14 2009-03-19 Theresa Ann Weston Building wrap for use in external wall assemblies having wet-applied facades
EP2085497A1 (en) * 2008-01-31 2009-08-05 FUJIFILM Corporation Method for producing functional film
EP2085496A1 (en) * 2008-01-31 2009-08-05 FUJIFILM Corporation Method for producing functional film
US20090200948A1 (en) * 2008-02-11 2009-08-13 Apjet, Inc. Large area, atmospheric pressure plasma for downstream processing
EP2298550A1 (en) * 2008-07-08 2011-03-23 Obun Printing Company, Inc. Writing paper and method for manufacturing writing paper
WO2011037798A1 (en) * 2009-09-22 2011-03-31 3M Innovative Properties Company Method of applying atomic layer deposition coatings onto porous non-ceramic substrates
WO2012073093A1 (en) * 2010-11-30 2012-06-07 Zhik Pty Ltd Manufacture of garment materials
US20130171335A1 (en) * 2011-12-28 2013-07-04 Yong-Suk Lee Thin film depositing apparatus and the thin film depositing method using the same
US20130216774A1 (en) * 2012-02-16 2013-08-22 Brian John Conolly Closed Cell Materials
US8741393B2 (en) 2011-12-28 2014-06-03 E I Du Pont De Nemours And Company Method for producing metalized fibrous composite sheet with olefin coating
US20150305421A1 (en) * 2012-02-16 2015-10-29 Brian John Conolly Heat Reflecting Composites with Knitted Insulation
US20160109435A1 (en) * 2014-10-16 2016-04-21 National Tsing Hua University Fabric-base biochemical detecting device and the fabricating method thereof
US9839873B2 (en) * 2011-08-15 2017-12-12 E I Du Pont De Nemours And Company Breathable product for protective mass transportation and cold chain applications
US10160184B2 (en) 2013-06-03 2018-12-25 Xefco Pty Ltd Insulated radiant barriers in apparel

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5579985B2 (en) 2005-04-01 2014-08-27 バカイ・テクノロジーズ・インコーポレーテッド Soundproof nonwoven material and manufacturing method thereof
US20080022645A1 (en) * 2006-01-18 2008-01-31 Skirius Stephen A Tacky allergen trap and filter medium, and method for containing allergens
US7837009B2 (en) 2005-04-01 2010-11-23 Buckeye Technologies Inc. Nonwoven material for acoustic insulation, and process for manufacture
US8058188B2 (en) * 2005-04-13 2011-11-15 Albany International Corp Thermally sprayed protective coating for industrial and engineered fabrics
US20090019825A1 (en) * 2007-07-17 2009-01-22 Skirius Stephen A Tacky allergen trap and filter medium, and method for containing allergens
WO2007084953A3 (en) * 2006-01-18 2009-04-09 Brian Boehmer Tacky allergen trap and filter medium
CA2656493C (en) * 2006-06-30 2015-06-23 James Richard Gross Fire retardant nonwoven material and process for manufacture
JP2011502236A (en) * 2007-10-31 2011-01-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Vibration absorber
US20090142488A1 (en) * 2007-11-29 2009-06-04 Willard Ashton Cutler Passivation of porous ceramic articles
US20090156079A1 (en) 2007-12-14 2009-06-18 Kimberly-Clark Worldwide, Inc. Antistatic breathable nonwoven laminate having improved barrier properties
US20090173570A1 (en) * 2007-12-20 2009-07-09 Levit Natalia V Acoustically absorbent ceiling tile having barrier facing with diffuse reflectance
US20090173569A1 (en) * 2007-12-20 2009-07-09 E. I. Du Pont De Nemours And Company Acoustic absorber with barrier facing
US20100159195A1 (en) * 2008-12-24 2010-06-24 Quincy Iii Roger B High repellency materials via nanotopography and post treatment
CN102549210A (en) 2009-09-28 2012-07-04 纳幕尔杜邦公司 Electrostatic charge dissipative materials by vacuum deposition of polymers
WO2011084806A1 (en) 2010-01-06 2011-07-14 Dow Global Technologies Inc. Moisture resistant photovoltaic devices with elastomeric, polysiloxane protection layer
KR101007775B1 (en) 2010-03-09 2011-01-12 김재천 Method of hydrophilic thin layer for mirror using hydrophilic polymer compound
CA2802859A1 (en) * 2010-06-14 2011-12-22 The Regents Of The University Of Michigan Superhydrophilic and oleophobic porous materials and methods for making and using the same
US8551895B2 (en) 2010-12-22 2013-10-08 Kimberly-Clark Worldwide, Inc. Nonwoven webs having improved barrier properties
US8840970B2 (en) 2011-01-16 2014-09-23 Sigma Laboratories Of Arizona, Llc Self-assembled functional layers in multilayer structures
US20130004690A1 (en) * 2011-06-29 2013-01-03 Mikhael Michael G Hydrophilic expanded fluoropolymer composite and method of making same
WO2013009684A1 (en) * 2011-07-08 2013-01-17 The University Of Akron Carbon nanotube-based robust steamphobic surfaces
US9249313B2 (en) 2011-09-21 2016-02-02 The United States Of America As Represented By The Secretary Of The Air Force Synthesis of functional fluorinated polyhedral oligomeric silsesquioxane (F-POSS)
WO2013173722A3 (en) 2012-05-17 2014-01-23 The Regents Of The University Of Michigan Devices and methods for electric field driven on-demand separation of liquid-liquid mixtures
US9002041B2 (en) * 2013-05-14 2015-04-07 Logitech Europe S.A. Method and apparatus for improved acoustic transparency
US9474994B2 (en) 2013-06-17 2016-10-25 Donaldson Company, Inc. Filter media and elements
US9394408B2 (en) 2013-08-29 2016-07-19 The United States Of America As Represented By The Secretary Of The Air Force Controlled polymerization of functional fluorinated polyhedral oligomeric silsesquioxane monomers
CA2927003A1 (en) 2013-10-09 2015-04-16 The Regents Of The University Of Michigan Apparatuses and methods for energy efficient separations including refining of fuel products
US9988536B2 (en) 2013-11-05 2018-06-05 E I Du Pont De Nemours And Company Compositions for surface treatments
US20150329692A1 (en) * 2014-05-13 2015-11-19 Celgard, Llc Functionalized porous membranes and methods of manufacture and use
US9968963B2 (en) * 2015-08-31 2018-05-15 Sigma Laboratories Of Arizona, Llc Functional coating

