JP2008538136A - Radiation-sensitive protective article - Google Patents

Abstract

Disclosed are compositions and methods for forming radiopaque polymeric articles. In one embodiment, radiological inspection apparatus and methods are used to determine the presence and attributes of such radiopaque polymer articles. The radiopaque polymer article of the present invention mixes a radiopaque material, such as barium, bismuth, tungsten or compounds thereof, with a powdered polymer, pelletized polymer or polymer solution, emulsion or suspension in solvent or water. Can be created by doing. In addition to creating radiation-sensitive objects, the radiopaque polymeric materials of the present invention can also be used to make radiation protection articles such as radiation protection clothing and bomb containment vessels. Also, increased radiation protection can be achieved through the use of nanomaterials. The principles of the present invention can be used to provide protection against other types of hazards including flame, chemical, biological and projectile hazards.

Description

The present invention relates to radiation-detectable protective articles. The radiation-detectable articles of the present invention can be easily detected through the use of X-rays and other radioactive emissions. The methods and compositions for producing such radiation-sensitive articles also apply to the creation of articles that protect against radiation and other types of hazards such as flame, chemical, biological and projectile hazards. be able to.

This application claims priority from US patent application Ser. No. 11 / 019,952 filed on Dec. 20, 2004 (the contents of this application are incorporated herein by reference for all purposes). This application was filed on July 16, 2003 and is a continuation-in-part of application 10 / 620,954, issued as U.S. Pat.No. 6,841,791, entitled `` Multiple Hazard Protection Articles And Methods For Making Them '' This application was filed on Sep. 9, 2002, issued as U.S. Pat.No. 6,828,578 entitled `` Lightweight Radiation Protective Articles And Methods For Making Them '' and U.S. Pat.No. 6,828,578 on Dec. 7, 2004. This is a continuation-in-part of application No. 10 / 238,160 issued as B2, which was filed on August 27, 2001 and issued as US Patent No. 6,459,091 B1 on October 1, 2002 No. 09 entitled “Lightweight Radiation Protective Garments” No. 940,681, a continuation-in-part application, filed December 7, 1998 and issued as US Patent No. 6,281,515 on August 28, 2001, entitled "Lightweight Radiation Protective Garments" This is a continuation-in-part of No. 09 / 206,671. The disclosure in each of these prior applications is incorporated herein by reference.

BACKGROUND OF THE INVENTION Radiation has been used in many ways by humans. The most well known destructive use of radiation is atomic bombs. The electromagnetic radiation emitted by the atomic bomb penetrates deeply into human tissue and damages human cells. In recent years, the threat posed by atomic bombs has increased with the increasing realization of terrorism and the very realistic possibility that terrorists can use nuclear waste that can be easily entered and exited to produce “dirty bombs”. There is no doubt. Such destructive threats to humanity from nuclear bombs have created the need for cost-effective radiation protection, including the need for lightweight radiation protection suits. Ideally, such lightweight radiation protection clothing should simultaneously provide protection against other types of hazards such as flames, chemical, biological, projectile hazards and other forms of electromagnetic radiation. I will. In this way, first responders, such as firefighters, paramedics, police officers, or military personnel, can use one piece of clothing to provide themselves with protection against all types of hazards that they can expect to face. it can. Such a “universal” protective garment is the applicant's co-pending application filed July 16, 2003 entitled “Multiple Hazard Protection Articles And Methods For Making Them”, the disclosure of which is incorporated herein by reference. 10 / 620,954 (Patent Document 1).

  Many constructive uses have also been developed to take advantage of radiation. These constructive uses include medical x-rays and nuclear power plants. However, other constructive uses of radiation have not yet been discovered. For example, many industries use automated high-speed machines to produce products quickly and inexpensively. The food industry is one such industry. For example, the manufacture and packaging of many popular brand breakfast cereals is largely done by machines. In order to market this mass-produced breakfast cereal, breakfast cereal makers often include extras or “freebies”, such as a model of a popular superhero, in a cereal box. This prize is usually inserted and sealed by the machine during the packaging process.

  The need for quality control procedures arises when high speed automated manufacturing methods are used. Returning to the boxed cereal example, if the boxed cereal assembly machine runs out of prizes or the prize inserter becomes clogged, many serial boxes may be sealed, shipped and sold without prizes. unknown. In the case of children's cereals, boxed cereals are often bought for prizes in the box, and if the manufacturer cannot pack the prizes in the cereal box, it can lead to customer anger and disappointment.

