WO2004021811A2 - Multiple hazard protection articles and methods for making them - Google Patents
Multiple hazard protection articles and methods for making them Download PDFInfo
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- WO2004021811A2 WO2004021811A2 PCT/US2003/028099 US0328099W WO2004021811A2 WO 2004021811 A2 WO2004021811 A2 WO 2004021811A2 US 0328099 W US0328099 W US 0328099W WO 2004021811 A2 WO2004021811 A2 WO 2004021811A2
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- WIPO (PCT)
- Prior art keywords
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- sodium
- compounds
- radiation protective
- tungsten
- Prior art date
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Classifications
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
- G21K1/10—Scattering devices; Absorbing devices; Ionising radiation filters
-
- 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
- D06M17/00—Producing multi-layer textile fabrics
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H1/00—Personal protection gear
- F41H1/02—Armoured or projectile- or missile-resistant garments; Composite protection fabrics
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/10—Organic substances; Dispersions in organic carriers
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F3/00—Shielding characterised by its physical form, e.g. granules, or shape of the material
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F3/00—Shielding characterised by its physical form, e.g. granules, or shape of the material
- G21F3/02—Clothing
Definitions
- the present invention relates to articles, including fabrics, compounds and film layers, which can provide protection against life threatening hazards, such as radiation, chemicals, biological agents, metal projectiles and fire.
- the fabrics and films of the present invention are used to produce garments with multiple hazard protection and superior heat dissipating properties.
- radiopaque materials are incorporated into polymeric films, such as in Shah's U.S. Patent No. 5,245,195 and Lagace's U.S. Patent No. 6,153,666.
- HazardGard I® and microporous-film based fabrics such as DuPont's NexGen® or Kappler's Proshield 2®. These chemical protective fabrics typically provide protection against biological agents also.
- the bullet proof vests and bomb suits of the prior art tend to have poor heat dissipation properties. These bullet proof vests and bomb suits can be so uncomfortable to wear when it is hot that the user will choose to forego protection, rather than risk becoming overheated. This poor heat dissipation also has another disadvantage in military applications. When a soldier's body heat is allowed to build up inside a bullet proof vest or bomb suit, the soldier will have a high so-called "heat signature" in the other areas of the soldier's body where heat can be released. This uneven "heat signature" will allow that soldier to be easily located by an enemy's thermal imaging equipment. For the sake of survival in a high technology battlefield, it is better for the soldier to dissipate heat rapidly throughout his or her body and thereby have an even "heat signature.”
- the present invention is directed to articles, including fabrics and film layers, which can protect against multiple hazards, including radiation, chemical, biological agents, metal projectiles and fire hazards.
- the fabrics and films of the present invention are used to produce garments with multiple hazard protection and superior heat dissipating properties.
- the protective fabric or film can be used to produce a poncho, protective tent, nuclear detection probe, wallpaper, house siding, roofing material, composite house foundation or a liner for a commercial aircraft cabin, airport scanner, food irradiation machine or x-ray room.
- the materials of the present invention can be incorporated into a paint or coating and applied to a wide variety of surfaces.
- a radiation protective compound is preferably created by mixing a radiation protective material, such as barium, bismuth, tungsten or their compounds, with a powdered polymer, pelletized polymer or liquid solution, emulsion or suspension of a polymer in solvent or water.
- the polymer may advantageously be selected from a broad range of plastics including, but not limited to, polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate and polyester.
- the radiation protective polymeric mixture is then preferably combined with one or more layers of fabric.
- the radiopaque polymer composite can be laminated onto one or more commercially available fabrics which provide protection against hazardous chemicals, biological agents, metal projectiles or fire.
- the commercially available fabrics include polyethylene fabrics such as DuPont's Tyvek®, polypropylene fabrics such as Kimberly- Clark's Kleenguard® or Kappler's Proshield®, plastic laminate fabrics such as DuPont's TyChem® or Kimberly Clark's HazardGard I®, microporous-film based fabrics such as DuPont's NexGen® or Kappler's Proshield 2®, carbon sphere composite fabrics such as Blucher GmbH's SaratogaTM and aramid fabrics such as DuPont's Kevlar® or Nomex®.
- a film capable of providing protection against hazardous chemicals, biological agents, fire or metal projectiles can be laminated or otherwise adhered to a radiation protective fabric or film of the present invention.
- This additional film can be formed from a variety of polymeric materials, such as polyethylene, polypropylene, polyurethane, neoprene, polytetrafluoroethylene (Teflon®), KaptonTM, MylarTM or combinations thereof.
- heat dissipating compounds such as copper, silver, aluminum gold, beryllium, tungsten, magnesium, calcium, carbon, molybdenum, and/or zinc, can be added to the radiation protective polymeric mixture before it is applied to one or more layers of fabric.
- a polymeric, heat dissipation layer can be specially created and adhered to the radiation protective fabric.
- the radiation protective fabric can be incorporated into a bullet proof vest or bomb suit.
- bullet proof vests and bomb suits are constructed with aramid and/or polyethylene fabric layers which are sewn together.
- a radiation protective fabric layer can be sewn between or laminated onto the aramid and/or polyethylene fiber layers.
- Chemical and biological protection can also be imparted by sewing in or laminating chemical protective films with the aramid and/or polyethylene bulletproof fabrics.
- known fire retardant fabrics such as the aramid Nomex® or Kevlar® fabrics produced by DuPont, can be combined with the bullet proof, radiation protective, chemically resistive, biologically resistive and/or heat dissipating fabric layers of the present invention either by sewing or laminating to create a garment which provides protection against many forms of life threatening hazards.
- a garment can be characterized as a "universal" protective garment.