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6218004B1 (en) * 1995-04-06 2001-04-17 David G. Shaw Acrylate polymer coated sheet materials and method of production thereof
US6497780B1 (en) * 1999-06-09 2002-12-24 Steven A. Carlson Methods of preparing a microporous article
US6599559B1 (en) * 2000-04-03 2003-07-29 Bausch & Lomb Incorporated Renewable surface treatment of silicone medical devices with reactive hydrophilic polymers
US20040028931A1 (en) * 2002-06-26 2004-02-12 Bletsos Ioannis V. Coated sheet materials and packages made therewith

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6218004B1 (en) * 1995-04-06 2001-04-17 David G. Shaw Acrylate polymer coated sheet materials and method of production thereof
US6497780B1 (en) * 1999-06-09 2002-12-24 Steven A. Carlson Methods of preparing a microporous article
US6599559B1 (en) * 2000-04-03 2003-07-29 Bausch & Lomb Incorporated Renewable surface treatment of silicone medical devices with reactive hydrophilic polymers
US20040028931A1 (en) * 2002-06-26 2004-02-12 Bletsos Ioannis V. Coated sheet materials and packages made therewith

Cited By (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7491433B2 (en) 2002-06-26 2009-02-17 E.I. Du Pont De Nemours And Company Coated sheet materials and packages made therewith
US20040028931A1 (en) * 2002-06-26 2004-02-12 Bletsos Ioannis V. Coated sheet materials and packages made therewith
US20060078700A1 (en) * 2002-06-26 2006-04-13 Bletsos Ioannis V Coated sheet materials and packages made therewith
US7805907B2 (en) * 2004-08-23 2010-10-05 E.I. Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US20080060302A1 (en) * 2004-08-23 2008-03-13 E. I. Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US20080057292A1 (en) * 2004-08-23 2008-03-06 E. I. Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US8431209B2 (en) 2004-08-23 2013-04-30 E I Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US20060040091A1 (en) * 2004-08-23 2006-02-23 Bletsos Ioannis V Breathable low-emissivity metalized sheets
US8497010B2 (en) 2004-08-23 2013-07-30 E I Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US20080187740A1 (en) * 2004-08-23 2008-08-07 E. I. Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US9515328B2 (en) 2005-04-25 2016-12-06 GM Global Technology Operations LLC Diffusion media, fuel cells, and fuel cell powered systems
US20060240312A1 (en) * 2005-04-25 2006-10-26 Tao Xie Diffusion media, fuel cells, and fuel cell powered systems
US20110070524A1 (en) * 2005-04-25 2011-03-24 Gm Global Technology Operations, Inc. Diffusion Media, Fuel Cells, and Fuel Cell Powered Systems
WO2006127946A2 (en) * 2005-05-25 2006-11-30 Gore Enterprise Holdings, Inc. Multi-functional coatings on microporous substrates
WO2006127946A3 (en) * 2005-05-25 2007-03-01 Gore Enterprise Holdings Inc Multi-functional coatings on microporous substrates
WO2006130122A1 (en) * 2005-06-02 2006-12-07 Institut 'jozef Stefan' Method and device for local functionalization of polymer materials
US20100047532A1 (en) * 2005-06-02 2010-02-25 Miran Mozetic Method and device for local functionalization of polymer materials
US8247039B2 (en) 2005-06-02 2012-08-21 Institut “Jo{hacek over (z)}ef Stefan” Method and device for local functionalization of polymer materials
US20070037465A1 (en) * 2005-08-11 2007-02-15 Michel Nutz Porous metallized sheets coated with an inorganic layer having low emissivity and high moisture vapor permeability
US8025985B2 (en) 2005-08-11 2011-09-27 E. I. Du Pont De Nemours And Company Porous metallized sheets coated with an inorganic layer having low emissivity and high moisture vapor permeability
US8268395B2 (en) 2005-12-05 2012-09-18 E. I. Du Pont De Nemours And Company Method for providing resistance to biofouling in a porous support
US20070125700A1 (en) * 2005-12-05 2007-06-07 Jiang Ding Nanoweb composite material and gelling method for preparing same
US20070125703A1 (en) * 2005-12-05 2007-06-07 Chapman John S Method for providing resistance to biofouling in a porous support
US20070272606A1 (en) * 2006-05-25 2007-11-29 Freese Donald T Multi-functional coatings on microporous substrates