  As such, especially in high speed manufacturing technology, whether the manufactured product is made in full compliance with the company's manufacturing standards (e.g. include any premium), and that the product is free of foreign matter. It is necessary to be able to inspect immediately that it is not included. In the case of boxed cereals, this ensures that all of the cereal boxes that are considered to contain freebies actually contain freebies and do not contain foreign objects, such as stones or metal, that could accidentally get mixed into the final assembly. Including.

  Human visual inspections are often performed to maintain quality control, but visual inspections are difficult to perform effectively on products manufactured on high speed assembly lines. One challenge with visual inspection is to give the inspector enough time to perform an appropriate inspection without slowing down the manufacturing process. When trying to detect giveaways in a cereal box, this challenge is the fact that the cereal box is visually opaque and therefore not suitable for visual inspection of items such as giveaways in the cereal box. Complicated by.

U.S. Patent Application 10 / 620,954

SUMMARY OF THE INVENTION The present invention includes compositions and methods for forming radiopaque polymer articles. When these radiopaque polymer articles are used in high-speed automated manufacturing methods, their attributes and presence can be easily ascertained through the use of radiological inspection equipment.

  The radiopaque polymer article of the present invention mixes a radiopaque material such as barium, bismuth, tungsten or compounds thereof with a powdered polymer, palletized polymer or polymer solution, emulsion or suspension in solvent or water. Can be created by doing. The polymer is advantageously, but not limited to, polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate, polyester, acrylonitrile-butadiene-styrene, acrylic, polycarbonate, polyoxymethylene, acetal. Can be selected from a wide range of plastics, including polytetrafluoroethylene (TEFLON ™), ionomers, cellulose, polyetherketone, silicones, epoxies, elastomers, polymer foams and other polymer compounds.

  The radiopaque polymer mixture can then be used to form radiopaque polymer articles by a number of existing industrial methods such as injection molding, extrusion and thermoforming. For example, in the case of injection molding, the radiopaque polymer mixture can be heated in an extruder and then injected into a mold until it assumes the shape of the mold. After the radiopaque polymer mixture has cured into a suitable molded shape, it is removed from the mold. In the case of a superhero model, the molded model can be wrapped in cellophane and inserted into a cereal box as a prize.

  Radiopaque articles can also be advantageously formed by spraying, depositing or coating a radiopaque adhesive mixture onto an existing article. For example, a lightweight radiopaque material can be mixed with an adhesive, such as a gum adhesive or a liquid polymer, to form a radiopaque adhesive mixture. The radiopaque adhesive mixture is then applied to an existing article by spraying the radiopaque adhesive mixture onto the article or by immersing the article in the radiopaque adhesive mixture. You can do either.

  During the manufacturing process, a radiological inspection apparatus can be used to detect the presence and attributes of radiopaque polymer articles. In one embodiment, the X-rays are passed through a radiopaque polymer article itself or a radiopaque package containing the radiopaque polymer article. An X-ray detector is then placed on the opposite side of the radiopaque polymer article to detect where the radiation has been attenuated and where it has been transmitted. This X-ray detector can confirm the presence of a radiopaque polymer article and, if desired, verify the attributes of the radiopaque polymer article (e.g., correct dimensions, quantity, presence of defects, etc.) Can do. The X detector can also make sure that unwanted foreign objects, such as stones and scrap metal, are not mixed into the finished product.

  Numerous methods and compositions used to create radiopaque detectable objects can also be used to provide protection against a wide range of ionizing radiation, such as neutrons, ultraviolet light, gamma rays, and high frequencies. it can. In our co-pending prior application No. 10 / 620,954, the disclosure of which is incorporated herein by reference, the radiopaque polymeric compounds of the present invention may in some cases have other hazards (e.g., flames). , Chemical, biological, projectiles, etc.) are used to create radiation protective clothing that can also provide protection. Similarly, the same type of mixture can be sprayed onto clothing to attenuate radiation in the same way that an adherent mixture of radiation protection material can be sprayed onto an existing article to make it radiation sensitive.

  As another part of the present invention, recent advances in nanotechnology can be used to create better radiation detectable and radiation attenuating articles. In certain aspects, these radiation attenuating articles can also provide protection against other types of hazards such as flame, chemical, biological, projectile hazards and a wide range of electromagnetic radiation energy. These nanomaterials exhibit unique electrical, mechanical and optical properties due to their small size and high surface area to volume ratio. In the present invention, various nanomaterials can be used to enhance the mechanical, thermal, damping and barrier protection of the product.