- the principles of the present invention can also be applied to a broad range of other articles, including surgical hoods, hospital gowns, gloves, patient drapes, ponchos, partitions, coverings, jumpsuits, uniforms, fatigues, tents, envelopes, pouches, wallpaper, liners, drywall, house sidings, house foundations, radiation probes etc.
- transparent items with radiopaque qualities such as an impregnated eye shield, can be attached to or incorporated within the protective garments of the present invention.
- FIG. 1 shows a full body suit capable of protecting its user against one or more life threatening hazards.
- FIG. 2 shows a cross-section of a composite fabric having a central polymer layer with multiple forms of radiation protective material.
- FIG. 3 shows a cross-section of a two layer radiation protective composite fabric which illustrates how the fabric can be made both breathable and radiation protective.
- FIG.4 shows a cross-section of a multiple layer radiation protective article which provides enhanced radiation protection.
- FIG.5A shows the front view of medical apron capable of protecting its user against one or more life threatening hazards.
- FIG. 5B show the rear view of the medical apron of FIG. 5 A.
- FIG. 6 shows a two piece suit capable of protecting its user against one or more life threatening hazards.
- FIG. 7 shows a cross-section of a radiation protective drywall incorporating the radiation protective materials of the present invention.
- FIG. 8 shows a wall cross-section which incorporates radiation protective materials of the present invention.
- FIG. 9 shows a foundation cross-section which incorporates radiation protective materials of the present invention.
- FIG. 10 is a perspective view of a probe which incorporates radiation protective materials of the present invention.
- FIG. 11 shows a cross-section of a six layer fabric which provides multiple forms of hazard protection.
- FIG. 12 shows a bullet proof vest which incorporates radiation protective films or other protective fabrics of the present invention.
- FIG. 13 shows a preferred process for forming a radiation protective fabric or other material by applying a liquid polymer incorporating a radiation protective material between two sheets.
- FIG. 14 is an enhanced version of the process shown in FIG. 13 which creates an additional hazard protection layer.
- FIG. 15 shows a second process for fo ⁇ ning a radiation protective fabric or other material by applying a liquid polymer incorporating a radiation protective material between two sheets.
- FIG. 16 shows an enhanced version of the process shown in FIG. 15 which creates an additional hazard protection layer.
- FIG. 17 shows an expanded process for creating a fabric with multiple forms of hazard protection.
- FIG. 18 shows a preferred process for producing a polymer film incorporating radiation protective materials.
- FIG. 19 shows an alternative process for producing a polymer film incorporating radiation protective materials.
- FIG. 20 shows an enhanced version of the FIG. 19 process which creates a film having multiple hazard protective properties.
- FIG. 1 shows a full body suit 10 which is constructed from hazard protecting fabrics of the present invention.
- the full body suit 10 should preferably be a one-piece jumpsuit which covers every portion of the human body.
- Elastic bands 12, 14 can be used around the hand and foot areas to help insure a tight fit.
- the gloves 16, booties 18 and hood 20 can be separate pieces which overlap with the rest of the jumpsuit so as to leave no skin surface exposed.
- the full body suit 10 can also include hook and loop fasteners or a zipper flap 28 to allow the user to easily enter the full body suit 10.
- a transparent eye shield 24 is preferably included with the full body suit 10 to provide protection for the face.
- the eye shield 24 could be hinged, such as with comer rivets 26, in order to allow the user to flip the shield 24 up and down.
- the eye protection can be a stand alone device, such as safety glasses (not shown).
- the eye shield 24 preferably incorporates lead or similar radiation protective glass.
- FIG. 2 shows a cross-section of a composite fabric 50 with an intermediate radiation protective polymeric layer 60 that can be used for the full body suit of FIG. 1 to provide radiation protection.
- the intermediate polymeric layer 60 which includes radiation protective materials 62, 64, 66, 68 in addition to polymers 52, is sandwiched between two layers of fabric or other material 34, 36.
- the outside fabric or other material 34, 36 is preferably flat and pliable. It can be, for example, a non-woven, polymeric fabric, such as polypropylene, polyethylene, aramid fabric, rayon or any mixture of these.
- the outside fabric or other material can be a woven fabric, such as cloth, or can be another flat, pliable material, such as paper or film.
- barium sulfate, tungsten and bismuth are preferred choices for the present invention because, as compared with lead, for example, they are lighter in weight, less expensive and have fewer known heath hazards.
- Other radiation protective materials can also be used, including, but are not limited to, barium, other barium compounds (e.g., barium chloride), tungsten compounds (e.g., timgsten carbide and tungsten oxide), bismuth compounds, tantalum, tantalum compounds, titanium, titanium compounds, Diatrizoate Meglumine Inj.
- radiopaque materials can be purchased from a variety of chemical supply companies, such as Fisher Scientific, P.O. Box 4829, Norcross, Georgia 30091 (Telephone: 1-800-766-7000), Aldrich Chemical Company, P.O. Box 2060, Milwaukee, Wisconsin (Telephone: 1-800-558-9160) and Sigma, P.O. Box 14508, St. Louis, Missouri 63178 (Telephone: 1-800-325-3010).
- Fisher Scientific P.O. Box 4829, Norcross, Georgia 30091 (Telephone: 1-800-766-7000), Aldrich Chemical Company, P.O. Box 2060, Milwaukee, Wisconsin (Telephone: 1-800-558-9160) and Sigma, P.O. Box 14508, St. Louis, Missouri 63178 (Telephone: 1-800-325-3010).
- smaller particle sizes of the radiation protective materials such as submicron sizes, are preferred. Nonetheless, the added cost of purchasing such small size particles must be weighed against the importance of the additional protection achieved.
- Those of skill in the art will readily recognize that other radiation protective materials
- the radiation protective materials are embedded in a polymeric mixture 60.
- the polymeric mixture 60 preferably includes a polymer 52, one or more radiation protective materials 62, 64, 66, 68 and one or more additives.
