WO2004073755A1 - Dispositif de distribution de gaz et procedes d'utilisation correspondants - Google Patents
Dispositif de distribution de gaz et procedes d'utilisation correspondants Download PDFInfo
- Publication number
- WO2004073755A1 WO2004073755A1 PCT/US2004/005194 US2004005194W WO2004073755A1 WO 2004073755 A1 WO2004073755 A1 WO 2004073755A1 US 2004005194 W US2004005194 W US 2004005194W WO 2004073755 A1 WO2004073755 A1 WO 2004073755A1
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- WO
- WIPO (PCT)
- Prior art keywords
- reactant
- seal
- housings
- gas
- housing
- 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.)
- Ceased
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
- B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
- B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
- B65D75/325—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet being recessed, and the other being a flat not- rigid sheet, e.g. puncturable or peelable foil
- B65D75/327—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet being recessed, and the other being a flat not- rigid sheet, e.g. puncturable or peelable foil and forming several compartments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/20—Gaseous substances, e.g. vapours
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/26—Accessories or devices or components used for biocidal treatment
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
- A61L2202/10—Apparatus features
- A61L2202/15—Biocide distribution means, e.g. nozzles, pumps, manifolds, fans, baffles, sprayers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/685—Devices for dosing the additives
- C02F1/688—Devices in which the water progressively dissolves a solid compound
Definitions
- gas for retarding controlling, killing and preventing microbiological contamination e.g., bacterial, fungi, viruses, mold spores, algae, and protozoa
- gas for retarding controlling, killing and preventing microbiological contamination e.g., bacterial, fungi, viruses, mold spores, algae, and protozoa
- Such gases include, but are not limited to, chlorine dioxide, sulfur dioxide, nitrogen dioxide, nitric oxide, carbon dioxide, hydrogen sulfide, hydrocyanic acid, and dichlorine monoxide.
- chlorine dioxide has been found to be useful as a disinfectant antiseptic and sanitizer. It is used, e.g., to disinfect drinking water and various water supplies.
- chlorine dioxide finds use as a bleaching agent for flour, fats, and textiles. Chlorine dioxide also has shown great utility as an antiseptic for treating metal and plastic surfaces, as well as other substrates such as countertops, meat processing and packaging equipment, and dental and medical instruments and devices.
- reactant compositions in various forms such as powders, gels, liquids and tablets, and disposed between layers of material or within a sachet.
- Apparatus and methods that would allow for the safe and convenient delivery of a plurality of predetermined amounts of reactant at desired intervals and desired concentrations would be of value in a number of fields.
- such apparatuses and methods may be employed to automatically or manually generate desired concentrations of chlorine dioxide in a fluid at desired times from an apparatus that houses a plurality of individual gas generating devices or reactant mixtures.
- This invention relates generally to an apparatus and method for delivery of a gas, and more specifically to an apparatus and method for initiating a plurality of reactants or individual reactant devices coterminously or sequentially and/or for delivering a plurality of individual gas generating devices.
- the present invention provides an apparatus and methods for controlled delivery of a gas in a sequential manner and at predetermined levels.
- the present invention provides a unique system for storage of reactant or reactant devices and delivery of gas to a desired location at a desired rate or time.
- the present invention can be used for a variety of applications, including delivery of a gas to air, water, or surfaces for a variety of purposes including, but not limited to, bleaching, disinfection, deodorization, sanitization, and sterilization.
- the invention provides for an apparatus for delivery of a gas including a plurality of reactant housings defined by the apparatus, each of the reactant housings having a orifice; and a seal disposed about the orifice of at least one of the plurality of reactant housings.
- the apparatus is suitable for use in a humidifier or a water purification device.
- the plurality of reactant housings is in the form of a cassette. Additionally, the plurality of housings may be cavities in a strip. In one embodiment, the strip is capable of being rolled and may further be disposed in a compartment that includes an opening capable of dispensing the strip. Furthermore, the compartment may include a sealing device about the opening. In another embodiment, the plurality of reactant housings is in the form of a blister pack.
- the apparatus includes a reactant (e.g., a reactant tablet) in at least one reactant housing.
- a reactant device e.g., a sachet
- the gas is chlorine dioxide or sulfur dioxide.
- the apparatus may further include a retaining structure disposed within the reactant housing and/or a permeable layer disposed about the orifice. Additionally, the reactant housing may be defined in part by a barrier layer (e.g., a vapor barrier).
- the apparatus may further include a dispensing device suitable for disrupting the seal of at least one of the reactant housings. In one embodiment, the apparatus includes a plunger suitable for disrupting the seal of at least one of the reactant housings.
- the invention provides for a method of delivering a gas, including the step of disrupting the seal of at least one of the reactant housings of the apparatus such that a reactant is initiated and a gas is delivered.
- the step of disrupting the seal includes, but is not limited to, puncturing, breaking, or removing the seal.
- the disruption step may be automated.
- at least two reactant housings are disrupted (e.g., sequentially).
- the method further includes exposing the reactant to an environment comprising an initiating agent.
- the environment is liquid and the initiating agent is gaseous or liquid water.
- the environment is gaseous and the initiating agent is water vapor.
- the apparatus may be used for reducing biofilms; for the cleaning, sanitizing, or disinfection of food or beverage equipment; for the cleaning, sanitizing, or disinfection of dental equipment; or for the cleaning, sanitizing, or disinfection of medical equipment.
- Figure 2 is a cross sectional view of an exemplary embodiment of an apparatus constructed in accordance with the present invention that features a cassette housing;
- Figures 3 is a perspective view of an exemplary embodiment of an apparatus constructed in accordance with the present invention that includes a strip type cassette;
- Figure 4 is a perspective view of an exemplary embodiment of an apparatus constructed in accordance with the present invention that includes a strip type apparatus that is rolled;
- Figure 5 is a perspective view of an exemplary embodiment of an apparatus constructed in accordance with the present invention that includes a strip type apparatus that is rolled and enclosed in a housing;
- Figure 6 is a perspective view of an exemplary embodiment of an apparatus constructed in accordance with the present invention that includes a dispensing device.