  In the present invention, nanomaterials are used in at least three different ways. In one embodiment, the nanomaterial is disclosed above either to enhance radiation protection or to provide further protection, eg, protection against flame, chemical, biological and / or projectiles. Added to radiation protective polymer material. In a second embodiment, nanoparticles formed from a radiopaque material (e.g., barium, bismuth, tungsten, etc.) replace the bulky form of the same or similar radiopaque material in a radioprotective mixture. Used in. The use of such radiopaque nanomaterials allows for a more uniform distribution of radiopaque material in the polymer mixture and, as a result, higher levels of radiopaque material before the polymer becomes brittle. Can be concentrated. In a third aspect, the nanomaterial is formed as a separate nanomaterial layer. Such a separate nanomaterial layer can either be added to the product or can be formed as an independent product.

  Nanomaterials for use in the present invention include nanoparticles, nanotubes and nanoplatelets. The nanoparticles are mainly formed as solid particles, but can also consist of hollow nanospheres, nanoshells, hemispheres, parabolas, and the like. Nanoparticles can be formed of a variety of metal / nonmetal powders including oxides, sulfides and ceramic powders. Nanoplatelets are layered nanomaterials that include natural and synthetic nanoclays, such as silicic acid and transition metal dichalcogenides (ie, tantalum dichalcogenides that interact with lithium). Nanotubes are tube-like nanomaterials that have a diameter of a few nanometers, yet can be several microns long.

In the case of attenuating electromagnetic radiation such as radio waves, ultraviolet rays and ionizing radiation, the nanoparticles are made of conventional radiopaque materials such as tungsten, tantalum, barium or their compounds, shell structures such as metal coated magnetic particles, For example, it can be formed of Fe ₂ O ₃ / Au, SiO ₂ / Au or other coated semiconductor particles such as PbS / CdS. Nanoparticles with hollow metal, metal oxide / sulfide nanospheres or other compound nanospheres; parabolas, hemispheres and shell structures can also be used in the present invention. Shaped nanoparticles (eg, nanoparabolas, nanohemispheres, nanospheres, etc.) are believed to deflect, reflect and capture radiation in a manner similar to how a mirror deflects, reflects and captures light waves. Because these shaped nanoparticles are thought to attenuate radiation differently than powdered radiopaque nanoparticles, these shaped nanoparticles need not be formed from radiopaque materials. Alternatively, it may be formed from materials such as metal / semiconductor hybrid particles. For example, hybrid CdS coated Ag nanoparticles exhibit red shifted plasmon resonance absorption. This resonant absorption band of metal nanoparticles is a function of particle size. As the particle size decreases, the theoretical wavelength of maximum absorption intensity can be approached. By creating these nanospheres, nanohemispheres, and nanoparabolic structures with specific shapes and curvatures, optical properties can be used for smaller wavelengths of the light spectrum to reduce the frequency of radio, ultraviolet, and ionizing radiation frequencies. Electromagnetic radiation can be attenuated. Rather than being absorbed as in the case of heavy metals, electromagnetic radiation is effectively redirected, shifted or reflected so that its energy is reduced to lower levels or converted to heat.

  In order to increase the chemical properties and flame retardancy of the polymer mixture, nanomaterials of appropriate composition can be uniformly dispersed in the polymer mixture. For example, nanoclays, when properly dispersed in a polymer, form a tortuous path in the polymer matrix, making it difficult for harmful chemicals, biological agents and other gases such as oxygen to penetrate the polymer To enhance its chemical properties. To increase the flame retardancy of polymers, a small percentage of nanoclays or other nanoplatelets in the range of 2-10% can be combined with conventional flame retardants in the nanoscale or micron range, such as alumina trihydrate, water. It can be added along with magnesium oxide or other organic brominated and chlorinated compounds. Nanotubes can be used to increase the mechanical properties of the polymer mixture, such as tensile strength, flexibility, elastic modulus and electrical conductivity.

  There are three general methods for dispersing nanomaterials in polymer mixtures. The first method is the direct mixing of the polymer and nanomaterial, either as separate phases or in solution. The second method is in situ polymerization in the presence of nanomaterials, and the third method is in situ particle processing including in situ formation of nanomaterials and in situ polymerization. Nanomaterials can also be used in several applications such as evaporation, sputtering (glow discharge, ion beam, laser), ion plating, chemical vapor deposition (CVD), plasma enhanced CVD, thermal spraying, dip coating, fluidized bed and spray spraying. A number of substrates can also be coated by technique.

  Also note that nanomaterials tend to agglomerate and reduce their surface area, and therefore the desired properties of the resulting nanocomposite cannot be achieved unless properly dispersed and distributed in the polymer matrix. thing. In order to disperse the nanomaterial in the polymer and process the resulting mixture by standard manufacturing techniques, it is preferable to surface modify the nanomaterial. For example, in the case of nanoclays, the clay surface is modified by a method known as compatibilization so that the nanoclay is attracted to the resin matrix and thus thoroughly dispersed. The two most common compatibilization methods are onium ion modification and ion-dipole interaction.

