WO2003051498A1 - Plasma treatment of porous materials - Google Patents
Plasma treatment of porous materials Download PDFInfo
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- WO2003051498A1 WO2003051498A1 PCT/US2002/032570 US0232570W WO03051498A1 WO 2003051498 A1 WO2003051498 A1 WO 2003051498A1 US 0232570 W US0232570 W US 0232570W WO 03051498 A1 WO03051498 A1 WO 03051498A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
- C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical 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
- D06M10/02—Physical 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
- D06M10/025—Corona discharge or low temperature plasma
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical 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
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical 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
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical 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
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical 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
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
- D06M10/10—Macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0092—Other properties hydrophilic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/755—Membranes, diaphragms
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249961—With gradual property change within a component
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
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- Y10T428/249978—Voids specified as micro
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249986—Void-containing component contains also a solid fiber or solid particle
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- Y—GENERAL 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
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- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/24999—Inorganic
Definitions
- This invention relates to using a plasma treatment method to change the hydrophilicity of porous articles, and the resulting articles.
- Porous articles have many uses. However, in some instances, a porous article does not have a hydrophilicity suitable for its desired use. For example, porous synthetic membranes desirable for filtering aqueous liquids are often hydrophobic.
- the hydrophilicity of an article can be changed by chemical or physical reactions that coat the article with, or otherwise attach onto the article, a material having a hydrophilicity suitable for the article's intended use. But even when this type of treatment can be done, it can be difficult to effectively treat the pore interiors of the articles.
- One aspect of the present invention features a plasma treatment method for changing the hydrophilicity of porous articles, both on the surface and in the pores such that the bulk wetting properties of the article are altered. It also features the resulting articles.
- One aspect of the invention features a method of modifying the hydrophilicity of a porous article comprising: providing a reaction chamber having a capacitively- coupled system comprising at least one grounded electrode and at least one electrode powered by an RF source; generating a plasma in the chamber thereby causing an ion sheath to form around at least one of the electrodes; locating a porous article in the ion sheath; and allowing reactive species from the plasma to react with the article surface and pore interiors whereby the hydrophilicity of the article is changed such that the bulk wetting properties of the article are improved.
- the treatment of the porous article may be continuous, h many cases, the article pore sizes are smaller than the mean free path of any species in the plasma.
- the ion sheath in which the article is placed is most often proximate the powered electrode.
- the porous articles may be foams, nonwoven materials, woven materials, membranes, frits, textiles, cloths, and microporous articles.
- the article may be treated on one or both sides, and may be post-treated with an oxygen plasma. Shadow masks may be used to create patterned or gradient treatment areas.
- the plasma may comprises materials such as carbon, hydrogen, silicon, nitrogen, sulfur, and oxygen.
- the reactor may comprise parallel plate electrodes or a drum electrode.
- Another aspect of the invention features an article comprising a microporous membrane having a pore size with a" lower limit of about 0.05 micrometers and an upper limit of about 1.5 micrometers, the membrane having on its surface and in its pores, a plasma-deposited composition that improves the bulk wetting properties of the article.
- Other aspects of the invention include an article comprising (1) a porous article having two major surfaces wherein one major surface has a hydrophilic plasma- deposited composition that improves the bulk wetting properties of the article, and the other major surface is hydrophobic; and (2) a porous article having a patterned plasma- deposited composition.
- “bulk wetting property” means the propensity of an article to absorb and soak up water
- microporous membrane means a membrane having pore sizes with a lower limit of about 0.05 ⁇ m and an upper limit of about 1.5 ⁇ m;
- plasma treatment means thin film deposition, surface modification, and any other plasma-induced chemical or physical reaction that can change the hydrophilicity of an article
- porous article means an article having open tortuous pathways from its surface to its interior.
- Another advantage of at least one embodiment of the invention is that it provides a durable hydrophilic treatment through the bulk of porous articles, including microporous membranes.
- Fig. 1 depicts the cross-section of a cylindrical parallel plate plasma apparatus for performing the plasma-treatment of the present invention.
- Fig. 2 depicts a single-drum apparatus for performing the plasma-treatment of the present invention.
- Fig. 3 shows infrared spectra of (a) untreated porous Sample CE3, (b) Sample 7-B and (c) Sample 7-B after it was washed with water.
- Fig. 4 is a digital image of scanning electron microscopic (SEM) pictures of (a) Example CE3 and (b) Example 7B.
- Fig. 5 is a digital image of the depth profile obtained by secondary ion mass spectrometry analysis (SIMS) for Sample 7-A (10 seconds exposure time of 2 nd plasma) and Sample 7-B (30 seconds exposure time of 2 nd plasma), respectively.
- SIMS secondary ion mass spectrometry analysis
- Fig. 6 is a digital image of a selectively treated porous article stained with the dye of (a) Sample 8A having treated regions with diameters of 0.75 cm and (b) Sample 8B having treated regions with diameters of 0.2 cm.
- the present invention provides a plasma treatment method to modify the hydrophilicity of a porous article.
- the degree of hydrophilicity of the resulting article can range from strong to weak, depending on the type and amount of treatment.
- the method involves providing a reaction chamber having a capacitively- coupled electrode system wherein an ion sheath is formed around at least one electrode when a plasma is generated in the system.
- the ion sheath is an area around an electrode in which ion bombardment is prevalent.
- the porous article to be treated is placed within the ion sheath.
- the method of the invention is especially effective for articles with small pores because the ion sheath can force chemical species from the plasma into small pores of the articles being treated. This results in a change in the hydrophilicity of the pore interiors, which alters the bulk wetting properties of the article. It was not expected that plasma treatment could be achieved within small pores having tortuous paths, especially in cases where the pores are smaller than the mean free path of any species in the plasma.
- the mean free path (MFP) for a particular species is the average distance traveled by a species before it collides with another species.
- the MFP depends in part on pressure because the proximity of species influences the collision frequency. For example, at 0.13 Pa (1 mTorr) and room temperature, the mean free path of an argon atom is 80 mm. Brian Chapman, Glow Discharge Processes, 153 (John Wiley & Sons, New York 1980. Most other gases, including those used in the present invention, are within three times (i.e. 26-240 mm) of this value at this pressure, hi the range of pressures useful for plasma treatment, the mean free path of argon varies from 80 mm to 0.08 mm (or 80 microns) with changes in the pressure. Other gases would have similar variations.