- the present invention is based, in part, on. the creation of an apparatus that allows for systematic and sequential delivery of gas.
- the invention provides an apparatus defining a plurality of reactant housings. A seal disposed about the orifice of the housing may be disrupted, thereby generating gas, for example, by exposing the reactants to an initiating agent and prompting the generation of the desired gas. According to the invention, the process may be repeated as necessary, so as to conveniently generate a specific amount of desired gas.
- the present invention provides an apparatus and a means for the repeated and/or sequential generation of a desired amount of gas.
- the present invention provides an apparatus and a means for generating an integer multiple of a specific amount of gas (for example, an integer multiple of the gas generated by the reactant in one housing).
- the present invention provides a gas delivery apparatus that is convenient and economical to package, store, insert into other devices, and use.
- reactant refers to a reactant or a mixture of reactants that generates gas in the presence of an initiating agent.
- reactants include, but are not limited to, metal chlorites (e.g., sodium chlorite), and acids (e.g., citric acid).
- the reactant or reactants can further include additives, such as the hydrotalcites, activated hydrotalcites or any of the metal hydroxides described in International Patent Publication No. WO 03/051406, hereby incorporated by reference.
- the reactant and any additives can be provided in the form of a powder, a liquid, a gel, a wax, or any other form suitable for use in the apparatus and methods of the present invention.
- initiating agent refers to any agent that initiates the generation of gas from the reactant.
- initiating agent includes, but is not limited to, gaseous or liquid water.
- Reactant housing refers to a housing for reactant.
- Reactant housing can be configured to accept various forms of reactant (e.g., gel, powder, tablet) and/or the housing can be shaped or configured such that head space is minimized in order to further stabilize the reactant.
- the reactant housing is defined in part by a barrier layer.
- Impermeable layer refers to a layer that substantially prevents or hinders passage of initiating agent. As contemplated herein, the impermeable layer does not participate in the generation of gas in that it does not facilitate contact between initiating agent and reactant. Impermeable layers can be constructed from various materials, including polymeric material, glass, metal, metallized polymeric material and/or coated papers. As used herein, barrier layers are impermeable layers. Preferred materials for impermeable layers and barrier layers may be any of the materials described throughout this application and in International Patent Publication No. WO 03/051406.
- Permeable layer refers to a layer that permits passage of gas generated by an apparatus of the present invention. Permeable layers typically are constructed from polymeric materials. In addition to the permeable layers described herein, the sachet layers and envelope layers described in International Patent
- WO 03/051406 are permeable layers, and any one or combination of layers can be employed in constructing the apparatus of the present invention and/or any reactant device used with the apparatus of the invention.
- the present invention discloses an apparatus for delivery of a gas.
- the apparatus generally includes a plurality of reactant housings defined by the apparatus, each reactant housing having an orifice.
- a seal is disposed about the orifice of at least one of the plurality of housings.
- the apparatus may be in a variety of forms including, but not limited to, a cassette, a strip and a blister pack.
- the housings may be defined by a cavity or walls that can be formed by any known technique including, for example, injection molding and/or heat welding various plastic parts together (e.g., welding walls and barrier layers).
- the apparatus can also be constructed from other materials such as metal or metal foils.
- multiple housings contain reactant.
- the reactant may contain other components or layers as desired, for example, to retain any byproducts and/or to control the efficiency of the reaction.
- the reactant can be in liquid, solid or gel form.
- the reactant can be impregnated in a composition or material, such as a wax or a clay.
- the reactant preferably comprises an aqueous soluble acid and a reactant that upon acid activation generates a gas.
- a gas for example, for the generation of chlorine dioxide, preferably the reactant comprises an aqueous soluble acid and an aqueous soluble chlorite.
- the reactant for the generation of sulfur dioxide, preferably the reactant comprises an aqueous soluble acid and an aqueous soluble sulfife.
- Other examples of gas generating reactions are disclosed above.
- any acid can be used as a reactant.
- weak acids are preferred, as they typically are safer to handle, produce less undesirable byproducts, and are less reactive.
- multifunctional acids are preferred. Multifunctional acids are acids that have more than one reactive site.
- the trifunctional acid, citric acid is preferred.
- the aqueous soluble acid is selected from the group consisting of phosphoric acid, fumaric acid, glycolic acid, acetic acid, ascorbic acid, oxalic acid, maleic acid, lactic acid, tartaric acid, citric acid and mixtures thereof.
- the aqueous soluble acid is selected from the group consisting of ascorbic acid, phosphoric acid, oxalic acid, maleic acid, lactic acid, tartaric acid, citric acid and mixtures thereof. Most preferably, the aqueous soluble acid is ascorbic acid, oxalic acid, citric acid and mixtures thereof.
- the aqueous soluble chlorite is selected from a group consisting of sodium chlorite and potassium chlorite and mixtures thereof. Preferably, sodium chlorite is used.
- the weight ratio of the aqueous soluble chlorite to the aqueous soluble acid is between about 1 :1 to about 1 :8, most preferably from about 1 :2 to about 1:5.
- a pH between about 1.5 to 5.5, more preferably a pH of about 2, is maintained by using an excess of acid. Because the reactants are concentrated within the reactant housing and/or a reactant device, less acid is needed to drive the reaction to completion and the pH remains low because the acid is concentrated. Furthermore, chlorite is consumed by acid and therefore the presence of chlorite is minimized.
- the reactant may include additives, for example, a moisture scavenger to prevent premature reaction.
- the gas generated can include one or a combination of gases including, but not limited to, chlorine dioxide, sulfur dioxide, and hydrogen sulfide.
- the gas generated includes chlorine dioxide.
- the reactant is contained within a reactant device.
- Reactant devices for controlled and efficient delivery of a gas such as chlorine dioxide, are described in, for example, U.S. Patent Nos. 6,602,466 and 6,607,696 by Hamilton et al, and International Patent Publication Nos. WO 03/051406 and WO 03/05407, which patents and patent publications are incorporated herein by this reference.