  By incorporating nanomaterials into the polymer mixture of the present invention or creating high purity nanolayers, a radiation protection shield is created to make the article radiation detectable, radiation protective (ultraviolet, high frequency, electromagnetic radiation, X-rays). Or gamma radiation) or `` universal '' protection (i.e. protection against one or more hazards, e.g. neutron radiation, flame, chemical, biological or projectile hazards) it can. The resulting radiopaque polymer mixture further comprises a chemical film, antiballistic fabric (woven fabric or woven fabric) or flame retardant as described in the previously cited patent application, whether or not it contains nanomaterials. Can be laminated to the material.

DETAILED DESCRIPTION OF THE INVENTION Referring first to FIG. 1, an example of a radiopaque polymer article 10 of the present invention is shown. In this case, the radiopaque polymer article 10 is a giveaway that can be inserted into a cereal box in the form of a plastic toy model. Radiopaque polymer article 10 is preferably formed from a polymer mixture comprising one or more radiopaque materials and one or more polymers. The formulation of one or more radiopaque materials is important for this polymer mixture. The reason is that the polymer itself is transparent to many forms of radiation, such as X-rays, and as such, it is not possible to produce a radiopaque polymer article that is effective using only the polymer. It is not possible.

  As radiopaque materials, barium sulfate, tungsten and bismuth are preferred choices for the present invention because they are less known health hazards compared to, for example, lead. Barium, other barium compounds (eg barium chloride), tungsten compounds (eg tungsten carbide and tungsten oxide), bismuth compounds, tantalum, tantalum compounds, tin, titanium, titanium compounds, Diatrizoate Meglumine (for injection) ) USP (sold by Nycomed under the trade name HYPAQUE ™), Acetrizoate Sodium, boron, boric acid, boron oxide, boron salts, other boron compounds, beryllium, beryllium compounds, bunamiosyl sodium, Sodium diatrizoate, etiozido oil, iobenzamic acid, iocarmic acid, iosetamic acid, iodipamide, iodixanol, iodized oil, iodoalphionic acid, o-sodium iodohypurate, iodo Sodium phthalein, iodopyracet, ioglycic acid, iohexol, iomegramic acid, iopamidol, iopanoic acid, iopentol, iophendylate, iophenoxic acid, iopromide, ioproic acid, iopidol, iopidone, iotalamic acid, Iotrolan, ioversol, ioxagric acid, ioxirane, ipodate, meglumine acetorizoate, meglumine ditrizoate methiodal sodium, metrizamide, metrizoic acid, fenobuthiozil, phentetiothalein sodium, propiperiod , Sodium iodomethamate, sozoiodolic acid, thorium oxide and trypanoate sodium Other radiopaque materials, including but not limited to, can be used. These radiopaque materials are available from a variety of chemical suppliers such as Fisher Scientific, PO Box 4829, Norcross, Georgia 30091 (telephone (not shown for public order and morals violations)), Aldrich Chemical Company, PO Box 2060, Milwaukee, It can be purchased from Wisconsin (telephone (not shown for public order and morals violations)) and Sigma, PO Box 14508, St. Louis, Missouri 63178 (telephone (not shown for public order and morals violations)). One skilled in the art will readily appreciate that other radiopaque materials formulated with the same metal can be used interchangeably with those described above.

  The polymer used in the polymer mixture of the present invention is preferably polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate, polyester, polyisoprene, polystyrene, polysulfone, acrylonitrile-butadiene- A wide range including styrene, acrylic, polycarbonate, polyoxymethylene, acetal, polytetrafluoroethylene (TEFLON ™), ionomer, cellulose, polyetherketone, silicone, epoxy, elastomer, polymer foam and other polymer compounds It can be selected from, but not limited to, plastic.

  Conventional additives may be included in the polymer mixture to improve the flexibility, strength, durability or other properties of the final product, and / or to ensure that the polymer mixture has the proper uniformity and consistency. May help to guarantee. These additives may be used as appropriate plasticizers (e.g. epoxy soybean oil, ethylene glycol, propylene glycol), emulsifiers, surfactants, suspending agents, leveling agents, drying accelerators, adhesives, flow May be an improver and a flame retardant.