- the pore size is smaller than the mean free path of the species in the plasma (i.e., smaller than about 20 microns)
- the free radical species generated in the plasma will collide with the pore walls near the pore opening.
- the free radicals will react with molecules in the pore walls near the pore opening rather than traveling into the depths of the pores. Therefore, one would not expect the plasma treatment to penetrate into the depths of the pores, especially when the pores have tortuous paths.
- Porous articles suitable for use in the present invention include foams, nonwoven materials, woven materials, membranes, frits, textiles, and microporous articles. These articles may have pore sizes of about 0.05 micrometers or greater. Particularly suitable articles are microporous films prepared by thermally-induced phase separation (TIPS) methods such as those described in U.S. Patent Nos. 4,539,256 (Shipman), 4,726,989; 5,120,594 (Mrozinski); and 5,260,360 (Mrozinski et al.) which describe such films containing a multiplicity of spaced, randomly dispersed, equiaxed, nonuniform shaped particles of a thermoplastic polymer. These films typically have pore sizes with a lower limit of about 0.05 micrometers and an upper limit of about 1.5 micrometers.
- TIPS thermally-induced phase separation
- Suitable polymers for the above articles include polyolefins such as, e.g., polypropylene, polyethylene, poly-(4-methyl-l-pentene), and combinations thereof, halogenated vinylpolymers (e.g., polyvinyl chloride), polystyrene, polycarbonates, polyesters, polyamides, and combinations thereof.
- the nonwovens can be formed by a variety of methods, including but not limited to, carding, use of a rando-webber, spunbonding, hydrolacing, or blown microfibers.
- the textiles and cloths can be formed as nonwovens or as knit or woven materials.
- the textiles and cloths preferably have a basis weight in the range of about 10 to 500 grams per square meter more preferably about 15 to 200 grams per square meter.
- Porous frits synthesized from polymers, metals, glasses and ceramics are available commercially in various pore sizes. The pore size typically varies between 1 and 250 microns and the frits may have a void volume of between 20 and 80%.
- Typical applications of frits include filtration, support media for membrane cartridges, solvent filters, diffusers, fluidization supports, bio- barriers, nibs for writing instruments, chromatographic support media, catalysis support media, etc.
- the articles can be any shape, e.g., rods, cylinders, etc., as long as they can be placed within an ion sheath that surrounds an electrode. Typically the articles will be sheet-like with two major parallel surfaces.
- the articles may be discrete articles or may be continuous sheets of material. They may have any level of hydrophobicity or hydrophilicity before they are treated. Apparatus
- An apparatus suitable for the present invention provides a reaction chamber having a capacitively-coupled system with at least one electrode powered by an RF source and at least one grounded electrode.
- a suitable reaction chamber is evacuable and is capable of maintaining conditions that produce plasma treatment. That is, the chamber provides an environment which allows for the control of, among other things, pressure, the flow of various inert and reactive gases, voltage supplied to the powered electrode, strength of the electric field across the ion sheath, formation of a plasma containing reactive species, intensity of ion bombardment, and rate of deposition of a film from the reactive species.
- Aluminum is a preferred chamber material because it has a low sputter yield, which means that very little contamination occurs from the chamber surfaces.
- other suitable materials such as graphite, copper, glass or stainless steel, may be used.
- the electrode system may be symmetric or asymmetric.
- asymmetric electrodes are preferable.
- Preferred electrode surface area ratios between grounded and powered electrodes for an asymmetric system are from 2:1 to 4:1, and more preferably from 3 : 1 to 4: 1.
- the ion sheath on the smaller powered electrode will increase as the ratio increases, but beyond a ratio of 4:1 little additional benefit is achieved. It is generally preferred that the powered electrode be the smaller because DC bias on a smaller grounded electrode would be shunted to ground.
- the powered electrode may be cooled, e.g., with water.
- Plasma created from the gas within the chamber, is generated and sustained by supplying power (for example, from an RF generator operating at a frequency in the range of 0.001 to 100 MHz) to at least one electrode.
- the RF power source provides power at a typical frequency in the range of 0.01 to 50 MHz, preferably 13.56 MHz or any whole number (e.g., 1, 2, or 3) multiple thereof.
- the RF power source can be an RF generator such as a 13.56 MHz oscillator.
- the power source may be connected to the electrode via a network that acts to match the impedance of the power supply with that of the transmission line (which is usually 50 ohms reactive) so as to effectively transmit RF power through a coaxial transmission line.
- a network that acts to match the impedance of the power supply with that of the transmission line (which is usually 50 ohms reactive) so as to effectively transmit RF power through a coaxial transmission line.
- a description of such networks can be found in Brian Chapman, Glow Discharge Processes, 153 (John Wiley & Sons, New York 1980).
- One type of matching network which includes two variable capacitors and an inductor, is available as Model # AMN 3000 from RF Power Products, Rresson, NJ.
- the articles to be treated may be placed in, or passed through, the evacuable chamber.
- a multiplicity of articles may be simultaneously exposed to the plasma during the process of this invention.
- plasma treatment can be achieved, for example, by placing the articles in direct contact with the smaller electrode of an asymmetric configuration. This allows the article to act as an electrode due to capacitive coupling between the powered electrode and the article. This is described in M. M. David, et al., Plasma Deposition and Etching of Diamond-Like Carbon Films, AIChE Journal, vol. 37, No. 3, p. 367 (1991).
- the article is optionally pulled through the vacuum chamber continuously. The result is a continuous plasma treatment of the elongated article.
- Figure 1 illustrates a parallel plate apparatus 10 suitable for the present invention, showing a grounded chamber 12 from which air is removed by a pumping stack (not shown). Gases to form the plasma are injected radially inward through the reactor wall to an exit pumping port in the center of the chamber.
- Article 14 is positioned proximate RF-powered electrode 16. Electrode 16 is insulated from chamber 12 by Teflon support 18.
- FIG. 2 illustrates single-drum apparatus 100 suitable for the present invention.
- This apparatus is described in more detail in U.S. Pat. No. 5,948,166.
- the primary components of apparatus 100 are rotating drum electrode 102 that can be powered by a radio frequency (RF) power source, grounded chamber 104 that acts as a grounded electrode, feed reel 106 that continuously supplies article 108, which is to be treated, and a take-up reel 110, which collects the treated article.
- RF radio frequency
- Article 108 is a long sheet that, in operation, travels from feed reel 106, around drum electrode 102 and on to take-up reel 110.