- reactant is generally enclosed, at least in part, by at least one- layer through which the generated gas can pass.
- the devices can be comprised of single or multiple layers (e.g., sachets and envelopes).
- the enclosures containing the reactant can include a permeable material and an impermeable material wherein the impermeable material is substantially impervious to the initiating agent and/or the generated gas.
- the enclosures also may include a rigid material that supports a permeable layer (e.g., as described and shown in Figure 6).
- Other reactant devices that can be used in accordance with the present invention include those depicted in U.S. Patent Nos. 6,238,643, 6,132,748 and 6,174,508 and International Patent Publication No. WO 02/00332.
- the reactant device may be bonded, for example, heat sealed, to the apparatus.
- each reactant housing can contain one or a multiple or reactant devices.
- the term "seal" generally refers to a layer disposed about the orifice of a reactant housing.
- the seal is an impermeable layer disposed about the orifice.
- the seal serves, in part, to hold the reactant or reactant device in position within the housing. Additionally, the seal may serve to prevent exposure of the reactants to the initiating agent.
- the seal may be made of any material that may be disrupted by, for example, breaking, puncturing, peeling, removing, etc. Exemplary materials include, but are not limited to, foil or plastic.
- the seal may be made integrally with the apparatus, or, alternatively, the seal may be sealed, bonded or otherwise affixed to the orifice of the housing. For peelable seals, the seal may be heat bonded or otherwise adhered to the housing such that it can be removed without disrupting the housing.
- the seal includes a break groove.
- the break groove allows for easier breaking of the seal so as to expose the reactant or the reactant device.
- the break groove may include any indentation, marking, seam or cut that eases disruption of the seal, but that does not undermine the ability of the seal to perform its desired function (e.g. , to hold the reactant in position and/or to prevent exposure of the reactant to an initiating agent).
- the break groove may be formed on either or both sides of the seal (i.e., on the side of the layer facing the interior of the apparatus, or alternatively on the side of the layer facing the exterior of the apparatus).
- the break groove is formed in the center of the housing and extends the length of the housing.
- the seal may include hinges to further aid in the disruption of the seal.
- the hinges may include any indentation, marking, seam or cut that allows for easier disruption of the seal about the hinges.
- the hinges may be formed on either side of the seal, although, preferably the hinges are formed on the external side of the seal (i.e., the side of the seal facing the exterior of the apparatus).
- the hinges are, preferably, substantially near the ends of the seal adjacent the ends of the housing orifice.
- the hinges extend the length of the housing.
- the apparatus further includes at least one permeable layer disposed about the orifice of the housing.
- the permeable layer is positioned between the seal and the orifice of the housing such that it defines a reactant volume and serves to control generation and release of the gas.
- the permeable layer may be sealed, bonded or otherwise affixed to the orifice of the housing by techniques well known in the art.
- a permeable material or layer is disposed about the orifice, between the orifice and the seal.
- the use of one or more permeable layers can be used to limit the diffusion of the initiating agent into the reactant housing, and to limit the diffusion of reactant and reactant byproducts out of the reactant housing, particularly when the reactant is not disposed in a sachet or other reactant device within the housing.
- the reactants are and remain concentrated within the reactant housing and the pH remains localized increasing the efficiency of the reaction.
- the reactants are further isolated and the reaction is further localized to the reactant device.
- the permeable layer preferably is constructed of a material that is durable and . stable. Preferably, it also is capable of fusing to a like material upon the application of heat or ultrasonics for construction purposes, e.g. , so that the layer can be fused about the perimeter of the orifice of the reactant housing by any known method, such as heat sealing, ultrasonic sealing, radio frequency sealing, and sealing with adhesives.
- the permeable layer(s) employed can be chosen to control the diffusion of the reactants out of the reactant housing, control the rate of gas release from the apparatus and control the initiation of the reactants.
- a hydrophilic permeable layer will increase the rate at which water and/or water vapor diffuses into the reactant housing, and the pore size and thickness of the permeable layer also will effect the passage of water, reactants and gas into and out of the reactant housing.
- the permeable layer can be constructed of various materials, including polymeric material or coated papers, perforated films, membranes, extruded membranes, woven and non- woven materials, spun materials, selective transmission films, and any other material with a controlled pore distribution having a mean pore size between about 0.001 ⁇ m and about 50 ⁇ m.
- a woven material is any material woven from cotton, metal, polymer threads, metal threads or the like into a cloth or mesh.
- Extruded membranes which include cast membranes, can be employed, e.g., a 0.65 micron pore size, 230 to 260 micron thick, hydrophilic polyethylene membrane sold under the trade designation MPLC from Millipore (Bedford, MA), and a 0.65 micron pore size, extruded hydrophobic polyethylene material sold under the trade designation DOHP by Millipore (Bedford, MA).
- the cast membrane 3 micron pore Nylon 6,6 material sold under the trade designation BIODYNE A by Pall (Port Washington, NY).
- Non-woven membranes are membranes formed from materials such as cellulose or polymers.
- cast membranes include 0.45 pore, hydrophilic Nylon 6,6 membranes with a polypropylene backbone sold under the designation BA05 by Cuno Incorporated (Meriden, CT); 0.45 pore, hydrophilic polypropylene membrane available from 3M (City, State); and 0.45 pore size, 180 to 240 micron thick, hydrophilic Nylon 6,6 membranes sold under the designations 045ZY and 045ZN by Cuno Incorporated. (Meriden, CT). Also suitable are hydrophobic, liquid water permeable non-woven polyethylenes, such as the TYVEK® 1025D polyethylene material from DuPont Company (Wilmington, DE).
- Suitable permeable layers include membranes having a pore size between about 0.01 ⁇ m and about 50 ⁇ m. More preferably, the pore size is between about 0.05 ⁇ m and about 40 ⁇ m, and most preferably, the pore size is between about 0-1 ⁇ m and 30 ⁇ m.
- Suitable membranes include those having a thickness between about 50 microns and 500 microns, more preferably between about 100 microns and 400 microns, and most preferably between about 150 microns and 300 microns.