  The proportions of these various polymer mixture components can vary. The use of a larger proportion of conventional sized radiopaque material generally allows the radiation detection technology to more easily confirm the presence and attributes of radiopaque polymer articles. Nevertheless, if the proportion of radiopaque material of conventional size is too high compared to the polymer, the polymer mixture becomes brittle and easily disintegrates when dried or cooled. The inventors have found from their work that more than 50% by weight of the polymer mixture can be barium sulfate, tungsten, bismuth or other conventional size radiation protection material, with the remainder of the mixture consisting of polymer. I found that I could do it.

  In one preferred embodiment, the polymer mixture contains about 85% by weight of a conventional size radiopaque material and about 15% by weight of polymer. In this preferred embodiment, the radiopaque materials used in the polymer mixture are tungsten (75%), barium sulfate (20%) and bismuth (5%). The presently preferred polymer for this preferred embodiment is a mixture of ethylene vinyl acetate (EVA) and polyethylene.

  It may be appropriate to consider the use of lead as one of the radiopaque materials for polymer blends. Because of its potential health hazard, lead will not be as preferred as many of the other radiopaque materials listed above, but it still has a role in some radiopaque polymer blends It may be.

  A number of known manufacturing methods can be advantageously used to form the radiopaque polymer articles of the present invention. For example, the radiopaque polymer mixture of the present invention can be first melted in an extruder and then pushed into the mold of an injection molding machine in a molten form by a piston. FIG. 2 shows such an injection molding machine 20. In the embodiment of FIG. 2, a radiopaque polymer mixture 24 is charged into a hopper 26. The hopper 26 then sends the radiopaque polymeric material 24 to the extruder 30 which melts the polymer mixture 24 to a dough-like consistency through the use of an extrusion heater 32. Extrusion screw 34 moves the molten polymer mixture toward mold 40. The molten polymer mixture leaves the extruder 30 and is injected into the mold 40 through the extrusion nozzle 36 under pressure at the same time. As the polymer mixture cools in mold 40, it can be removed from mold 40 in finished form. Further examples of injection molding apparatus and methods are described in Walter US Pat. No. 6,572,801 B1, the disclosure of which is incorporated herein by reference.

  Thermoplastic resins, thermosetting resins and elastomers can all be injection molded. By using multiple inlets (not shown) to the mold 40, a co-injection molding process allows the molding of parts having different materials, colors and / or features. In addition, other types of molding techniques can be used depending on the shape, thickness, weight range, tolerance, surface roughness and economic batch size of the injection molded article. These other types of molding techniques include rotational molding methods, blow molding methods, foam molding methods, compression molding methods, resin transfer molding methods, die casting methods, sand casting methods, for large hollow sealed or semi-sealed structures, Investment casting method, polymer casting method, shape rolling method, die forging method, extrusion method, press forming method, roll forming method, spinning method, thermoforming method, lay-up method, powder method, laser prototype making method and adhesion method However, it is not limited to these.

  Many other known plastic molding techniques can be used to form the radiopaque polymer articles of the present invention. For example, the polymer mixture of the present invention can again be placed in the hopper of an extruder and heated, where it can be deposited on the conveyor belt as a thin film in molten form. Then, a reduced pressure is applied to the thin film, and the molten film is attracted so as to be in close contact with the mold cavity, thereby forming the thin film into a desired shape. Such vacuum forming techniques are described in further detail in Gilbert US Pat. No. 6,319,456 B1, the disclosure of which is incorporated herein by reference. Alternatively, instead of drawing the thin film into a vacuum mold, the thin film sheet can be simply cut into a desired planar shape.

  As a further alternative, an article such as a superhero can be preformed and then rendered radiopaque by the application of a thin radiopaque layer. In such cases, mixing a lightweight radiopaque material with an adhesive, such as a gum adhesive or a liquid polymer, can advantageously form a radiopaque layer. The radiopaque adhesive mixture is then applied to the preformed article either by spraying the outer surface of the article or by immersing the article in a solution of the radiopaque adhesive mixture. be able to.

  The mold used in the injection molding method shown in FIG. 2 may be, for example, the shape of the superhero model 10 shown in FIG. Injection molding is used today to produce many other types of plastic articles that can benefit from becoming a radiopaque polymer article of the present invention in addition to prizes. For example, plastic straws are often attached to children's juice cartons so that children can drink without spilling juice. Similarly, plastic tableware, such as a spoon or fork, may be attached to a serving of food when embedded in a plastic container. If a straw or other tableware is missing from the food container, the user must either discard the product or try to eat it manually from the container, thereby managing the associated dirt Either. If the straw or other tableware in this example is made of the radiopaque polymer of the present invention, all containers that leave the assembly line are attached to the radiopaque straws or other It can be confirmed that the tableware is provided.