- Reels 106 and 110 are optionally enclosed within chamber 104, or can be outside chamber 104 as long as a low-pressure plasma can be maintained within the chamber.
- the curvature of the drum provides intimate contact between the article and the electrode, which ensures that the article remains within the ion sheath, irrespective of other operating conditions such as pressure. This can allow a thick article to be kept within the ion sheath even at high pressures (e.g., 40-133 Pa (300 to 1000 mTorr)). Because the article is supported and -carried by the drum, this intimate contact also enables the treatment of delicate materials. The intimate contact also ensures that plasma treatment is captured by the article, thereby keeping the electrode clean. It also allows for effective single-sided treatment when this is desired. However, dual-sided treatment can be achieved by passing the article through the apparatus twice, with one side being treated per pass.
- a drum electrode also provides a long treatment zone (pi x diameter) and provides symmetric distribution of power across the electrode, which can have operational advantages.
- the drum may be cooled or heated to control the temperature of the article being treated.
- linear dimensions in the direction of current flow are made small in comparison to the wavelength of the RF radiation, eliminating the problem of standing waves.
- One suitable apparatus for this invention is a reactor comprising two drum shaped powered electrodes within a grounded reaction chamber, winch has two to three times the surface area of the powered electrodes.
- the drums can be configured so that the article to be treated can travel around and over the two drums in a manner that allows it to be plasma-treated on both sides (one side is treated on each drum).
- the drums may be located in a single chamber or in separate chambers, or may be in the same chamber, but separated, such that different treatments can occur around each drum.
- one drum may provide a treatment that employs carbon while the other provides a treatment that employs oxygen such that the two sides of the resulting article have different levels of hydrophilicity.
- the reactor When multiple electrodes are used, they may be powered by a single RF supply or powered separately. When a single supply is used, the power is sometimes distributed unequally between the electrodes. This may be corrected by using a different power supply for each electrode with oscillator circuits linked to a master power supply through a phase angle adjuster. Thus any power coupling between the electrodes through the plasma may be fine-tuned by adjusting the phase angle between the voltage waveforms of the master and slave power supplies. Flexibility in power coupling and adjustment between the different electrodes may be achieved by this approach.
- the reactor might include other magnetic or electric means such as induction coils, grid electrodes, etc.
- An aspect of the invention is further directed to a method of plasma-treating article.
- the method is carried out in a suitable capacitively-coupled reactor system such as those described above.
- the article to be treated optionally may be pre-cleaned by methods known to the art to remove contaminants that may interfere with the plasma treatment.
- a useful pre-cleaning method is exposure to an oxygen plasma. For this pre-cleaning, pressures in the reactor are maintained between 1.3 Pa (10 mTorr) and 27 Pa (200 mTorr). Plasma is generated with RF power levels of between 500 W and 3000 W. Other gases may be used for pre-cleaning such as, for example, argon, air, nitrogen, hydrogen or ammonia, or mixtures thereof.
- the chamber Prior to the plasma treatment process, the chamber is evacuated to the extent necessary to remove air and any impurities. This may be accomplished by vacuum pumps at a pumping stack connected to the chamber. Inert gases (such as argon) may be admitted into the chamber to alter pressure.
- Inert gases such as argon
- a source gas containing the species to be deposited is admitted into the chamber via an inlet tube.
- the source gas is introduced into the chamber at a desired flow rate, which depends on the size of the reactor, the surface area of the electrodes, and the porosity of the article to be treated. Such flow rates must be sufficient to establish a suitable pressure at which to carry out plasma treatment, typically 0.13 Pa to 130 Pa (0.001 Torr to 1.0 Torr).
- the flow rates are typically from about 50 to about 500 standard cubic centimeters per minute (seem).
- the source gases typically remain in their vapor form.
- a plasma Upon application of an RF electric field to a powered electrode, a plasma is established, hi an RF-generated plasma, energy is coupled into the plasma through electrons.
- the plasma acts as the charge carrier between the electrodes.
- the plasma can fill the entire reaction chamber and is typically visible as a colored cloud.
- the plasma also forms an io ⁇ sheath proximate at least one electrode, hi an asymmetric electrode configuration, higher self-bias voltage occurs across the smaller electrode.
- This bias is generally negative and in the range of 100 to 2000 volts.
- This biasing causes ions within the plasma to accelerate toward the electrode thereby forming an ion sheath.
- the ion sheath appears as a darker area around the electrode.
- Within the ion sheath accelerating ions bombard species being deposited from the plasma onto, and into the pores of, the article.
- the depth of the ion sheath normally ranges from approximately 1mm (or less) to 50 mm (or more) and depends on factors such as the type and concentration of gas used, pressure in the chamber, the spacing between the electrodes, and relative size of the electrodes. For example, reduced pressures will increase the size of the ion sheaths. When the electrodes are different sizes, a larger (i.e., stronger) ion sheath will form around the smaller electrode. Generally, the larger the difference in electrode size, the larger the difference in the size of the ion sheaths. Also, increasing the voltage across the ion sheath will increase ion bombardment energy.
- the article is exposed to the reactive species within the ion sheath.
- the species within the plasma react on the article's surface and in its pores.
- Plasmas used to treat the porous articles contain species that, when deposited on the articles, can form compositions that change the hydrophilicity of the articles.
- a suitable plasma could contain two or more of oxygen, nitrogen, silicon, carbon, hydrogen, and sulfur in various combinations and ratios.
- the hydrophilicity of the final article may be controlled by a number of factors, for example, the components of the plasma, the length of treatment, and the partial pressure of the plasma components.
- the plasma treatment results in attachment of species to the article surface (including pore surfaces) via covalent bonds.
- the deposited hydrophilic composition may constitute a full layer over the entire exposed article surface (including pore surfaces), maybe more sparsely distributed on the article, or deposited as a pattern through a shadow mask.
- the plasma may also be used to deposit a reactive species that could later be reacted with a material having the desired hydrophilicity.
- a porous article may be treated with a plasma containing silicon, oxygen, and hydrogen such that a diamond-like glass (DLG) is formed on and in the article.
- the article may then be subjected to an oxygen plasma, which will convert the methyl groups of the DLG to oxides, thereby making the article more hydrophilic than it would be with the DLG.
- DLG and its properties are described in U.S. Pat. App. 09/519449.