- the polymer 52 may be selected from a broad range of plastics including, but not limited to, polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate (EVA) and polyester.
- the additives are typically chemicals to improve the flexibility, strength, durability or other properties of the end product and/or to help insure that the polymeric mixture has an appropriate uniformity and consistency.
- additives might be, in appropriate cases, plasticizers (e.g., epoxy soybean oil, ethylene glycol, propylene glycol, etc.), emulsifiers, surfactants, suspension agents, leveling agents, drying promoters, flow enhancers etc. Those skilled in the plastic processing arts are familiar with the selection and use of such additives.
- plasticizers e.g., epoxy soybean oil, ethylene glycol, propylene glycol, etc.
- emulsifiers e.g., surfactants, suspension agents, leveling agents, drying promoters, flow enhancers etc.
- the proportions of these various polymeric mixture ingredients can vary. Using a greater proportion of radiation protective materials will generally impart greater radiation protection. Nonetheless, if the proportion of radiation protective materials is too high, the polymeric mixture will become brittle when dried or cooled and easily crumble apart. The inventors have found from their work that over 50% of the polymeric mixture, by weight, can be barium sulfate, tungsten, bismuth or other radiation protective materials, with most of the rest of the mixture consisting of the polymer.
- the inventors typically use a polymeric mixture for their radiation protective compound containing approximately 85% by weight of radiation protective materials and approximately 15% by weight of polymer.
- the currently preferred combination of radiation protective materials used in the DEMRONTM polymeric mixture are tungsten (75%), barium sulfate (20%) and bismuth (5%).
- the currently preferred polymers used in the DEMRONTM polymeric mixture are ethyl vinyl acetate (EVA) and polyethylene.
- the currently preferred outside fabric layers used for DEMRONTM are a woven cloth and a non-woven fabric, such as DuPont's Tyvek® and TyChem® flashspun polyethylene fabrics.
- Using the Tyvek® and/or TyChem® fabrics for DEMRONTM has the advantage of adding chemical and biological protection properties to DEMRONSTM radiation protection properties.
- the intermediate polymeric layer 60 illustrated in FIG. 2 includes several types of radiation protective materials 62, 64, 66, 68.
- These radiation protective materials 62, 4, 66, 68 can be, for example, a barium compound 62, a tungsten compound 64, a bismuth compound 66 and an iodine compound 68.
- the radiation protective article can be more effective in blocking different forms of radiation than a similar article with a single radiation protective material.
- some radiation protective materials might be more effective in blocking beta particles , while others will be more effective in blocking gamma rays.
- the article will have a greater ability to block both beta particles and gamma rays.
- lead as one of the radiation protective materials for such a hybrid application, or even more generally, for the type of plasticized articles disclosed herein. While, because of its potential health hazards, lead would not be as prefe ⁇ ed as the other radiation protective materials previously listed, lead nonetheless might have a role in a plasticized radiation protective mixture or in certain other plastic film applications.
- two radiation protective layers 110, 112 of the type previously described can be perforated and staggered as illustrated in FIG. 3. As shown in FIG. 3, the two radiation protective layers 110, 112 are separated by a gap 114. To prevent the gap 114 from collapsing, the gap 114 can be filled with a very porous woven or non- woven fabric, such as cloth (not shown). Both of the two radiation protective layers 110, 112 have been perforated to create patterns of holes 116, 118, 120.
- radioactive particles which travel in an essentially straight line, would be blocked by at least one of the two layers, while air, which can bend around obstructions, will still be allowed to pass through.
- the radiation protective materials previously described or aluminum could be formed into fibers and woven into a garment or interwoven with conventional garment material, such as cloth, to provide both the flexibility of a cloth garment and the radiation protection of metallic lead garment.
- the radiation protective material can also be incorporated within a variety of clear plastics or glass to create, for example, a clear eye shield 24 of the type shown in FIG. 1 having radiopaque qualities.
- perforated or unperforated sheets of pure radiation protective materials, such as aluminum can be inserted into an article to impart radiopaque qualities.
- FIG.4 shows a second approach to enhancing radiation protection through a particular multi-layer construction 80.
- each of the layers 81, 82, 83 of this multi-layer product 80 have different thicknesses. While a layer of one thickness 81 might be capable of stopping radiation 84 with certain wave characteristics, it might allow radiation of different wave characteristics 86 to pass right through. Nonetheless, by backing up the first layer 81 with additional layers of different thicknesses, there is a greater chance of stopping different types of radiation, regardless of their wave characteristics.
- the layers 81, 82, 83 might be constructed with different radiation protective materials.
- the barium, tungsten and/or bismuth radiation protective materials have been found by the inventors to provide cost effective protection against alpha and beta particles, but not as much protection against neutrons.
- boron and/or beryllium films might advantageously have approximately 50% by weight of radiation protective materials and approximately 50% by weight of polymer and additives.
- an effective approach would be to combine a polymeric layer with barium, tungsten and/or bismuth compounds 81 with a polymeric layer having boron and/or beryllium compounds 82.
- a synergistic effect might also be achieved by combining the different radiation protective materials 62, 64, 66, 68 as shown in FIG.
- FIGS. 5 A, 5B and 6 show that a wide variety of garments can be formed from the hazard protecting films and fabrics of the present invention and are not limited to the full body suit 10 shown in FIG. 1.
- FIG. 5 A shows the front view of a medical apron 130 which is constructed from the hazard protective films and/or fabrics of the present invention.
- the illustrated apron 130 covers the chest 132, upper arms 134 and neck 136 of the user with a hazard protecting film or fabric, such as the radiation protective fabric previously discussed.