- the permeable layer preferably has a bubble point between about 3 psi and about 100 psi, more preferably between about 5 psi and about 80 psi, and most preferably between about 10 psi and about 70 psi.
- the hydrophobic material preferably has a flow time between about 10 sec/500ml and about 3,500 sec/500ml for 100% IPA at 14.2 psi.
- the material has a flow time between about 60 sec/500ml and about 2,500 sec/500ml for 100% IPA at 14.2 psi, and most preferably, the material has a flow time between about 120 sec/500ml and about 1 ,500 sec/500ml for 100% IPA at 14.2 psi.
- the hydrophilic material preferably has a flow time between about 5 sec/500 ml and about 800 sec/500 ml for 100% IPA at 14.2 psi. More preferably, the material has a flow time between about 20 sec/500ml and about 400 sec/500ml for 100% IPA at 14.2 psi, and most preferably, the material has a flow time between about 50 sec/500ml and about 300 sec/500ml for 100% IPA at 14.2 psi. Measurement of flow time is routine and well known in the art.
- Suitable hydrophilic materials include the polyethersulfone, 110 micron thick, 0.65 micron pore size membrane sold under the trade designation Micro PES 6F hydrophilic flat membrane by Membrana GmbH (Wuppertal, Germany).
- Yet another alternative embodiment includes a permeable layer that has a first surface that is hydrophilic and a second surface that is hydrophobic, for example, a material having a hydrophilic surface facing the outside of the reactant housing and the hydrophobic surface on the inside of the reactant housing.
- the exterior, hydrophilic surface aids the initiation of the reaction since water will readily wet a hydrophilic surface and enter the reactant housing.
- the hydrophobic, interior surface limits water passage out of the housing. This keeps the reactants concentrated within the reactant housing while allowing the gas to escape thus exploiting the advantages of the discoveries disclosed herein.
- One such material suitable for use in the present invention is a non-woven membrane 0.65 micron pore size diameter formed from a hydrophobic material, such as polypropylene, that has been chemically functionalized with amines and carboxyl groups to produce a charge, hydrophilic surface.
- a hydrophobic material such as polypropylene
- the ratio of reactant housing volume to reactant volume also can be manipulated to control the concentration of the reactants, intermediates, byproducts, etc. within the housing. Increasing the concentration of reactants generally increases reaction efficiency.
- the reactant housing volume is less than about 20 times the volume of reactant, more preferably less than about 10 times the volume of the reactant. Most preferably, it is less than 6, 4, 3, 2, and even 1.25 times the volume of the reactants.
- the permeable layer can be constructed from hydrophobic, liquid water permeable material, such as polyethylene or polypropylene. These materials preferably are between about 1 mil and about 10 mils thick with a water intrusion pressure of about 30 millibars or 30 millibars or less. Suitable hydrophobic materials include, but are not limited to, non- woven polyethylene such as the TYVEK® non-woven polyethylenes from DuPont Company (Wilmington, DE), e.g., the TYVEK® 1025D non- woven polyethylene which has an intrusion pressure of less than 30 millibars.
- non- woven polyethylene such as the TYVEK® non-woven polyethylenes from DuPont Company (Wilmington, DE), e.g., the TYVEK® 1025D non- woven polyethylene which has an intrusion pressure of less than 30 millibars.
- Hydrophilic membranes also can be employed having e.g., a pore size between about 0.01 microns and about 50 microns. More preferably, the pore size is between about 0.05 microns and 40 microns, and most preferably, the pore size is between about 0.1 and about 30 microns.
- Preferred membranes also include, but are not limited to, the microporous ultra high density polyethylene membrane sold under the trade designation MPLC from Millipore (Bedford, MA), and the microporous Nylon 6,6 membrane sold under the designation 045ZY by Cuno Incorporated (Meriden, CT).
- water vapor selective refers to a material that selectively allows permeation of water vapor and substantially impedes permeation of liquid water. More preferably, the material excludes permeation of liquid water. Typically, the water vapor selective material is hydrophobic. The skilled practitioner typically refers to water vapor selective material as water impermeable, although water vapor can permeate the layer, and refers to materials that allow permeation of liquid water as water permeable. Suitable water vapor selective materials can be made from a variety of materials including, but not limited to, polytetrafluoroethylene (PTFE), polypropylene (PP), polyethylene (PE), and fluorinated ethylene propylene (FEP).
- PTFE polytetrafluoroethylene
- PP polypropylene
- PE polyethylene
- FEP fluorinated ethylene propylene
- Water vapor selective material also is particularly advantageous because it substantially impedes or excludes the diffusion of water soluble species, such as water soluble reactants, additives, and reaction byproducts, out of the apparatus.
- Membranes that allow liquid water permeation allow soluble species such as soluble reactants to permeate the apparatus and enter the environment.
- Prior attempts have been made to ameliorate or avoid escape of soluble species by using insoluble reactants or by binding or otherwise disposing the soluble species on insoluble materials such as clays and molecular sieves. This is not advantageous because it introduces additional steps and/or expense to the preparation of the apparatus.
- the water vapor selective materials of the present invention are advantageous because they impede or preclude the permeation of the soluble reactants, additives, and byproducts, thus removing the need to include or generate insoluble reactants, byproducts and/or additives.
- Water vapor selective materials also are advantageous because their use eliminates the need to use any further permeable layers to retain soluble species in the apparatus, which also introduces additional steps and expense in the construction of the apparatus.
- the water vapor selective material has a thickness between about 5 microns and about 400 microns thick, a pore size between about 0.05 microns and about 10 microns, and a water intrusion pressure between about 30 millibars and about 4,000 millibars.
- the water vapor selective material is adhered to or otherwise supported by a support layer that allows liquid water to permeate the support layer, and the overall thickness of both the water vapor selective layer and the support layer is between about 1 mil and 20 mils. More preferred, are water vapor selective materials having a thickness between about 15 microns and about 200 microns thick, a pore size between about 0.25 microns and about 5 microns, and a water intrusion pressure between about 100 millibars and about 1,500 millibars. Preferably, this layer has a water permeable support layer such that the total thickness of both layers is between about 2 mils and about 10 mils.