- hydrocarbons are particularly preferred as sources. Suitable hydrocarbon sources include acetylene, methane, butadiene, benzene, methylcyclopentadiene, pentadiene, styrene, naphthalene, and azulene. Mixtures of these hydrocarbons may also be used.
- Another source of hydrogen is molecular hydrogen (H 2 ).
- Sources of silicon include silanes such as SiH 4 , Si 2 H 6 , tetramethylsilane, hexamethyldisiloxane, tetraethylorthosilicate (TEOS).
- Sources of oxygen include oxygen gas (O 2 ), hydrogen peroxide (H 2 O 2 ), water (H 2 O), nitrous oxide (N 2 O), and ozone (O 3 ).
- Sources of nitrogen include nitrogen gas (N 2 ), ammonia (NH 3 ), and hydrazine (N 2 H 6 ).
- Sources of sulfur include sulfur dioxide (SO 2 ), and hydrogen sulfide (H 2 S).
- hydrophilizing plasma treatments include acrylic and methacrylic acid, acrylamides, methacrylamides, maleic and fumaric acid, vinyl ethers, pyrolhdones, alcohols, glycols, etc. may be used to alter the hydrophilicity.
- the resulting deposits are highly crosslinked and commonly known as plasma polymers.
- nitrides and oxides such as amorphous films of silicon nitride, silicon oxide, boron nitride, titania, aluminum nitride, aluminum oxide, etc, oxynitrides, etc. Furthermore, these might include the attachment of functional groups such as amine, hydroxyl, carboxyl, silanol, etc.
- treatment comprises deposition of a film, it typically occurs at rates ranging from about 1 to 100 nm/second (about 10 to 1000 Angstrom per second (A/sec)), depending on conditions including pressure, power, concentration of gas, types of gases, relative size of electrodes, etc. hi general, deposition rates increase with increasing power, pressure, and concentration of gas, but the rates will approach an upper limit.
- the articles also may be treated in a manner to provide different degrees of hydrophilicity in different areas of the article. This can be achieved, for example, by using contact masks to selectively expose portions of the porous article to the plasma treatment.
- the mask may be attached to the article or may be a separate web that moves with the article.
- the hydrophilic areas may be in any shape that can be achieved using a shadow mask, e.g., circles, stripes, squares, etc.
- Figures 6A and 6B are a digital image of the articles described in Example 8.
- the articles comprise polyethylene porous TIPS membranes on which diamond-like glass (DLG) was deposited through a contact mask having numerous circular holes. The methyl groups on the surface of the DLG were then converted to oxides by a post oxygen-plasma treatment to render the articles more hydrophilic.
- the articles were then stained with methylene blue, which was absorbed only by the hydrophilic sections of the articles.
- Articles having hydrophilicity gradients may also be produced. This can be achieved by exposing different areas of an article to the plasma treatment for different lengths of time. If a hydrophobic article is treated, this could provide, for example, an article in which the hydrophilicity of an article changes gradually (or stepwise) from extreme hydrophilicity to extreme hydrophobicity.
- Articles having patterned hydrophilic areas may be particularly useful for applications that require (1) keeping multiple aqueous samples separated, (2) high throughput assays for biotech applications (so many samples can be assayed at the same time without any cross-talk), and (3) bio chip applications.
- This invention may be illustrated by way of the following examples including the described test methods used to evaluate and characterize the plasma treated articles produced in the examples.
- the contact angle for water was measured on the surface of a porous sample with a Model No: DAT 1100 Fibrodat contact angle measurement instrument available from Thwing Albert Instrument Company.
- a sample was placed on one side of double-coated adhesive tape that was patterned with eight wells and affixed onto an eight-well sample holder. Drops of deionized water were observed under 3 OX magnification as they were deposited onto the sample over each well.
- the contact angles were monitored for 30 seconds and then recorded. The values reported are an average of three measurements, each from a different well.
- Water flow was determined by measuring the time taken to pass a given amount of water through a treated porous sample having a thickness of 22 ⁇ m (0.9 mils. A disc with a diameter of 47 mm was cut from the sample. The disc was placed in a filter support over a flask connected to a vacuum pump. Time was measured for 100 ml of water to flow through the sample.
- a drop of tap water was placed on the surface of the treated porous sample. If the treatment did not render the surface hydrophilic, the water drop beaded on the surface. If the surface was hydrophilic because the treatment was just on the surface, the water drop spread on the surface of the sample without soaking into the pores. In treatments caused the surface energy within the pores to change, the water drop not only spread on the surface but also soaked through the pores to the other side of the membrane.
- 60 Second Absorption - A sample of known size was weighed and then soaked in tepid water. The sample was removed from the water with tweezers and hung by a corner using a spring clamp. After 60 seconds the sample was transferred to a weighing pan. 60 Second Absorption was recorded as (weight after 60 second drip - dry weight) / size in square meters.
- This value was a measurement of time in seconds required to pass 50 cc of air through a film according to ASTM D-726 Method B. A value of greater than 10,000 sec/50 cc was assigned if no air flow was observed for 100 seconds from the start of the test.
- Presence of plasma treatment within the depth of a porous sample was measured by Secondary Ion Mass Specfroscopy using a quadrupole SIMS available from Physical Electronics, Minneapolis, Minnesota, to obtain a depth profile of the sample. Analysis was done using a 5keN Cs+ primary ion beam, with a current of 450 nA, rastered over an area of 800x800 ⁇ m. The aperture for collecting the ion was set at 10%. Charge compensation was obtained using a 400 eV electron gun rastered over an area of 500 X 500 ⁇ m.
- Plasma Reactor A commercial parallel-plate capacitively coupled plasma reactor (commercially available as Model 2480 from PlasmaTherm of St. Russia), typically used for reactive ion etching, was used to carry out plasma treatments of porous samples.
- the reactor had a chamber that was cylindrical in shape with an internal diameter of 762 mm (30 inches) and height of 150 mm (6 inches) and a circular powered electrode having a diameter of 686 mm (27 inches) mounted inside the chamber.
- the powered electrode was attached to a matching network and a 3 kW RF power supply that was operated at a frequency of 13.56 MHz.
- the chamber was vacuum pumped with a Roots blower backed by a mechanical pump. Unless otherwise stated, the base pressure in the chamber was 0.67 Pa (5 mTorr). Process gases were metered into the chamber either through mass flow controllers or a needle valve. Unless otherwise stated, all the plasma treatments were done with the sample located on the powered electrode of the plasma reactor.
- This example illustrates the effect of a water wetting treatment on a porous film.