- wrap around straps 138 are constructed at the lower waist portion of the apron 130 to allow the apron 130 to be firmly secured to the user's body. These wrap around straps 138 might advantageously include hook and loop fasteners (not shown) to firmly hold the strap ends 139 together.
- FIG. 5B provides a rear view of the FIG. 5 A medical apron 130.
- This rear view shows how the wrap around straps 138 are crossed in the back so that the ends 139 can meet at the front of the apron 130.
- This rear view also shows upper body connecting strap 140 which keeps the apron fitting tightly to the user's upper torso.
- hook and loop fasteners can advantageously be used to removably fasten at least one end of the upper body connecting strap 140 to the medical apron 130.
- an open area 142 is left in the back of the medical apron 130 so that all the apron fits more easily to the user's body.
- This area 142 is left open on the assumption that the user's front and sides will be exposed to the hazard, rather than the user's back. Of course, if the user's back is at risk, this area 142 should not be left open.
- FIG. 6 shows that the hazard protecting films and fabrics of the present invention can be formed into a two piece suit 150.
- This two piece suit includes pants 152, jacket 154 and hood 158 constructed out of the hazard protecting films and fabrics of the present invention.
- a belt 156 can be used to hold the jacket 154 tightly against the pants 152.
- a gas mask 159 can be used to provide protection against inhalation of hazardous gases.
- this two piece suit 150 is advantageous for military applications where flexibility is needed. For example, on a hot day, a soldier may only want to wear the pants 152 and belt 156 in order to keep cool, while having the jacket 154, hood 158 and gas mask 159 are kept nearby in case a chemical, radiation or biological threat becomes imminent.
- FIGS. 7-10 illustrate that the hazard protecting materials of the present invention are not limited in their usefulness to fabrics and garments.
- FIG. 7 illustrates, for example, how radiation protective materials can be incorporated into common drywall 120.
- the radiation protective materials of the present invention such as barium sulfate, tungsten or bismuth, can be mixed with the gypsum commonly used in drywall and then inserted 122 between two layers of cardboard 124, 126.
- FIGS. 8 and 9 illustrate how the hazard protecting materials of the present invention can also be used on other construction applications.
- FIG. 8 shows a cross- section of the type of wall 160 which might be used for a house or other building.
- This wall 160 might include drywall 162, insulation 166, exterior sheathing 164, exterior drainage paper 168 and housing wrap 169.
- the hazard protections of the present invention can be incorporated into any and all of these wall layers. Incorporation of radiation protection into common drywall has already been discussed in connection with FIG. 7.
- Radiation protective materials such as barium sulfate, tungsten or bismuth, can also be mixed into or spray adhered to insulation materials 166.
- the housing wrap 169 used in construction is often a polymeric film such as DuPont's Tyvek®.
- a polymeric film such as DuPont's Tyvek®.
- radiation protection can be added to a flashspun polyethylene Tyvek® type fabric by laminating a radiation protective polymeric mixture on to the Tyvek® type fabric.
- radiation protection can be added to the materials commonly used for exterior sheathing 164 and exterior drainage paper 168.
- FIG. 9 illustrates how hazard protection can be added to the foundation 170 of a house or other building.
- a foundation may consist of reinforced concrete 174 upon which floorboards 172 and the house's or building's wall 160 stand.
- radiation protective materials such as barium sulfate, tungsten compounds or bismuth compounds, can be mixed into the reinforced concrete 174 used in the foundation 170.
- a layer of film or fabric 176 of the present invention can be inserted between the reinforced concrete 174 and floorboards 172 of the foundation 170.
- radiation protective materials can either be mixed into the exterior roofing material (e.g., ceramic tiles), laminated onto the exterior roofing material (e.g., shingles) and/or a hazard protecting film or fabric 176 of the type shown in FIG. 9 can be inserted between the exterior roofing material and the internal roofing structure.
- exterior roofing material e.g., ceramic tiles
- exterior roofing material e.g., shingles
- a hazard protecting film or fabric 176 of the type shown in FIG. 9 can be inserted between the exterior roofing material and the internal roofing structure.
- FIG. 10 illustrates how the composite radiation protective compounds of the present invention can be used to create injection molded objects.
- the injection molded object illustrated in FIG. 10 is a radiation measuring probe 180 which can be inserted into the earth and used to help find deposits of radioactive materials.
- This radiation measuring probe 180 includes a slidable outer sleeve 182, an inner housing 184, a detection window 188 and a flange 186 which is used as a stop for the slidable outer sleeve 182.
- the problem with such radiation measuring probes is that they let in so much extraneous radiation through the outer sleeve 182 and inner housing 184 that it is difficult to get a reliable reading of whether the detected radiation is coming from the direction of the detection window 188.
- the outer sleeve 182, inner housing 184 and flange 186 can be constructed from the type of polymeric mixture incorporating radiation protective materials which has previously been described. As before, adding a greater proportion of radiation protective materials to the mixture will generally impart greater radiation protection but, if the proportion of radiation protective materials is too high, the polymeric mixture will become brittle when dried or cooled and easily crumble apart. As such, the proportions of polymer and radiation protective materials should be selected to create a sturdy probe when produced through an injection molding process which would otherwise have a sufficient amount of radiation protective materials to block background radiation.
- FIG. 11 a composite fabric cross-section 200 is illustrated which can provide protection against life threatening hazards in addition to that posed by radiation, such as toxic chemicals, infectious biological agents, fire and metal projectile hazards.
- a composite fabric cross-section 200 is illustrated which can provide protection against life threatening hazards in addition to that posed by radiation, such as toxic chemicals, infectious biological agents, fire and metal projectile hazards.
- this multiple hazard protection composite fabric there are the previously mentioned three layers of composite fabric with a radiation protective polymer mixture 34, 36, 60 (see, FIG. 2).
- additional layers 210, 220, 230 which can protect against different hazards.