  Because the straw or other tableware in this example touches the user's mouth, non-toxic radiopaque materials such as barium sulfate, iodine, It may be important to select bismuth or a combination of them or their compounds. A further factor to consider when selecting a suitable radiopaque material is the degree of radiation attenuation that the material provides. For example, in the example of a straw and juice box, a cardboard juice box is free to transmit radiation. Therefore, a radiopaque compound with strong attenuation is not required to produce sufficient radiation contrast between the straw and the box. More specifically, in the examples of straws and juice boxes, radiopaque compounds having a relatively weak attenuation, such as iodine compounds, can be used, and radiopaque compounds having a strong attenuation, such as Bismuth compounds can be used at lower concentrations.

  Other packaging industries will also benefit from the principles of the present invention. In disposable medical products, most of the device is made of plastic, and if the contents are missing, the entire device is likely to fail. Using the radiopaque plastic of the present invention, it can be ensured that all contents of the medical device are present by X-ray inspection of the sealed medical package at the factory. Also in the medical field, catheters can be manufactured with radiopaque materials using the principles of the present invention, which allows careful monitoring of catheter insertion into the human body using an X-ray machine. Will be. By so monitoring the catheter insertion, the physician will be able to ensure that the catheter reaches the correct position within the patient.

  As a further application, guns, knives and explosives are now made of plastic, which cannot be detected by X-ray scanners used at airports. If such plastic guns, knives and / or explosives are in the hands of terrorists, they can be abused to threaten aircraft crew and passengers. Using the principles of the present invention, the government mandates that all plastic guns, knives and explosives be formulated with one or more radiopaque materials of the present invention, X-rays used at airports. It could be easily detectable by a scanning machine. Given the importance of detecting guns, knives and explosives at airports, the government is likely to want to require radiopaque compounds with high attenuation, such as bismuth compounds, to be used for these applications .

  Referring now to FIG. 3, a radiation detection apparatus 50 and method for detecting the radiopaque polymer article 10 of the present invention is shown. In the method shown in FIG. 3, a box or other container 52 containing the radiopaque polymer article 10 moves along the conveyor belt 60 in a high speed manufacturing process. In this preferred embodiment, an x-ray tube 70 is used to generate radiation to detect the presence or absence of the radiopaque polymer article 10 in a box or other container 52. The X-ray tube 70 is controlled by an X-ray controller 72 that transmits a control signal to the high voltage generator 74. The high voltage generator 74 generates an X-ray 76 by applying a high voltage between the anode and the cathode of the X-ray tube 70. A lead plate 78 with a slit 79 is disposed between the X-ray tube 70 and a box or other container 52. This lead plate 79 serves to focus the x-rays on a box or other container 52 to be inspected and to prevent external x-rays from harming manufacturing workers.

  X-rays are detected by an X-ray detector 80 after passing through a box or other container 52 to be examined. The X-ray detector 80 can include a scintillator and one or more MOS image sensors. In such an arrangement, incident X-rays are converted into visible light by a scintillator, and the visible light is detected by a MOS image sensor. On the other hand, the MOS image sensor outputs a detection signal 82 having characteristics corresponding to the amount of incident X-rays detected.

  A data processor 84 is used to analyze the detection signal 82 received from the X-ray detector 80. Since the box 52 itself transmits X-rays uniformly, a detection signal without discontinuities will indicate that the radiopaque polymer article 10 is missing from the box 52. In contrast, because radiopaque polymer article 10 blocks some of the radiation, a detection signal with a sharp discontinuity will usually indicate the presence of radiopaque polymer article 10 in the box. Let's go.

  Further confirmation that the radiopaque polymer article 10 is actually in the box 52 can be made by measuring the level or pattern of X-rays detected by the X-ray detector 80. For example, the amount of radiation detected by the X-ray detector 80 for the box 52 having the radiation-detectable article 10 can be measured and loaded as a template into the data processor 84 memory. The data processor 84 then compares the level for each subsequent box 52 on the conveyor 60 with the stored template value, and if the two values match within a predetermined tolerance, the box 52 is actually radiation-free. The data processor 84 can conclude that it includes the permeable polymer article 10. In contrast, if the data processor 84 concludes that the box 52 lacks the radiopaque polymer article 10, it signals an alarm 86 to alert the person in charge of the missing box 12 be able to. Alternatively, the data processor 84 can instruct the operation unit 88 to either stop the assembly line or eject a missing box from the assembly line.