- a porous article (microporous polyethylene membrane made according to U.S. Pat. No. 4,539,256 Ex 8 except the film was stretched 6 times in one direction, with a pore size of about 0.09 micrometer) was treated in the Plasma Reactor with plasma containing silicon, carbon, hydrogen and oxygen.
- a plasma was ignited with radio frequency (RF) power of 450 watts.
- RF radio frequency
- Plasma treatment was continued for two minutes. After extinguishing the plasma, the gas flows were stopped, the chamber pressure brought down to below 10 mTorr, after which the chamber was vented to atmosphere. The sample was flipped over and the treatment was repeated on the other side.
- Comparative Example 1 was " made in a manner similar to Example 1 except the membrane was suspended outside the ion sheath. The membrane was placed about 25 mm (1 in.) above the powered electrode and outside the ion sheath on a plastic frame that sat on top of the powered electrode. The suspended membrane treated this way was catasfrophically damaged due to the heat from the plasma that existed on each side of the membrane.
- Comparative Example 2 was made in a manner similar to Example 1 except the reactor was different and treatment occurred outside an ion sheath.
- the reactor was a PS 0524 Plasma Coating Treatment System obtained from Himont Plasma Science, now known as 4 th State, Belmont, California. During the plasma treatment the oxygen flow rate was 210 seem, the TMS flowrate was 18 seem, the chamber pressure was 35.3 Pa (265 mTorr), and the power was 500 W.
- the membrane was threaded midway between a powered electrode and a grounded electrode that were separated by a distance of about 86 mm (3 3/8 in ). Thus the membrane was over 40 mm from each electrode and well outside any ion sheath. The web moved at a rate of 3 meters/minute (10 feet/min.), resulting in a treatment time of 20 seconds.
- the oxygen flow rate was 210 seem
- the chamber pressure was 35 Pa (260 mTorr)
- the power was 500 W.
- the web moved at a rate of 3 meters/minute (10 feet/min.), resulting in a treatment time of 20 seconds.
- Example 1 and Comparative Examples 1 and 2 were tested for water soak.
- Example 1 exhibited good water wettability characteristics of water soaking through the membrane. It also had no visible thermal damage from the plasma treatment, hi contrast, Comparative Examples 1 and 2 exhibited no soaking of water through the membrane.
- This example illustrates the effect of a water- wetting treatment on a second type of porous article.
- Example 2 was made as Example 1 except the porous article was a polypropylene blown microfiber non- woven web with a basis weight of 40 grams/sq meter, a thickness of about 150 ⁇ m (6 mils) and an effective pore diameter of about 3.3 microns. " ,
- Example 2 exhibited good water wettability without any observed thermal damage. A drop of water readily soaked all the way through the article without leaving any traces of unabsorbed water on its surface.
- This example illustrates the effect of a three-step water- wetting treatment on the type of porous article described in Example 2.
- a porous article (polypropylene non- woven membrane) was treated in the Plasma Reactor with three plasmas in series, (1) O 2 plasma, (2) TMS/O 2 plasma and (3) O 2 plasma.
- the membrane was exposed to each of the three plasmas while it was within an ion sheath proximate the powered electrode. Squares of membrane of about 12.7 cm x 12.7 cm were mounted on the powered electrode of the Plasma Reactor.
- the reaction chamber was pumped down to a base pressure of less than 1.3 Pa (10 mTorr). Next, O 2 gas was metered into the chamber at a flow rate of 120 seem until a chamber pressure of 4.9 Pa (37 mTorr) was reached.
- the first plasma was ignited and sustained at a power of 500 watts for 1 minute.
- This plasma treatment was to prime the membrane.
- a TMS/O 2 mixture was metered into the chamber with the flow rates of TMS and oxygen maintained at 24.3 seem and 500 seem, respectively.
- the total pressure in the chamber was 20.0 Pa (150 mTorr).
- the second plasma was sustained with this mixture at a power of 500 watts for five minutes.
- the chamber pressure was 50 mTorr and plasma power was maintained at 500 watts for two minutes.
- the sample was flipped over and the three-step treatment was repeated on the other side.
- the three-step treatment produced a non-woven polypropylene membrane with excellent water soak. A drop of water placed on the treated nonwoven membrane readily soaked all the way through the membrane without leaving any traces of unabsorbed water on its surface. The treatment also produced a coating that had a "water-clear" transparency.
- Examples 4-5 were made as Example 3 except the porous samples were different and the process conditions were changed as shown in Table 1.
- the porous sample for Example 4 was a solid cylindrical high-density polyethylene frit having a pore size of 25 microns, a diameter of 3.1 mm (0.125 in) and a length of 9.5 mm (0.375 in), available from Porex Corporation, Fairburn, Georgia.
- the porous sample for Example 5 was a cellulose sponge with a thickness of about 25 mm (3M Grade 21 commercial grade sponge, available from 3M Company).
- Example 4 was completely wettable and it soaked up water completely. To assess the depth of the treatment, a solution of methylene blue in water was used to soak into the frit and the frit was cut with a sharp blade to assess the absorption as a function of depth. Surprisingly, the solution soaked into the pores completely througliout its depth with no noticeable gradient in blue color. This demonstrates the excellent treatment obtained in the pores through the entire depth of the article. In contrast, little if any blue color was noticed within the pores of an untreated sample of the frit used in Example 4.
- Example 5 The treated sponge of Example 5 soaked up significantly more water than an untreated sample of the same type of sponge. This again indicates the extent of treatment within the pores.
- Example 6 was made using the same type of article as Example 1 and in a manner similar to Example 1 except the composition of the plasma was varied for each of nine samples and process conditions were different. Each sample was made with RF power of 300 W and a total chamber pressure of 20 Pa (150 mTorr). Sample A was treated with the three-step plasma treatment of Example 3 except the plasma exposure times for each step were 10, 30, and 10 seconds, respectively. Sample B was treated with a single-step 30 second plasma formed from silane (SiH 4 ) gas available as a 2% concentration in argon from Praxair Specialty Gases, Kingham, Arizona, and oxygen at the flow rates shown in Table 3. Sample C to Sample I were treated with single-step 30 second plasmas formed from gas compositions having progressively decreasing ratios of TMS to O 2 as shown in Table 3. *
- Comparative Example 2 was an untreated porous sample of the same material used in Example 6.
- Example 7 was made in a manner similar to Example 1 except the sample was different, process conditions were changed, and a mask was used.