- water vapor selective materials having a thickness between about 20 microns and about 100 microns thick, a pore size between about 1 micron and about 3 microns, and a water intrusion pressure between about 200 millibars and about 750 millibars.
- this layer has a water permeable support layer such that the total thickness of both layers is between about 3 mils and about 8 mils.
- a thinner layer is preferred because the thinner the layer, the more rapidly water vapor can diffuse into the apparatus and initiate the reaction, and the more rapidly gas can diffuse out of the apparatus.
- a thicker material is preferred, such as between about 5 mils and about 20 mils.
- a relatively smaller surface area of the material can be used.
- a suitable reactant device can be constructed from a rigid frame with at least one permeable layer, e.g., a water vapor selective layer and optionally a barrier layer.
- pore size of the water vapor selective layer can be selected to produce the desired release at specific depths of water in which the apparatus will be used. A smaller pore size will correspond to deeper operation by increasing the amount of hydraulic water pressure that the membrane will experience while remaining impermeable to liquid water.
- Water vapor selective layers suitable for use in constructing the apparatus of the present invention preferably have water vapor permeability of between about 2,000 g/m 2 /24hrs and about 150,000 g/m 2 /24hrs, as determined by JIS L 1099-1985 (Method B), "Testing Methods for Water Vapour Permeability of Clothes," from the Japanese Standards Association.
- Water vapor selective layers preferably have a resistance to liquid water permeation of at least about 30 millibars as determined by ISO 811-1981 "Textile fabrics - Determination of resistance to water penetration - Hydrostatic pressure test" published by the International Organization for Standardization.
- the water vapor selective layer or layers of the present invention can include a support layer to increase the strength of the layer, and/or to increase its ability to bond to the other materials used to construct the apparatus.
- the support layer preferably allows diffusion or passage of initiating agent to the surface of the water vapor selective layer.
- the support layer can be spun, perforated or have large pores that allow passage of liquid water and vapor to the surface of the water vapor selective layer.
- the support layer can be affixed to the water vapor selective layer by any means, for example, lamination, casting, co-extrusion, and or adhesive layers.
- the permeable layer is positioned such that the water vapor selective layer faces the interior of the reactant housing.
- the support layer itself can be hydrophilic and or hydrophobic.
- the material can be used to attract and deliver liquid water and/or vapor to the surface of the water vapor selective material.
- Suitable support layers include, but are not limited to, polyethylene, polypropylene, nylon, acrylic, fiberglass, and polyester in the form of woven, non-woven, and mesh layers.
- the support layer thickness is between about 1 mil and 20 mils.
- Suitable water vapor selective materials previously described herein include the 0.60 pore size, hydrophobic, polypropylene (PP) membrane having a thickness between about 250 microns and about 300 microns sold under the designation 060P1 by Cuno Incorporated (Meriden, CT). Also suitable is the 0.65 micron pore size, hydrophobic polyethylene material sold under the trade designation DOHP by Millipore (Bedford, MA).
- Another water vapor selective material, suitable for use in a rapid release apparatus includes a 1.75 mil thick, hydrophobic polytetrafluoroethylene (PTFE) layer thermally bonded to a 5 mil thick, hydrophobic polyethylene (PE) support layer sold under the trade designation BHA-TEX® by BHA Technologies (Kansas City, MO).
- FIGS 1A, IB and 1C depict an exemplary embodiment of an apparatus contracted in accordance with the present invention.
- the apparatus 10 generally forms a one piece circular cassette.
- the cassette 10 features a plurality of reactant housings 30, defined in part by partitions 50, which in this exemplary embodiment includes radial walls 52 andconcentric cylindrical walls 54, 56, but could include any structure to define the housings.
- the housings, as shown, are formed to accommodate at least one reactant device 120.
- the apparatus further includes a retaining structure 40.
- the retaining structure is a bar positioned within the housing so as to retain a reactant device 140.
- the retaining structure may be of any shape or material so as to hold a reactant device within the housing.
- the retaining structure is integrally formed with the cassette, however, this is not necessary.
- the exemplary embodiment of Figure 1 further includes a cylindrical wall 54, which can be employed to attach the cassette to a fixture such as a spindle (not shown).
- the fixture can simply be a spindle that holds the cassette in place for manual delivery of the reactant or, for example, can be part of a device for mechanically and periodically delivering gas by disruption of one or more seals.
- the cassette can rotate about the spindle for convenient sequential delivery.
- Figure IB depicts a cross section of reactant housings taken along line IB -IB of Figure 1A.
- the reactant device 120 of this particular embodiment is held in place by radial wall 52, interior wall 54, exterior wall 56 (not shown in Figure IB), cassette retaining bar 40, and a barrier layer 140.
- Figure IB further depicts a means for exposing the reactant, for example, by actuating a plunger 100 that breaks a middle seam 14 along the break grooves 20 thereby allowing the seal to open about the hinges 80.
- the break grooves 20 are formed in the center of the seal and extend the length of the seal.
- the hinges 80 are formed along the ends of the seal of the orifice 75 and extend the length of the seal (not shown).
- the exemplary apparatus also features a barrier layer 140, in part, defining the housing.
- the barrier layer serves to hold the reactant in position within the housing.
- the barrier layer is an impermeable layer.
- the barrier layer may further serve to prevent exposure of the reactant to an initiating agent (e.g., vapor).
- the barrier layer may be formed of any material known in the art.
- the barrier layer e.g., a vapor barrier
- the barrier layer should be made of material known in the art that is substantially impervious to the initiating agent.
- the barrier layer can be sealed, bonded or otherwise affixed to the cassette after the reactant is placed into a housing of the cassette.
- the apparatus allows the ready insertion of a plurality of reactant devices or reactants into the housing for deliveiy at desired times in desired amounts.