  For more accurate detection, the X-ray detector 80 may have a pattern of detection pixels that each detect X-ray transmission in a small defined area. In order to establish a template, X-rays are applied to the box 52 containing the radiopaque polymer article 10, and the X-rays are detected by a pixel pattern. Then, the X-ray level detected for each pixel is stored in the memory of the data processor 84 as a template for future inspection. The data processor 84 then compares, for each pixel, the level of radiation detected for each box 52 that was inspected in the manufacturing process with the stored template. Whether the article 10 is included is determined within a predetermined tolerance. The data received from the detailed detection pixels can then be used to determine the shape (eg, outer contour) of the radiopaque polymer article. Moreover, the use of detection pixels also allows analysis of whether there are cracks, cuts or other defects in the radiopaque polymer article 10. The use of pixel data in a radiographic inspection apparatus to detect the presence of cracks or breaks in an article is described in further detail in Sawada US Pat. No. 6,574,303 B2, the disclosure of which is incorporated herein by reference. .

  In addition to detecting the presence and attributes of the desired object in the box, the radiological inspection apparatus 50 shown in FIG. 3 simultaneously or alternatively replaces unwanted contaminants such as stone, mud or scrap metal. It can also be detected. Because such contaminants are likely to attenuate radiation differently than both the box and the radiation transmissive polymer article, data processor 84 uses suspicious differences in detected radiation attenuation to alarm Either 86 can be sounded, or the operation unit 88 can be used to stop the conveyor 60.

  Thus far, the methods and compositions for forming radiopaque detectable articles have been described with emphasis. Nevertheless, many of the same principles apply to the harmful effects of radiation, including ultraviolet, electromagnetic, radio frequency, neutrons, X-rays and gamma rays, and other hazards (e.g. flames, chemical, biological and projectiles). It can be applied to the manufacture of articles to be protected. For example, in our co-pending prior application No. 10 / 620,954, the disclosure of which is incorporated herein by reference, the radiopaque polymeric compounds of the present invention are resistant to radiation and other hazards. Used to create protective clothing. Similarly, in the previous example, the same type of mixture in the same way that an adhesive mixture of lightweight radiation protection material can be sprayed onto a preformed object and glued or coated to make it radiation sensitive. Can be sprayed, glued or coated onto clothing to make it radiation protective.

  FIG. 4 shows a whole body suit 100 constructed from the radiation protective polymer blend of the present invention. In order to provide complete surface protection, the full body suit 100 is preferably a one-piece jumpsuit that covers every part of the human body. Elastic bands 112, 114 can be used around the hand and foot areas to help ensure a tight fit. Alternatively, the glove 116, the boot 118, and the hood 120 can be separate pieces that overlap the rest of the jumpsuit and leave no skin surface exposure. The full body suit 110 may also include a velcro fastener or zipper flap 119 to help the user enter the full body suit 110. Preferably, a transparent eye shield 124 is included in the full body suit 110 to provide facial protection. For convenience, the eye shield 124 may be hinged by, for example, a corner rivet 126 so that the user can pivot the shield 124 up and down. Alternatively, the eye protection may be an independent device, such as safety glasses (not shown). To provide radiation protection, the eye shield 124 is preferably formulated with lead or other radiopaque compound capable of attenuating radiation.

  Referring to Figure 6, when formed into an article, in addition to the dangers posed by radiation, there are a number of life-threatening dangers including toxic chemicals, infectious biological agents, flames and metal projectile dangers. A composite cross-section 200 is shown that can provide protection against. As part of this multi-dangerous protective composite material, two fabric layers 204, 208 can be provided with a radiation protective polymer mixture 206 in between. To these three layers 204, 206, 208, additional layers 210, 220, 230 can be added to protect against various hazards. For example, a non-porous chemical protective layer 210 and / or 220 can be added to the three radiation protective layers 204, 206, 208. This non-porous chemical layer can be a polymer film 210 laminated to three radiation protection layers 204, 206, 208 and / or sewn or otherwise adhered to the three radiation protection layers. It can also be any of the chemical protective cloths 220.

  The chemical protective layers 210, 220 can be constructed of known chemical protective polymers and / or fabrics. For example, one known class of chemical protective fabrics are nonwoven fabrics such as flash spun polyethylene fabrics sold under the trade name Tyvek® by DuPont, polypropylene fabrics such as Kimberly-Clark's Kleenguard®, Kappler's Proshield 1 ™, Lakeland's Safeguard 76 ™, a blend of polyethylene and polypropylene, and cellulosic fabrics, such as DuPont's Sontara ™ and Kimberly Clark's Prevail ™. Similar types of non-woven fabrics include a plastic film class laminated on one or both sides of the non-woven fabric, such as DuPont's TyChem® series fabrics, Kimberly Clark's HazardGard I, II® fabrics, Kappler's CPF ( Trademark) and Responder series of fabrics and ILC Dover Ready 1 fabric (TM). These nonwovens are typically combined with three radiation protection layers 204, 206, 208 by stitching or otherwise attaching the fabrics together.