- the porous sample was a microporous polyethylene membrane made in a manner similar to U.S. Pat. No. 4,539,256, Example 7 except the film was stretched six times in one direction. The average pore size was about 0.09 micrometers.
- the porous sample was exposed to a plasma treatment similar to the three-step treatment of Example 3 except process conditions and exposure times were different. The process conditions and exposure times are shown in Table 4.
- Comparative Example 3 an untreated porous sample, made of the same material used for Example 7, and Sample 7B were measured with Gurley Air Flow, Contact Angle, Water Flow, Infra Red (IR), and Scanning Electron Microscopy (SEM) techniques. The results are shown in Table 5 or described following the Table.
- Figure 3 illustrates the IR spectra of (a) untreated sample CE3, (b) Sample 7-B and (c) Sample 7-B after it was washed with water.
- the IR spectra for (b) and (c) had additional IR bands that were not detected for (a). The bands indicated the presence of
- Si-OH and unoxidized silanes are Si-OH and unoxidized silanes.
- Figure 4 shows SEM pictures of (a) untreated porous sample- CE3 and (b)
- Figure 5 illustrates the depth profile obtained by SJMS (secondary ion mass spectrometry) analysis for Sample 7-A (10 seconds exposure time of 2 nd plasma) and
- Sample 7-B (30 seconds exposure time of 2 nd plasma), respectively.
- the figure illustrates the depth profile of silicon content in the pores by comparing silicon concentration to sputtering time.
- a sputtering time of 500 seconds corresponds to a thickness of about 0.24 microns. Because the membrane was 0.9 mil (22.5 microns) thick, as can be seen, the silicon is found through the entire depth of the membrane in
- Sample 7-B (30 sec TMS/O 2 ). In contrast, the silicon is not found through the entire depth of Sample 7-A (10 sec TMS/O 2 ).
- Example 8 This example illustrates the use of a mask to plasma treat pre-selected regions of a porous sample.
- Example 8 was made as Example 1 except masks were used and the plasma treatment was the three-step method similar to Example 3 except different exposure times were used.
- the porous sample was a microporous polyethylene membrane made in a manner similar to U.S. Pat. No. 4,539,256 Ex 8 except the film was stretched six times in one direction.
- Sample A was made with a mask that had an area of 76 x 102 mm (3x4 in) and 96 circular holes, each with a diameter of about 7.5 mm. The mask was placed on the porous sample while the sample was on the powered electrode. The plasma conditions are shown in Table 6. When the sample was turned over for another plasma treatment, the mask was repositioned on the surface of the sample opposite the surface of the powered electrode.
- Sample B was made as Sample A except the mask had 384 holes with diameters of about 2 mm within the same area (76 x 102 mm).
- the masks were removed from each sample and the samples were evaluated for water wettability. Only the circles treated with plasma were hydrophilic. The rest of the film did not wet with water.
- Figure 6 is a picture of treated porous samples (a) Sample 8A and (b) Sample 8B, stained with the dye.
Abstract
Description
Claims
Priority Applications (9)
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JP2003552421A JP4768225B2 (en) | 2001-12-14 | 2002-10-11 | Method for improving hydrophilicity of porous articles |
EP02786390A EP1453595B1 (en) | 2001-12-14 | 2002-10-11 | Plasma treatment of porous materials |
MXPA04005625A MXPA04005625A (en) | 2001-12-14 | 2002-10-11 | Plasma treatment of porous materials. |
KR1020047009155A KR100970025B1 (en) | 2001-12-14 | 2002-10-11 | Plasma Treatment of Porous Materials |
CA002469739A CA2469739A1 (en) | 2001-12-14 | 2002-10-11 | Plasma treatment of porous materials |
BRPI0214908-7A BR0214908B1 (en) | 2001-12-14 | 2002-10-11 | method of modifying the hydrophilicity of a porous article. |
AU2002351473A AU2002351473A1 (en) | 2001-12-14 | 2002-10-11 | Plasma treatment of porous materials |
DE60208440T DE60208440T2 (en) | 2001-12-14 | 2002-10-11 | PLASMA TREATMENT OF POROUS MATERIALS |
AT02786390T ATE314135T1 (en) | 2001-12-14 | 2002-10-11 | PLASMA TREATMENT OF POROUS MATERIALS |
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US10/023,267 US6878419B2 (en) | 2001-12-14 | 2001-12-14 | Plasma treatment of porous materials |
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US20100151114A1 (en) * | 2008-12-17 | 2010-06-17 | Zimmer, Inc. | In-line treatment of yarn prior to creating a fabric |
US20100159195A1 (en) * | 2008-12-24 | 2010-06-24 | Quincy Iii Roger B | High repellency materials via nanotopography and post treatment |
WO2010129783A1 (en) | 2009-05-06 | 2010-11-11 | 3M Innovative Properties Company | Apparatus and method for plasma treatment of containers |
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FR2947814B1 (en) * | 2009-07-13 | 2011-10-14 | Serigne Dioum | FLUID DEPOLLUTION PRODUCT AND METHOD OF OBTAINING |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0418922A (en) * | 1990-05-11 | 1992-01-23 | Nok Corp | Production of mosaic electrifying membrane |
EP0788833A1 (en) * | 1996-02-12 | 1997-08-13 | Conte S.A. | Process for increasing the wettability of a porous body and device for carrying out the process |
Family Cites Families (59)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3632494A (en) | 1967-11-06 | 1972-01-04 | Warner Lambert Co | Coating method and apparatus |
US4438154A (en) | 1982-04-28 | 1984-03-20 | Stanley Electric Co., Ltd. | Method of fabricating an amorphous silicon film |
US4539256A (en) | 1982-09-09 | 1985-09-03 | Minnesota Mining And Manufacturing Co. | Microporous sheet material, method of making and articles made therewith |