WO2008057759A3 (en) * 2006-11-02 2008-06-26 Apjet Inc Treatment of fibrous materials using atmospheric pressure plasma polymerization
US9157191B2 (en) 2006-11-02 2015-10-13 Apjet, Inc. Treatment of fibrous materials using atmospheric pressure plasma polymerization
US20080107822A1 (en) * 2006-11-02 2008-05-08 Apjet, Inc. Treatment of fibrous materials using atmospheric pressure plasma polymerization
US20080113573A1 (en) * 2006-11-13 2008-05-15 Erick Jose Acosta Partially fluorinated amino acid derivatives as gelling and surface active agents
US7473658B2 (en) 2006-11-13 2009-01-06 E. I. Du Pont Nemours And Company Partially fluorinated amino acid derivatives as gelling and surface active agents
US20090047498A1 (en) * 2007-08-13 2009-02-19 E. I. Dupont De Nemours And Company Method for providing nanoweb composite material
US20090075033A1 (en) * 2007-09-14 2009-03-19 Theresa Ann Weston Building wrap for use in external wall assemblies having wet-applied facades
EP2085497A1 (en) * 2008-01-31 2009-08-05 FUJIFILM Corporation Method for producing functional film
US8980374B2 (en) 2008-01-31 2015-03-17 Fujifilm Corporation Method for producing functional film
US20090196997A1 (en) * 2008-01-31 2009-08-06 Fujifilm Corporation Method for producing functional film
US8133533B2 (en) 2008-01-31 2012-03-13 Fujifilm Corporation Method for producing functional film
EP2085496A1 (en) * 2008-01-31 2009-08-05 FUJIFILM Corporation Method for producing functional film
US20090196998A1 (en) * 2008-01-31 2009-08-06 Fujifilm Corporation Method for producing functional film
US8361276B2 (en) 2008-02-11 2013-01-29 Apjet, Inc. Large area, atmospheric pressure plasma for downstream processing
US20090200948A1 (en) * 2008-02-11 2009-08-13 Apjet, Inc. Large area, atmospheric pressure plasma for downstream processing
US8800485B2 (en) 2008-02-11 2014-08-12 Apjet, Inc. Large area, atmospheric pressure plasma for downstream processing
EP2298550A4 (en) * 2008-07-08 2013-01-09 Obun Printing Company Inc Writing paper and method for manufacturing writing paper
EP2298550A1 (en) * 2008-07-08 2011-03-23 Obun Printing Company, Inc. Writing paper and method for manufacturing writing paper
US20110117330A1 (en) * 2008-07-08 2011-05-19 Obun Printing Company, Inc. Writing paper and method for manufacturing writing paper
CN102575346A (en) * 2009-09-22 2012-07-11 3M创新有限公司 Method of applying atomic layer deposition coatings onto porous non-ceramic substrates
CN102782179B (en) * 2009-09-22 2015-11-25 3M创新有限公司 An article comprising a porous substrate having a conformal layer thereon
WO2011037798A1 (en) * 2009-09-22 2011-03-31 3M Innovative Properties Company Method of applying atomic layer deposition coatings onto porous non-ceramic substrates
US8859040B2 (en) 2009-09-22 2014-10-14 3M Innovative Properties Company Method of applying atomic layer deposition coatings onto porous non-ceramic substrates
CN102782179A (en) * 2009-09-22 2012-11-14 3M创新有限公司 Articles including a porous substrate having a conformal layer thereon
WO2012073093A1 (en) * 2010-11-30 2012-06-07 Zhik Pty Ltd Manufacture of garment materials
US9839873B2 (en) * 2011-08-15 2017-12-12 E I Du Pont De Nemours And Company Breathable product for protective mass transportation and cold chain applications
US8741393B2 (en) 2011-12-28 2014-06-03 E I Du Pont De Nemours And Company Method for producing metalized fibrous composite sheet with olefin coating
US20130171335A1 (en) * 2011-12-28 2013-07-04 Yong-Suk Lee Thin film depositing apparatus and the thin film depositing method using the same
US20150305421A1 (en) * 2012-02-16 2015-10-29 Brian John Conolly Heat Reflecting Composites with Knitted Insulation
US8993089B2 (en) * 2012-02-16 2015-03-31 Zhik Pty Ltd Closed cell materials
US20130216774A1 (en) * 2012-02-16 2013-08-22 Brian John Conolly Closed Cell Materials
US10160184B2 (en) 2013-06-03 2018-12-25 Xefco Pty Ltd Insulated radiant barriers in apparel
US20160109435A1 (en) * 2014-10-16 2016-04-21 National Tsing Hua University Fabric-base biochemical detecting device and the fabricating method thereof
CN105527282A (en) * 2014-10-16 2016-04-27 郑兆珉 Fabric-base biochemical detecting device and the fabricating method thereof