- Another advantage is that the apparatus allows multiple reactant devices or reactant amounts into the device prior to affixing the barrier layer.
- the cassette can be reused by removal of the barrier layer, reinsertion of new reactants and affixing a new barrier layer onto the apparatus.
- Figure 2 depicts an alternative embodiment of a cross section of an apparatus made in accordance with the invention.
- the cassette of Figure 2 features a one piece molded cassette 200 defining a plurality of reactant housings 215 (e.g., formed by a molding process used to make the cassette).
- the reactant device 240 of this particular embodiment is held in place by a radial wall 230 and a barrier layer 250.
- Figure 2 illustrates one mechanism for delivery of gas that includes a plunger 220, to break the seal 210 at the break groove 225 along hinges 280.
- Gas generation can alternatively be initiated by rupturing a frangible pouch that is positioned in the reactant housing and that contains an initiating agent (e.g., water).
- gas delivery can be initiated by allowing the plunger to continue past the seal to disrupt the barrier layer, thereby releasing the gas generating device from the cassette into an environment that includes initiating agent.
- Figure 3 depicts another exemplary embodiment of an apparatus in accordance with the present invention.
- the apparatus 300 features a series of reactant housings which, in this embodiment, are cavities 315 formed in a strip 305.
- the strip 305 can be comprised of either flexible or rigid material, depending on the desired application and delivery mechanism.
- the housings are filled with reactant 310. In other embodiments, the housings are filled with reactant devices.
- a permeable layer 320 and a seal 330 are disposed on the strip.
- a permeable layer 320 is disposed on the strip, enclosing the reactants and the housing and defining a reaction volume.
- the permeable layer can include any of the permeable layers described herein, for example, a water vapor selective layer.
- a seal 330 is then disposed on top of the permeable layer 320.
- the seal preferably is substantially impervious to the initiating agent, thereby, preventing the initiating agent from reaching the reactants.
- the reactant in each housing can be individually initiated as desired by disrupting the seal for example, by (mechanically or by hand) breaking, puncturing, or removing the seal.
- Figure 4 Another exemplary embodiment is shown in Figure 4 that generally includes a strip 400 of reactant housings which are defined by a series of cavities 405 formed in the strip 400.
- the cavities 405 are filled with reactant 410.
- the cavities may be filled with reactant devices.
- Figure 4 further depicts a seal 420 disposed about the cavities 405.
- the strip may have one or more permeable layers (not shown) and/or a seal disposed about the orifice.
- the seal is disposed on the permeable layer such that it can be removed without disrupting the permeable layer.
- the strip is rolled 430 for convenient storage and dispensing.
- Such apparatus can take the form of a blister pack strip.
- Figure 5 depicts a compartment 440 for holding a rolled strip 430 similar to that depicted in Figure 4.
- the compartment includes an opening 450 through which the strip 400 is dispensed.
- the compartment is impermeable to initiating agent.
- the compartment includes a sealing device adjacent the opening to seal the strip within the compartment from initiating agent (e.g., water vapor) in the environment.
- initiating agent e.g., water vapor
- the apparatuses of the present invention may be enclosed in a compartment for convenient dispensing of the gas generating devices.
- the compartment may be of any shape or material suitable for holding the strips or cassettes of the present invention.
- the housing includes an opening through which the gas generating devices (e.g., contained within the housings of a strip) may be dispensed.
- the opening can include a sealing device.
- a seal disposed about the housing orifice is unnecessary.
- the apparatus is a strip disposed in a compartment substantially impervious to initiating reagent.
- a retaining stracture and/or a permeable layer may be sufficient to hold the reactant or reactant devices in the reactant housing.
- reactant and reactant devices can be dispensed using a housing similar to the one shown in Figure 5.
- reactant devices that are connected, but not necessarily encapsulated or enclosed in housings can be dispensed from a device similar to that shown in Figure 5.
- sachets and other reactant devices may be attached or separably attached in a strip. Accordingly, if • the orifice is hermetically sealed around the devices that are to be dispensed such that the seal is impervious to the initiating agent, e.g. water vapor or water, and the housing also is impervious to the initiating agent, the reactant devices can be packaged, shipped, stored and dispensed over an extended period of time in and from the container.
- the initiating agent e.g. water vapor or water
- Figure 6 depicts yet another exemplary an apparatus and method of dispensing gas generating devices from an apparatus made in accordance with the present invention.
- a plurality of gas generating devices 610 are disposed in the reactant housings 620 of the apparatus 670.
- the reactant devices 610 include a rigid stracture 630 that contains reactant 640 and that is sealed inside the rigid stracture 630 with a permeable layer 650.
- These reactant devices are positioned within the housings 620 of the apparatus 670 during assembly of the apparatus 670 and the housings 620 are sealed on both sides by a seal 660.
- the seal is made of a material that can be punctured by applying pressure to the gas generating device contained in each housing of the cassette.
- the seals 660 are shown in Figure 6 prior to their being sealed to the apparatus 670.
- the barrier layer would be sealed to the housing during assembly, shipped and stored with the seals affixed.
- the dispensing device 680 e.g., a plunger
- the reactant device 610 is ejected from the opposite side of the housing 610 through the seal 660 on the opposite side of the housing 610. The process is repeated as necessary so as to achieve the desired amount of gas.
- the apparatus includes a dispensing device which is suitable for disrupting the seal of at least one of the reactant housings.
- the dispensing device may include a plunger.
- the apparatuses of the present invention may be made by a variety of processes well known in the art, including, but not limited to, molding, thermoforming, and injection molding. Moreover, the apparatuses of the present invention may be made of any material suitable for the intended purpose and the method of manufacture. Preferably, the apparatus is made of a polymeric material or composite.
- The. apparatus may be either flexible or rigid. For example, where the apparatus is a strip to be rolled and enclosed within a housing, the apparatus should be flexible. Alternatively, where the apparatus is for use with a spindle as depicted in Figure 1, the apparatus is preferably rigid. • .
- the seals about the reactant orifice housings need not be applied in a continuous strip, but can be discreet and applied and removed individually.