US5034265A (en) | 1983-08-01 | 1991-07-23 | Washington Research Foundation | Plasma gas discharge treatment for improving the compatibility of biomaterials |
DE3337763A1 (en) | 1983-10-18 | 1985-05-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München | METHOD AND DEVICE FOR THE SURFACE MODIFICATION OF THE POROUS INTERNAL WALL OF MEMBRANES |
US4749588A (en) | 1984-09-07 | 1988-06-07 | Nobuhiro Fukuda | Process for producing hydrogenated amorphous silicon thin film and a solar cell |
US4643876A (en) | 1985-06-21 | 1987-02-17 | Surgikos, Inc. | Hydrogen peroxide plasma sterilization system |
JPH0647059B2 (en) * | 1985-06-22 | 1994-06-22 | 住友電気工業株式会社 | Liquid film |
US4869922A (en) | 1986-01-24 | 1989-09-26 | Ausimont S.P.A. | Method of coating with polyfluorocarbons |
US4806246A (en) | 1986-04-11 | 1989-02-21 | Applied Membrane Technology, Inc. | Pore size control using plasma polymerization techniques |
US4760005A (en) | 1986-11-03 | 1988-07-26 | Xerox Corporation | Amorphous silicon imaging members with barrier layers |
US4726989A (en) | 1986-12-11 | 1988-02-23 | Minnesota Mining And Manufacturing | Microporous materials incorporating a nucleating agent and methods for making same |
US5871811A (en) * | 1986-12-19 | 1999-02-16 | Applied Materials, Inc. | Method for protecting against deposition on a selected region of a substrate |
US4968918A (en) | 1987-07-06 | 1990-11-06 | Kanebo, Ltd. | Apparatus for plasma treatment |
US4946903A (en) | 1989-03-27 | 1990-08-07 | The Research Foundation Of State University Of Ny | Oxyfluoropolymers having chemically reactive surface functionality and increased surface energies |
US5120594A (en) | 1989-11-20 | 1992-06-09 | Minnesota Mining And Manufacturing Company | Microporous polyolefin shaped articles with patterned surface areas of different porosity |
US4980196A (en) | 1990-02-14 | 1990-12-25 | E. I. Du Pont De Nemours And Company | Method of coating steel substrate using low temperature plasma processes and priming |
JP2739129B2 (en) | 1990-02-21 | 1998-04-08 | 日本碍子株式会社 | Manufacturing method of composite member |
US5102738A (en) | 1990-11-01 | 1992-04-07 | Kimberly-Clark Corporation | High hydrohead fibrous porous web with improved retentive absorption and acquision rate |
US5486357A (en) * | 1990-11-08 | 1996-01-23 | Cordis Corporation | Radiofrequency plasma biocompatibility treatment of inside surfaces |
US5462781A (en) | 1991-06-14 | 1995-10-31 | W. L. Gore & Associates, Inc. | Surface modified porous expanded polytetrafluoroethylene and process for making |
DE4122834A1 (en) | 1991-07-10 | 1993-01-14 | Siemens Ag | Coating light waveguide fibres - by forming hydrogen-contg. carbon on fibres by plasma deposition of gaseous hydrocarbon |
US5260345A (en) | 1991-08-12 | 1993-11-09 | The Procter & Gamble Company | Absorbent foam materials for aqueous body fluids and absorbent articles containing such materials |
US5443743A (en) | 1991-09-11 | 1995-08-22 | Pall Corporation | Gas plasma treated porous medium and method of separation using same |
US5224441A (en) | 1991-09-27 | 1993-07-06 | The Boc Group, Inc. | Apparatus for rapid plasma treatments and method |
US5234529A (en) | 1991-10-10 | 1993-08-10 | Johnson Wayne L | Plasma generating apparatus employing capacitive shielding and process for using such apparatus |
US5260360A (en) | 1991-10-18 | 1993-11-09 | Minnesota Mining And Manufacturing Company | Oil, water and sweat repellent microporous membrane materials |
US5308673A (en) | 1992-05-07 | 1994-05-03 | Minnesota Mining And Manufacturing Company | Stitchbonded absorbent articles and method of making same |
US5275766A (en) * | 1992-10-30 | 1994-01-04 | Corning Incorporate | Method for making semi-permeable polymer membranes |
JPH06184533A (en) | 1992-12-21 | 1994-07-05 | Mitsubishi Cable Ind Ltd | Production of coated stimulable phosphor |
JPH06299146A (en) | 1993-04-20 | 1994-10-25 | Mitsubishi Cable Ind Ltd | Production of silica-coated fluorescent material |
EP0624896B1 (en) | 1993-05-13 | 1999-09-22 | Applied Materials, Inc. | Contamination control in plasma contouring the plasma sheath using materials of differing rf impedances |
JPH06327950A (en) * | 1993-05-26 | 1994-11-29 | Nitto Denko Corp | Filtration membrane for liquid its production and filter used therefor |
US5494744A (en) * | 1994-10-12 | 1996-02-27 | Kimberly-Clark Corporation | Method of applying a protein coating to a substrate and article thereof |
AU3458095A (en) | 1994-11-03 | 1996-05-09 | Johnson & Johnson Medical, Inc. | Liquid repellent sterilizable material |
SE514726C2 (en) | 1995-02-27 | 2001-04-09 | Sca Hygiene Prod Ab | Process for the production of hydroentangled nonwoven material with increased wet strength and material prepared by the process |
US5783641A (en) | 1995-04-19 | 1998-07-21 | Korea Institute Of Science And Technology | Process for modifying surfaces of polymers, and polymers having surfaces modified by such process |
US5980814A (en) * | 1995-09-01 | 1999-11-09 | Mcneil-Ppc, Inc. | Method for making an apertured film coated with a surface-active agent |
US6468642B1 (en) * | 1995-10-03 | 2002-10-22 | N.V. Bekaert S.A. | Fluorine-doped diamond-like coatings |
US6116185A (en) | 1996-05-01 | 2000-09-12 | Rietzel; James G. | Gas injector for plasma enhanced chemical vapor deposition |
EP0949200A1 (en) | 1996-06-05 | 1999-10-13 | R-Amtech International, Inc. | Method for forming conformal diamond-type carbon coatings, hard diamond-type carbon coating and porous filtration element using the same |
US6243112B1 (en) * | 1996-07-01 | 2001-06-05 | Xerox Corporation | High density remote plasma deposited fluoropolymer films |