- a nonporous chemical protective layer 210 and or 220 can be added to the three radiation protective layers 34, 36, 60.
- This nonporous chemical layer can either be polymer film 210 which is laminated onto the three radiation protective layers 34, 36, 60 and/or a chemical protective fabric 220 which is sewn or otherwise adhered onto the three radiation protective layers.
- This chemical protective layer 210, 220 can be constructed of known chemical protective polymers and/or fabrics.
- one known class of chemically protective fabrics are non-woven textiles, such as the flashspun polyethylene fabric sold by DuPont under the tradename Tyvek®, polypropylene fabrics such as Kimberly-Clark's KleenguardTM, Kappler's Proshield 1TM, Lakeland's Safeguard 76TM, fabrics mixing polyethylene with polypropylene and cellulose based fabrics such as DuPont's SontaraTM and Kimberly Clark's PrevailTM.
- a similar type of non-woven textile would be the class of plastic films laminated onto one or both sides of a nonwoven fabric including DuPont's TyChem® series of fabrics, Kimberly Clark's HazardGard I, HTM fabrics, Kappler's CPFTM and Responder series of fabrics and ILC Dover's Ready 1 fabricTM. These non-woven textiles would typically be combined with the three radiation protective layers 34, 36, 60 by sewing or otherwise adhering the fabrics together. [0061] Chemical protection can also be imparted by using polyvinyl chloride and/or chlorinated polyethylene films, such as ILC Dover's ChemturionTM. These films could be laminated or extruded onto the three radiation protective layers 34, 36, 60 of the present invention.
- Another class of chemical protective layers are polymer films with microscopic pores laminated onto fabric such as Gore-tax® or polypropylene based fabrics such as DuPont's NexGenTM, Kimberly Clark's Kleenguard UltraTM, Lakeland's Micro-MaxTM and Kappler's Proshield 2TM. Chemical protection can further be provided by materials incorporating an absorbent layer, such as the carbon/fabric combinations sold by Blucher GmbH and Lanx.
- Another class of chemically protective fabrics are woven fabrics coated with rubber or plastic on one or both sides.
- coated chemically protective fabrics include polyvinyl chloride and nylon composites, polyurethane/nylon composites, neoprene/aramid composites, butyl/nylon composites, chlorinated polyethylene/nylon composites, polytetrafluoroethylene (i.e., Teflon® )/fiberglass composites and chlorobutyl aramid composites.
- the chemical protective layer 210, 220 is preferably nonporous, it will also provide protection against infectious biological agents. r
- the fabric shown in FIG. 11 can provide a broad measure of protection with only the addition of a chemical protective layer 210, 220 to the three radiation protective layers 34, 36,60, further or alternative layers 210, 220, 230 can nonetheless also be chosen to protect against additional hazards or promote heat dissipation.
- layer 220 in FIG. 11 could be another woven or nonwoven fabric layer and layer 230 could be a fire protection layer, such as a layer produced from the Nomex® fire resistant aramid fabric manufactured by DuPont.
- fire resistant materials include combinations of the Nomex® and Kevlar® aramid fabrics such as that sold by Southern Mills, combinations of melamine resin with aramid fibers, combinations of polytetrafluoroethylene (i.e., Teflon®) with aramid fibers, combinations of rayon with aramid fibers, combinations of polybenzimidazole with aramid fibers, combinations of polyphenylenebenzobisoxazole with aramid fibers, combinations of polyimide with aramid fibers and MylarTM plastic films.
- layer 230 could be a bullet or shrapnel resistant layer produced from bullet stopping aramid and/or polyethylene fibers.
- layer 230 of a heat dissipation material may alternatively be prudent to form layer 230 of a heat dissipation material.
- One way of forming such a heat dissipation layer is to mix compounds with high thermal conductivity, such as silver, copper, gold, aluminum, beryllium, calcium, tungsten, magnesium, zinc, iron, nickel, molybdenum, carbon and/or tin, with a polymer in the same way that the radiation protective materials are mixed with polymers to form radiation protective layer 60.
- a six layer hazard protecting fabric 200 is illustrated in FIG. 11, those of skill in the art will readily recognize that a multiple hazard protecting fabric can be created with more or less than six layers.
- the woven or non-woven fabric layers 34, 36, 220 illustrated in FIG. 11 can be omitted. It is also possible to combine different hazard protecting or heat dissipating layers together into a single layer.
- the radiation protective layer 60 of the present invention has been found to provide superior heat dissipating properties on its own, these heat dissipating properties can be enhanced by adding strong thermal conductors, such as silver, copper and/or aluminum, to the mixture of radiopaque materials in the radiation protective layer 60.
- FIG. 12 a bullet proof vest 300 is illustrated which has additional hazard protecting properties.
- Most of the bullet proof vest 300 is of conventional design, similar to that shown in Borgese's U.S. Patent No. 4,989,266, the disclosure of which is hereby incorporated by reference.
- the bullet proof protection is primarily provided by layers of polyethylene fibers 314 and/or aramid fibers 316.
- Commercially available polyethylene fabrics used for bulletproof vests include Honeywell's SpectraTM series of ultra high molecular weight polyethylene fabrics and Honeywell's SpectraguardTM ultra high molecular weight polyethylene fabrics which also include fiberglass.
- the bullet proof vest has one or more layers of aramid fibers 316 sandwiched between layers of polyethylene fibers 314. To obtain greater levels of protection against bullets and shrapnel, one typically creates a greater number of layers of aramid fibers 314 and/or polyethylene fibers 316. Additional strength can be created by laying plies of the bulletproof material at 90 degree orientations to one another and encapsulating them between layers of thermoplastic. Ceramics and plates can be added to provide even higher levels of protection.