- the cassettes can have many configurations, shapes and dimensions adaptable to the purpose at hand, e.g., when relatively large or small amounts of gas are desired, the reactant devices, housing and apparatus can be scaled up or down as appropriate.
- the present invention provides for a one-piece cassette, which requires less tooling, thus resulting in lower manufacturing costs.
- Those skilled in the art may design the apparatus with other features as appropriate such that one cassette size and configuration can be used in a variety of devices and for a variety of purposes. This flexibility allows for the manufacture of the cassette with one mold, cast, or form, thereby, further lowing manufacturing costs.
- the cassette can be recycled or reused, e.g., by refilling the cassette with reactant and reseating the reactant housings.
- the present invention further provides methods for generating gas.
- the seal (and, optionally, a retaining stracture) of an apparatus, as described herein is disrupted so as to expose the reactant or reactant devices to an initiating agent, thereby generating gas.
- the terms "disrupt”, “disrupting”, and “disrupted” refer to any process that removes the respective layer (e.g., seal, retaining stracture, barrier layer, etc.) as a substantial barrier to the orifice of the housing by, for example, rapturing, breaking, puncturing, opening or simply removing the layer.
- a plunger or similar device or mechanism may puncture the seal (as shown in Figures IB and 2).
- the plunger or alternative mechanism does not need to retract if the mechanism is small profile. Therefore, dispensing can be manual or automatic, and the mechanism can be less complex than if retraction were necessary. Alternatively, the plunger may retract.
- the methods of the present invention allow for sequential and repeated ⁇ generation of gas in desired amounts.
- the apparatuses and methods of the invention may be part of an automated or manual system to generate a desired amount of gas as necessary. For example, the seals (and retaining structures) of a plurality of housings may be disrupted sequentially so as to generate the desired amount of gas.
- either the plunger or the cassette may rotate following the disruption of the seal, so that the plunger is aligned with a non- disrupted seal and prepared to disrupt another seal as necessary.
- the system is designed to deliver gas in a controlled and sequential manner.
- the present invention can be used to control the rate and amount of the gas generated, e.g., by controlling the amounts of reactants retained in each housing, by modifying the reactant or reactant devices within the housings of the apparatus to control the rate and efficiency of the reaction, and/or by controlling the rate at which the reactants are exposed to initiating agent and/or delivered from the cassette.
- the apparatus can be used to deliver the reactant or reactant devices at desired times and rates to an environment, such as a water reservoir.
- the apparatus can retain the reactant or reactant devices during delivery, which can be effected by, e.g., removing or disrupting a barrier to initiation of the reactants, such as a water vapor barrier when the initiating agent is water.
- the apparatus can be designed for manual and/or mechanical delivery of gas at desired times such as the filling of a water reservoir (e.g., in a water tank in a boat or camper, a humidifier, water lines, or dental lines), and can be used to periodically deliver gas to control contaminants such as bacteria, viruses and the like.
- the apparatuses and methods disclosed herein may be used in a variety of systems, including, for example, bleaching, disinfection, deodorization, sanitization and sterilization.
- the apparatus and methods disclosed herein may be used on such equipment including, but not limited to, food or beverage equipment, dental equipment, or medical equipment.
- the apparatus and methods disclosed herein may be used in, but not limited to, military and camping equipment, water purification apparatuses, clean-in-place process equipment, spray bottles and canisters.
- the apparatus and methods disclosed herein may be used in solution dispensing devices.
- the apparatus may be used in a spray bottle in which chlorine dioxide is generated by the methods and apparatuses disclosed herein and subsequently used to clean surfaces of, for example, food or beverage equipment:!
- chlorine dioxide can be used for the disinfection of water, e.g., municipal water treatment: as a disinfectant for foods, beverages, fruits and vegetables; and for the cleaning and disinfection of medical, dental and food equipment.
- Chlorine dioxide has been shown to be an effective disinfectant at concentrations as low as 0.2 mg/L.
- Chlorine dioxide is a desirable replacement for chlorine, the traditional water treatment chemical, because it has been found to inactivate microbes at lower levels and over a wider pH range.
- chlorine dioxide can be used to reduce or eliminate biofilms because it penetrates the cell wall of naturally occurring, colony-building microorganisms and disrupts the proteins necessary for reproduction.
- chlorine dioxide does not produce chlorinated byproducts, e.g., trihalomethanes.
- it has been found to be active against pathogens that are resistant to chlorine. It can be used as a slimicide in paper or pulp machines, for wastewater treatment, and for industrial water treatment, e.g., cooling or recycle streams. It can be used for odor control or as an aerial biocide and viracide.
- Sulfur dioxide also has a variety of uses, such as a mold and fungus inhibitor for use in shipping and storing fruits and vegetables. Based on the teachings disclosed herein the practitioner of ordinary skill will appreciate the numerous other applications for which the present invention can be used and provides a heretofore unmet need.
- the apparatuses and methods of the present invention may be used in consumer or commercial devices that include water reservoirs and/or conduits such as humidifiers, cisterns, coffee makers, beverage machines, water coolers, water towers, heating systems employing water, and the like, to periodically clean, sanitize or disinfect the water in the reservoir and/or any associated fluid lines.
- Such an apparatus can include devices that automatically generate chlorine dioxide at set times (e.g., weekly or whenever the reservoir is refilled) at set concentrations (e.g., 50 ppm).
- the apparatus can be manually actuated to generate the chlorine dioxide gas and can be manipulated to select one or more concentrations (e.g., by actuating more than one reactant device).
- the apparatus can include a 1 device to automatically generate gas every time a reservoir is manually filled.
- a humidifier might include a device that is actuated by insertion of a refilled reservoir to generate gas, e.g., by rotating a cassette about a spindle that causes a pin (e.g., a spring- activated pin) to engage or otherwise disrupts a seal in one on or more reactants ; ; , housings.
- a pin e.g., a spring- activated pin
- the chlorine dioxide reactant device may be physically ejected from the apparatus into the reservoir.