US5948166A (en) | 1996-11-05 | 1999-09-07 | 3M Innovative Properties Company | Process and apparatus for depositing a carbon-rich coating on a moving substrate |
US5888594A (en) | 1996-11-05 | 1999-03-30 | Minnesota Mining And Manufacturing Company | Process for depositing a carbon-rich coating on a moving substrate |
JP3571180B2 (en) * | 1997-06-06 | 2004-09-29 | 日本バイリーン株式会社 | Method for treating the entire surface of a non-conductive porous body |
GB9715508D0 (en) | 1997-07-24 | 1997-10-01 | Scapa Group Plc | Industrial fabrics and method of treatment |
US6537932B1 (en) | 1997-10-31 | 2003-03-25 | Kimberly-Clark Worldwide, Inc. | Sterilization wrap, applications therefor, and method of sterilizing |
US6015597A (en) | 1997-11-26 | 2000-01-18 | 3M Innovative Properties Company | Method for coating diamond-like networks onto particles |
KR19990047370A (en) | 1997-12-04 | 1999-07-05 | 구자홍 | Refrigeration and air conditioning metal materials with improved hydrophilicity or hydrophobicity of the surface and methods for improving the same |
US6046758A (en) | 1998-03-10 | 2000-04-04 | Diamonex, Incorporated | Highly wear-resistant thermal print heads with silicon-doped diamond-like carbon protective coatings |
EP0985741A1 (en) | 1998-09-07 | 2000-03-15 | The Procter & Gamble Company | Modulated plasma glow discharge treatments for making super hydrophobic substrates |
ATE241433T1 (en) | 1998-09-21 | 2003-06-15 | Procter & Gamble | PERMANENTLY MOISTENABLE FABRIC WITH LIQUID |
CA2340449A1 (en) | 1998-09-21 | 2000-03-30 | Arseniy Radomyselskiy | Durably wettable liquid pervious webs prepared using a remote plasma polymerization process |
JP2000117880A (en) | 1998-10-15 | 2000-04-25 | Toray Ind Inc | Functional structure and its production |
JP2000239963A (en) | 1999-02-24 | 2000-09-05 | Mitsubishi Paper Mills Ltd | Hydrophilic nonwoven fabric |
JP2003505229A (en) | 1999-07-21 | 2003-02-12 | ホリングワース・アンド・ボーズ・カンパニー | Electret filter media with plasma treatment |
JP2001313286A (en) * | 2000-02-24 | 2001-11-09 | Tokyo Electron Ltd | Parallel-plate dry etching apparatus |
US6696157B1 (en) | 2000-03-05 | 2004-02-24 | 3M Innovative Properties Company | Diamond-like glass thin films |
DE602004007270T2 (en) * | 2004-10-01 | 2008-02-21 | Delphi Technologies, Inc., Troy | Method and system for detecting a vehicle rollover |
-
2001
- 2001-12-14 US US10/023,267 patent/US6878419B2/en not_active Expired - Fee Related
-
2002
- 2002-10-11 WO PCT/US2002/032570 patent/WO2003051498A1/en active IP Right Grant
- 2002-10-11 MX MXPA04005625A patent/MXPA04005625A/en active IP Right Grant
- 2002-10-11 JP JP2003552421A patent/JP4768225B2/en not_active Expired - Fee Related
- 2002-10-11 AU AU2002351473A patent/AU2002351473A1/en not_active Abandoned
- 2002-10-11 BR BRPI0214908-7A patent/BR0214908B1/en not_active IP Right Cessation
- 2002-10-11 CA CA002469739A patent/CA2469739A1/en not_active Abandoned
- 2002-10-11 DE DE60208440T patent/DE60208440T2/en not_active Expired - Lifetime
- 2002-10-11 EP EP05111377.7A patent/EP1632280B1/en not_active Expired - Lifetime
- 2002-10-11 KR KR1020047009155A patent/KR100970025B1/en not_active IP Right Cessation
- 2002-10-11 EP EP02786390A patent/EP1453595B1/en not_active Expired - Lifetime
- 2002-10-11 AT AT02786390T patent/ATE314135T1/en not_active IP Right Cessation
-
2005
- 2005-03-18 US US11/084,318 patent/US7125603B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0418922A (en) * | 1990-05-11 | 1992-01-23 | Nok Corp | Production of mosaic electrifying membrane |
EP0788833A1 (en) * | 1996-02-12 | 1997-08-13 | Conte S.A. | Process for increasing the wettability of a porous body and device for carrying out the process |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 199210, Derwent World Patents Index; Class A88, AN 1992-075699, XP002238263 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7462494B2 (en) | 2003-06-09 | 2008-12-09 | 3M Innovative Properties Company | Method for laser desorption mass spectrometry using porous polymeric substrates with particle fillers |
JP2006272076A (en) * | 2005-03-28 | 2006-10-12 | Seinan Kogyo Kk | Surface modifying method using ion beam |
EP1790770A2 (en) * | 2005-11-23 | 2007-05-30 | Tesalca-99, S.A. | Procedure for obtaining nonwoven fabrics with hydrophilic areas and hydrophobic areas |
EP1790770A3 (en) * | 2005-11-23 | 2007-11-28 | Tesalca-99, S.A. | Procedure for obtaining nonwoven fabrics with hydrophilic areas and hydrophobic areas |
EP2242725A1 (en) * | 2007-12-21 | 2010-10-27 | 3M Innovative Properties Company | Liquid filtration systems |
EP2242725A4 (en) * | 2007-12-21 | 2012-08-29 | 3M Innovative Properties Co | Liquid filtration systems |
EP2242725B1 (en) | 2007-12-21 | 2016-04-06 | 3M Innovative Properties Company | Liquid filtration systems |
US8591752B2 (en) | 2011-12-07 | 2013-11-26 | Hitachi High Technologies Corporation | Plasma processing method |
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DE60208440T2 (en) | 2006-08-24 |
EP1453595A1 (en) | 2004-09-08 |
US7125603B2 (en) | 2006-10-24 |
AU2002351473A1 (en) | 2003-06-30 |
DE60208440D1 (en) | 2006-02-02 |
CA2469739A1 (en) | 2003-06-26 |
ATE314135T1 (en) | 2006-01-15 |
EP1632280A2 (en) | 2006-03-08 |
BR0214908A (en) | 2004-11-30 |
JP2005511297A (en) | 2005-04-28 |
EP1632280A3 (en) | 2008-01-09 |
EP1453595B1 (en) | 2005-12-28 |
KR20040074083A (en) | 2004-08-21 |
MXPA04005625A (en) | 2004-12-06 |
EP1632280B1 (en) | 2014-11-26 |
US20050181198A1 (en) | 2005-08-18 |
JP4768225B2 (en) | 2011-09-07 |
US6878419B2 (en) | 2005-04-12 |
KR100970025B1 (en) | 2010-07-16 |
BR0214908B1 (en) | 2011-02-22 |
US20030138619A1 (en) | 2003-07-24 |
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