- an additional layer 320 of the type illustrated in FIGS. 2, 4 or 11 can be inserted.
- This additional layer 320 can, in one embodiment, be a composite radiation protecting layer 50, 80 of the type shown in FIGS. 2 and 4.
- the bullet proof vest would achieve protection against radiation as well as bullets and shrapnel.
- the added layer 320 In the case of radiation protection alone, one would usually want the added layer 320 to be situated close to the user's body in order to take advantage of the superior heat dissipation properties of the radiation protective layer 50, 80 of the present invention. By contrast, in the case of a fabric imparting fire, chemical and/or biological protection, one would typically want that layer near the outside of the bullet proof vest in order to prevent those contaminants from permeating into the bullet proof vest 300.
- FIGS. 13-20 illustrate different manufacturing techniques which can advantageously be used to create hazard protective fabrics of the present invention.
- FIG. 13 illustrates a manufacturing technique that is particularly suited for mass production of radiopaque fabrics or other flat, pliable materials of the type illustrated in FIG. 2 for use in garments and other articles.
- the FIG. 13 process begins with one or more rolls 430, 432 of fabric or other flat, pliable material 34, 36 to which the polymer mixture will be applied.
- a non-woven, polymeric fabric, such as polypropylene, polyethylene, aramid, rayon or any mixture of these is preferred for this process because these polymeric fabrics have been found to bind well with the liquid polymeric mixture and, in some cases, provide inherent hazard protections.
- this process may also be accomplished using woven fabrics, such as cloth, and other flat, pliable materials, such as paper or films.
- a corona treatment may be applied to the fabric or other material by one or more corona treaters 438, 439.
- the radiation protective liquid polymer mixture is applied to one side of the unwound fabric or other material 34 through the use of an applicating unit 440.
- This applicating unit 440 would typically have a roller 442 to roll a thin layer (e.g., preferably 0.1 - 20 millimeters in thickness) of the liquid polymeric mixture onto one side of an unwound fabric or other material 34.
- the polymerized fabric 444 is then preferably passed through a hot air oven 446 to partially dry the thin layer of polymeric mixture before it is sent into a laminating unit 448.
- the coated fabric 444 is preferably combined under heat and pressure with a second sheet of fabric or other material 36 to create a sandwich-like radiation protective fabric 50.
- the sandwich-like radiation protective fabric or other material can then be perforated and/or embossed, as desired, in a perforating/ embossing unit 452.
- the finished radiation protective product will then be wound into a final roll 454 to be shipped to a suitable location for use in fabricating garments or other articles. While two layers of fabric or other material 34, 36 have been shown in this FIG. 4 example, one could alternatively apply the polymeric mixture to a single sheet of fabric or other material 34 (i.e., like an open faced sandwich).
- FIG. 14 shows an enhanced version of the process illustrated in FIG. 13 which can create a fabric with multiple hazard protections.
- the two rolls of fabric 430, 432 and applicating unit 440 can be used to create a sandwich-like radiation protective fabric of the type shown in FIG. 2.
- the two rolls of fabric 430, 432 can be rolls of bullet protecting aramid and/or polyethylene fiber fabrics.
- a third fabric roll 470 and a second applicating unit 476 can be added to the process.
- the fabric in roll 470 would typically be of the same woven, non-woven or bullet resistant fabric as rolls 430, 432.
- the second applicating unit 476 should then preferably impart a liquid polymeric mixture with a different, non-radiation type of hazard protection, such as a chemical, biological or fire protection.
- the liquid polymeric mixture from second applicating unit 476 could deposit a heat dissipating layer having strong thermal conductors, such as silver, copper or aluminum, being imbedded in a polymeric mixture.
- the sandwich-like radiation protective fabric is combined with the additional layer 480 of hazard protecting fabric to create a composite fabric 490 having multiple forms of hazard protection.
- the composite fabric 490 can then be perforated and/or embossed, as desired, in a perforating/embossing unit 452 and then wound into final roll 494. Nonetheless, where the additional layer imparts chemical and/or biological protection, this perforating/embossing step should be avoided.
- the polymeric mixture ingredients 570 are placed into the hopper 571 of a first extruder 572.
- the polymeric mixture 570 preferably includes a polymer, one or more radiopaque materials and one or more additives.
- these polymeric mixture ingredients 570 can enter the hopper 571 in a solid form.
- the polymeric mixture ingredients are preferably heated into a viscous liquid state and mixed together through the turning action of the motorized extruder screw 573.
- the combination of a perforated plate and rotary cutter 574 chops the exiting polymeric mixture into pellets 575. These pellets 575 are then preferably inserted into the hopper 576 of a second extruder 577. Again, through heating and a motorized screw 578, the polymeric mixture is melted. This time, when the polymeric mixture ingredients are pushed out of the extruder 577, a slotted plate at the end of the second extruder 579 is used to extrude a thin film of liquefied polymeric mixture 600. This thin film 600 might advantageously be on the order of 0.1 - 20 millimeters thick. In order to simplify the process steps, this thin film 600 could be produced by the first extruder 572 alone. Nonetheless, by eliminating the second extruder 577, there is a greater chance that the polymeric mixture will not be evenly mixed before it is extruded.
- the liquefied polymeric mixture in the FIG. 15 process is preferably sandwiched between two sheets of fabric or other material 590, 592.
- the fabric sheets are preferably unwound from fabric rolls 594, 596.
- Corona treaters 596, 598 may again be used to enhance the binding process.
- the thin film of liquefied polymeric mixture 600 is applied simultaneously between both sheets of fabric or other material 590, 592.
- FIGS. 16 and 17 show an enhanced version of the process illustrated in FIG. 15 which can create fabrics with multiple hazard protections.
- the FIG. 16 process includes an extruder 622 for producing a radiation protective film 626.