- the reaction or device may be retained in the apparatus by a retaining stracture or permeable membrane to be disposed of after some or all of the housings have been employed to generate gas.
- the apparatus can be used to periodically sanitize or maintain a sanitizing level of gas in a reservoir and/or conduit with gas (e.g., chlorine dioxide), preventing the growth of or eliminating contaminants, such as biofilm.
- gas e.g., chlorine dioxide
- This apparatus also is advantageous because it can be employed to prevent the dissemination of contaminants (e.g., bacteria) into the environment (e.g., by a humidifier) or into food or beverages (e.g., by a coffee machine or water cooler).
- the apparatuses and methods of the present invention may be used to sanitize or clean equipment such as medical, laboratory or dental equipment.
- the apparatus of the invention includes or is used with a device that automatically or manually effects a cleaning cycle.
- the apparatus can be employed to periodically run a cleaning cycle in equipment, e.g., by flushing the system with chlorine dioxide in solution, e.g., at 50 ppm, and optionally flushing with water.
- Such apparatus and methods can be particularly advantageous because they do not require a user to remember to run a cleaning cycle or load reactants or reactant devices every time a cleaning cycle is necessary or desirable.
- the apparatus and method can be made semi-automatic, e.g. , by employing a timer with a signal or light to remind the user that a cleaning cycle is due, and a means to manually actuate the cycle.
- a cassette is positioned in a spray bottle or other dispensing device or application device for cleaning fluid such that upon filling the reservoir of the spray bottle or other device with water, the apparatus can be actuated (e.g., by rotating a cassette), automatically or manually, thereby triggering the dispensing device to break the seal of a housing (e.g., with a spring-loaded plunger or pin), and thereby delivering gas to the reservoir. Following an appropriate amount of time (e.g., 10 minutes or 1 hour), sufficient chlorine dioxide is delivered to the bottle. (e.g., to effect a concentration of 50 parts per million) to create an effective sanitization solution.
- Such devices can be particularly advantageous, e.g. , in restaurants, hospitals, and other institutions where sanitization of surfaces is desired.
- the apparatuses provide ; convenient preparation of cleaning solutions.
- the invention provides one or more apparatus of the invention (e.g., one or more cassettes or strips) with instructions for use of the apparatus.
- the instructions e.g., can include information on how to obtain a desired concentration of gas in a reservoir, or how to install the apparatus into another device.
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Abstract
L'invention concerne des procédés et un dispositif permettant de déclencher une pluralité de réactions de génération de gaz individuelles coïncidemment ou séquentiellement. De manière générale, l'invention concerne un dispositif définissant une pluralité de logements de réactif. Un joint est disposé autour de l'orifice de l'un des logements de réactif et peut être rompu en vue du déclenchement de la génération d'un gaz par exposition du réactif à un initiateur. L'opération peut être réitérée à souhait, ce qui permet de générer de manière sûre et sans inconvénient des concentrations souhaitées de gaz à des intervalles de temps souhaités.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44906503P | 2003-02-20 | 2003-02-20 | |
| US60/449,065 | 2003-02-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004073755A1 true WO2004073755A1 (fr) | 2004-09-02 |
Family
ID=32908687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2004/005194 Ceased WO2004073755A1 (fr) | 2003-02-20 | 2004-02-20 | Dispositif de distribution de gaz et procedes d'utilisation correspondants |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2004073755A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017106685A1 (fr) * | 2015-12-18 | 2017-06-22 | Sabre Intellectual Property Holdings Llc | Procédés d'extraction d'huiles et de graisses à partir d'une matière solide à l'aide de dioxyde de chlore |
| US20220126254A1 (en) * | 2020-10-27 | 2022-04-28 | Selective Micro Technologies, Llc | Gas micro reactor utilizing membrane packaging |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2046577A (en) * | 1978-06-22 | 1980-11-19 | Freyberg Chem Fab Werner | Method and apparatus for fumigating |
| US4444310A (en) * | 1982-07-26 | 1984-04-24 | Becton, Dickinson And Company | Segmented multi-product package assembly |
| EP0291991A2 (fr) * | 1987-05-20 | 1988-11-23 | JOHNSON & JOHNSON MEDICAL, INC. | Organe de raccordement pour système d'injection de fluide et dispositif de valve pour injecteur |
| US5965264A (en) * | 1996-09-18 | 1999-10-12 | Bernard Technologies, Inc. | Powders providing controlled sustained release of a gas |
| US20010038805A1 (en) * | 2000-02-18 | 2001-11-08 | Richard Hamilton | Apparatus and method for controlled delivery of a gas |
-
2004
- 2004-02-20 WO PCT/US2004/005194 patent/WO2004073755A1/fr not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2046577A (en) * | 1978-06-22 | 1980-11-19 | Freyberg Chem Fab Werner | Method and apparatus for fumigating |
| US4444310A (en) * | 1982-07-26 | 1984-04-24 | Becton, Dickinson And Company | Segmented multi-product package assembly |
| EP0291991A2 (fr) * | 1987-05-20 | 1988-11-23 | JOHNSON & JOHNSON MEDICAL, INC. | Organe de raccordement pour système d'injection de fluide et dispositif de valve pour injecteur |
| US5965264A (en) * | 1996-09-18 | 1999-10-12 | Bernard Technologies, Inc. | Powders providing controlled sustained release of a gas |
| US20010038805A1 (en) * | 2000-02-18 | 2001-11-08 | Richard Hamilton | Apparatus and method for controlled delivery of a gas |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017106685A1 (fr) * | 2015-12-18 | 2017-06-22 | Sabre Intellectual Property Holdings Llc | Procédés d'extraction d'huiles et de graisses à partir d'une matière solide à l'aide de dioxyde de chlore |
| US20220126254A1 (en) * | 2020-10-27 | 2022-04-28 | Selective Micro Technologies, Llc | Gas micro reactor utilizing membrane packaging |
| US12036525B2 (en) * | 2020-10-27 | 2024-07-16 | Selective Micro Technologies, Llc | Gas micro reactor utilizing membrane packaging |
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