Also Published As

Publication number Publication date Type
US20070048512A1 (en) 2007-03-01 application
US20060257642A9 (en) 2006-11-16 application
US7157117B2 (en) 2007-01-02 grant

Similar Documents

Publication Publication Date Title
US5364678A (en) Windproof and water resistant composite fabric with barrier layer
US6497787B1 (en) Process of manufacturing a wet-laid veil
US6410084B1 (en) Porous membrane structure and method
Mahltig Nanosols and textiles
US4507342A (en) Polymers adherent to polyolefins
US4610915A (en) Two-ply nonwoven fabric laminate
US3326713A (en) Breathable and waterproof coated fabric and process of making same
US5753568A (en) Moisture-permeable, waterproof fabric and its production process
US4288499A (en) Polymers adherent to polyolefins
US4265962A (en) Low penetration coating fabric
Morent et al. Non-thermal plasma treatment of textiles
US20050087491A1 (en) Hybrid membrane, method for producing the same and use of said membrane
US20070009723A1 (en) Flame-retardant sheet and formed article therefrom
US4460643A (en) Nonwoven fibrous backing for vinyl wallcover
US4816124A (en) Metal-coated fibrous objects
US4278435A (en) Process for the partial metallization of textile structures
Song et al. Approaching super-hydrophobicity from cellulosic materials: A Review
US5849395A (en) Industrial fabric
EP0177364A2 (en) Process for preparation of water-proof sheets
US2552910A (en) Coated glass fibers and method of making same
US3646749A (en) Machine-washable metallized fibrous article and method of making same
US6723378B2 (en) Fibers and fabrics with insulating, water-proofing, and flame-resistant properties
US4696830A (en) Process for preparation of water-proof sheets
US20070037465A1 (en) Porous metallized sheets coated with an inorganic layer having low emissivity and high moisture vapor permeability
US20070166528A1 (en) Process for forming a durable low emissivity moisture vapor permeable metallized sheet including a protective metal oxide layer

Legal Events

Date Code Title Description
AS Assignment

Owner name: SIGMA LABORATORIES OF ARIZONA, INC., ARIZONA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MIKHAEL, MICHAEL G.;YIALIZIS, ANGELO;REEL/FRAME:015258/0959;SIGNING DATES FROM 20040408 TO 20040412

Owner name: SIGMA LABORATORIES OF ARIZONA, INC., ARIZONA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MIKHAEL, MICHAEL G.;YIALIZIS, ANGELO;SIGNING DATES FROM 20040408 TO 20040412;REEL/FRAME:015258/0959

AS Assignment

Owner name: SIGMA LABORATORIES OF ARIZONA, LLC, ARIZONA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SIGMA LABORATORIES OF ARIZONA, INC.;REEL/FRAME:018239/0857

Effective date: 20060717

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

MAFP

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553)

Year of fee payment: 12