- This radiation protective film is created by placing polymeric mixture ingredients 620 into a hopper 621.
- the polymeric mixture preferably includes a polymer, one or more radiopaque materials and one or more additives.
- the hopper 621 feeds the polymeric mixture ingredients 620 into the extruder 622.
- the polymeric mixture ingredients are preferably heated into a viscous liquid state and mixed together through the turning action of the motorized extruder screw 623.
- a slotted plate 624 at the end of the extruder is used to extrude a thin film of liquefied polymeric mixture 626.
- a preceding extruder similar to extruder 572 in FIG. 15, can be used to better insure that the polymeric mixture placed into the hopper 621 of extruder 622 is evenly mixed.
- the second extruder 632 in the FIG. 16 process is placed in parallel with the first extruder 622 to simultaneously produce a second film 636 which is combined with the radiation protective first film 626.
- the film 636 produced by the second extruder 632 provides a different type of hazard protection than the film 626 produced by the first extruder 622.
- the second extruder 632 might advantageously be used to produce a complementary chemical, biological or fire protection film 636.
- a complementary film 636 a different type of polymeric mixture is loaded into hopper 631, heated into a liquid form and mixed together through the turning action of the motorized extruder screw 633.
- a slotted plate 634 at the end of the extruder 632 is used to extrude a thin film of liquefied polymeric material 636.
- the liquefied polymeric films 626, 636 from the two extruders 622, 632 are then preferably combined as they are sandwiched between two sheets of fabric or other material 590, 592.
- the fabric sheets are preferably unwound from fabric rolls 594, 596. Corona treaters 596, 598 may again be used to enhance the binding process.
- the composite film 638 is inserted between the two sheets 590, 592, the two sheets 590, 592 are then preferably compressed and heated between the rollers of a laminating unit 602 and perforated and/or embossed, as desired, in a perforating/embossing unit 604.
- FIG. 17 illustrates how the principles of FIGS. 13-16 can be used to create a fabric with any number of hazard protecting properties.
- the FIG. 17 process starts with a roll of fabric or other material 656.
- a sheet 658 is pulled from this fabric roll 656 and used as a substrate to deposit a polymeric layer from extruder 660.
- the sheet 658 might be a bullet or shrapnel protecting fabric produced from aramid and or polyethylene fibers and the polymeric layer 661 might be the type of radiation protecting polymeric mixture previously described.
- the sheet 658 might be a chemical or fire resistant fabric, such as a flashspun polyethylene, polyvinyl chloride or polypropylene chemical protective fabric or an aramid fire resistant fabric.
- a chemical or fire resistant fabric such as a flashspun polyethylene, polyvinyl chloride or polypropylene chemical protective fabric or an aramid fire resistant fabric.
- an additional layer of hazard protecting material such as a chemical or biological protecting polymer layer
- a third type of hazard protecting polymer 681 such as a fire protecting or heat dissipating polymer
- this process could continue with as many further extruders as are need to impart all of the hazard protecting properties desired.
- the composite fabric is then heated and compressed at laminating unit 682.
- the final multiple hazard protecting fabric 684 is then taken up into roll 690 for convenient storage and use.
- this protective film process preferably starts by putting a suitable polymer mixture 732 into the hopper 734 of an extruder 730.
- this polymer mixture 732 preferably consists of a polymer, one or more radiation protective materials and any appropriate additives.
- the hopper 734 feeds the polymer mixture into the extruder 730, the polymer mixture is heated into a viscous liquid state and churned by the motorized extruder screw 736.
- a slotted plate 738 at the end of the extruder produces a film 740 of radiation protective polymer which is deposited on endless conveyor belt 742 and cooled.
- the endless conveyor belt 742 preferably has a: polished metal or Teflon® coating in order to prevent the film from needlessly sticking to the conveyor belt 742.
- a fan, blower or refrigeration unit (not shown) may be used.
- the protective film 740 has sufficiently cooled, it can be wound into a final roll 744 for convenient storage.
- the final roll 744 of hazard protective film can then be used for any number of the applications discussed herein, including the manufacture of garments, tents, envelopes, wallpaper, liners, house sidings, house roofings, house foundations etc.
- FIG. 19 shows a variation of the process illustrated in FIG. 18.
- the FIG. 19 process begins by putting the polymeric mixture 732 into the hopper 734 of an extruder 730.
- the polymeric mixture is again heated and churned by the motorized extruder screw 736. This time, though, the polymeric mixture is preferably heated to the consistency of a paste, rather than into a viscous liquid state.
- a slotted plate at the end of the extruder 738 again produces a film of hazard protective polymer 748 which is deposited on endless conveyor belt 742.
- the pasty film 748 exits the endless conveyor belt 742, it is fed into calender rollers 750, 752 which simultaneously heat and compress the pasty film 748.
- the polymer molecules will typically cross-polymerize to form longer molecular chains which results in a stronger material.
- the finished film 754 is pulled by take up rollers 755, 756 and then preferably wound into a final roll 758 for convenient storage and later use.
- FIG. 20 shows an enhanced version of the FIG.19 process which can be used to create a free standing film capable of providing multiple hazard protections.
- the FIG. 20 process involves using an extruder 730 to heat and chum a polymer mixture 732 into a pasty film 748.
- this pasty film 748 is a polymer having radiation protection capabilities.
- this pasty film 748 is fed into calender rollers 750, 752 which simultaneously heat and compress the pasty film 748. After leaving the calendering rollers 750, 752, the film 754 is pulled by take up rollers 755, 756, 758 and moved forward to a second set of calendering rollers 850, 852.
- the film 754 is combined with a second film 810 produced by second extruder 800.
- the second extruder 800 preferably produces a film 810 with a different type of hazard protection, such as chemical, biological, fire or heat protection.
- the two films 754, 810 are heated and compressed together.
- the composite film 854 is then pulled by a second set of take up rollers 854, 855, 858 and preferably wound into a final roll 870 for convenient storage and later use.
- the fabric can be removed from the barium sulfate solution and air dried. Drying can also be accomplished through use of a drying lamp or a microwave assembly. Since barium sulfate is capable of blocking radiation, the impregnation of barium sulfate into a fabric provides the ability to block radiation, while still allowing breathability.
- additives can include adhesives, fixatives and/or emulsifiers to enhance the adhesion and or thicken the solution of the radiation protective material.
- an adhesive such as Gum Arabic or Guar Gum
- the adhesive might be added to the fabric, rather than the barium sulfate solution. The pre-treated fabric would then be soaked or dipped in the barium sulfate solution.
- the radiation protective materials of the present invention can also be impregnated into fabric using alternative techniques.
- the radiation protective material is in particulate form in solution (e.g., as a precipitate)
- one alternative technique is to choose a fabric with pores that are smaller in size than the particles of radiopaque material, but larger in size than the solvent (e.g., water or alcohol) used for the radiopaque solution.
- the radiopaque solution can then be passed through the fabric in a manner where the fabric will act as a filter to filter out the radiopaque particles while allowing the solvent to pass through.
- the filter pore size should be on the order of 2 microns and co ⁇ espond to Whatman's pore size 5.
- the solution of radiopaque particles can be sprayed onto the fabric. Again, after the fabric has been sufficiently impregnated with the radiopaque material, it can then be dried and assembled into a garment or other type of article.
- a reaction chamber can be created with a solutions of complementary reagents on each side and the fabric is placed in the middle.
- these reagents might be barium chloride and sulfuric acid, respectively.
- a chemical reaction will occur between the barium chloride and sulfuric acid which will leave behind a barium sulfate precipitate in the fabric.
- the fabric can be formed with one reagent incorporated within the fabric (e.g., as either a compound or free radical) and then exposed to the other reagent in order to create a resulting radiopaque impregnation.
- one reagent incorporated within the fabric e.g., as either a compound or free radical
- the fabric might advantageously be formed with barium or sulfate as part of the fabric and then exposed to the other compound in order to create the barium sulfate impregnation.
- the type of plasticized protective fabrics described in the present application could, for example, be used as liners for vehicles, x-ray scanning machines, x-ray rooms or airplane cabins.
- the radiation protective fabrics or other materials of the present invention could also be formed into envelopes or pouches to protect sensitive materials (e.g., photographic film, electronics) from being damaged. Since the toxicity of lead is a real concern, the radiation protective materials of the present invention may also be used to replace lead in many of its current applications, including the solder used for printed circuitboards.
- the radiopaque materials of the present invention could be finely ground up and mixed into latex or oil based paints.
- Emulsifiers, binding agents or suspension agents may be added to such paints to keep the radiation protective materials well mixed so that they do not precipitate out of solution, emulsion or suspension.
- radiation protective materials Through the addition of such radiation protective materials, radiation protection can be painted or coated onto any number of surfaces in order to provide protection from the dangers of radiation.
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- Ceramic Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Laminated Bodies (AREA)
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- Chemical Or Physical Treatment Of Fibers (AREA)
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Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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AU2003268544A AU2003268544B2 (en) | 2002-09-09 | 2003-09-05 | Multiple hazard protection articles and methods for making them |
JP2004534753A JP5301757B2 (en) | 2002-09-09 | 2003-09-05 | Articles to protect against multiple hazards and methods for making them |
MXPA05002656A MXPA05002656A (en) | 2002-09-09 | 2003-09-05 | Multiple hazard protection articles and methods for making them. |
CN038241080A CN1689120B (en) | 2002-09-09 | 2003-09-05 | Multiple hazard protection articles and methods for making them |
KR1020127002435A KR101238426B1 (en) | 2002-09-09 | 2003-09-05 | Multiple hazard proctection articles and methods for making them |
EP03749514.0A EP1547096B1 (en) | 2002-09-09 | 2003-09-05 | Multiple hazard protection articles and methods for making them |
CA2498312A CA2498312C (en) | 2002-09-09 | 2003-09-05 | Multiple hazard protection articles and methods for making them |
IL167330A IL167330A (en) | 2002-09-09 | 2005-03-09 | Multiple hazard protection articles and methods for making them |
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US10/238,160 US6828578B2 (en) | 1998-12-07 | 2002-09-09 | Lightweight radiation protective articles and methods for making them |
US10/620,954 | 2003-07-16 | ||
US10/620,954 US6841791B2 (en) | 1998-12-07 | 2003-07-16 | Multiple hazard protection articles and methods for making them |
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Also Published As
Publication number | Publication date |
---|---|
CA2498312A1 (en) | 2004-03-18 |
JP5301757B2 (en) | 2013-09-25 |
MXPA05002656A (en) | 2005-06-08 |
AU2003268544A1 (en) | 2004-03-29 |
EP1547096B1 (en) | 2018-04-11 |
WO2004021811A3 (en) | 2005-01-13 |
CN1689120B (en) | 2012-05-09 |
RU2005110425A (en) | 2005-10-10 |
KR101343521B1 (en) | 2013-12-20 |
JP2005538356A (en) | 2005-12-15 |
EP1547096A2 (en) | 2005-06-29 |
RU2320037C2 (en) | 2008-03-20 |
CN1689120A (en) | 2005-10-26 |
EP1547096A4 (en) | 2010-04-14 |
AU2003268544B2 (en) | 2008-11-13 |
US20040004196A1 (en) | 2004-01-08 |
CA2498312C (en) | 2012-11-27 |
KR20050072742A (en) | 2005-07-12 |
US6841791B2 (en) | 2005-01-11 |
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