  Chemical protection can also be imparted by using polyvinyl chloride and / or chlorinated polyethylene films, such as Chemturion ™ from ILC Dover. These films can also be laminated or extruded onto the three radiation protection layers 204, 206, 208.

  Another class of chemical protective layers is a laminate of polymer films with microscopic pores on a fabric, such as Gore-tax® or polypropylene-based fabrics, such as DuPont's NexGen®, Kimberly Clark's Kleenguard. Ultra ™, Lakeland's Micro-Max ™ and Kappler's Proshield 2 ™. Chemical protection can further be provided by materials incorporating the absorbent layer, such as carbon / fabric combinations sold by Blucher GmbH and Lanx. Another class of chemical protective fabrics are woven fabrics coated on one or both sides with rubber or plastic. These coated chemical protective fabrics include polyvinyl chloride / nylon composite, polyurethane / nylon composite, neoprene / aramid composite, butyl / nylon composite, chlorinated polyethylene / nylon composite, polytetrafluoroethylene ( That is, there are Teflon® / glass fiber composites and chlorobutyl / aramid composites.

  The chemical protective layers 210, 220 are preferably nonporous and thus also provide protection against infectious biological agents.

  The fabric shown in FIG. 6 can provide a wide range of protection by simply adding one or more chemical protection layers 210, 220 to the three radiation protection layers 204, 206, 208, but nevertheless Additional layers or alternative layers 210, 220, 230 may be selected to protect against additional hazards or to promote heat dissipation. For example, if the chemical protective layer 210 is a plastic laminate, the layer 220 in FIG. 6 may be another woven or non-woven layer, and the layer 230 may be a flame protective layer, such as Nomex (registered by DuPont). It may also be a layer made from a fire-resistant aramid fabric. Other types of refractory materials include combinations of Nomex® aramid fabrics and Kevlar® aramid fabrics, such as those sold by Southern Mills, melamine resin and aramid fibers, polytetra Combination of fluoroethylene (i.e.Teflon®) and aramid fiber, combination of rayon and aramid fiber, combination of polybenzimidazole and aramid fiber, combination of polyphenylenebenzobisoxazole and aramid fiber, polyimide and aramid There are combinations with fibers and Mylar ™ plastic films. In addition, traditional flame retardant additives include aluminum trihydrate (ATH), magnesium hydroxide or organic brominated or chlorinated compounds. Alternatively, the layer 230 can be a bulletproof or anti-glare shot layer made from aramid and / or polyethylene fibers that do not penetrate the bullet.

  Alternatively, it may be wise to form a layer 230 of heat dissipation material. One method of forming such a heat dissipation layer is the same as mixing a radiation protection material with a polymer to form a radiation protection layer 206, and a high thermal conductivity compound such as silver, copper, gold, and the like. Aluminum, beryllium, calcium, tungsten, magnesium, zinc, iron, nickel, molybdenum, carbon and / or tin are mixed with the polymer.

  Although FIG. 6 shows a six-layer hazard protection cloth 200, those skilled in the art will readily recognize that multiple hazard protection cloths can be created using more or fewer layers. Let's go. For example, the woven or non-woven layers 204, 208 shown in FIG. 6 can be omitted. It is also possible to combine various danger protection or heat dissipation layers into one layer. For example, while the radiation protection layer 206 of the present invention has been found to provide excellent heat dissipation by itself, a strong heat conductor, such as silver, copper and / or aluminum, can be used for the radiation protection layer 206. By adding to the mixture of permeable materials, these heat dissipation properties can be enhanced.

  Referring now to FIG. 7, a bulletproof vest 300 having additional danger protection is shown. Most of the bulletproof vest 300 is a conventional design similar to that shown in Borgese US Pat. No. 4,989,266, the disclosure of which is incorporated herein by reference. Ballistic resistance is primarily provided by a layer of polyethylene fibers 314 and / or aramid fibers 316. Commercially available polyethylene fabrics used in bulletproof vests include Honeywell's Spectra ™ series ultra high molecular weight polyethylene fabric and Honeywell's Spectraguard ™ ultra high molecular weight polyethylene fabric further comprising glass fiber. Commercially available aramid fabrics used in bulletproof vests include DuPont's Kevlar® series aramid fabrics and Akzo's Twaron ™ series aramid fabrics. In this preferred example, the ballistic vest has one or more aramid fibers 316 sandwiched between layers of polyethylene fibers 314. To obtain a higher level of protection against bullets and shrapnel, typically a greater number of layers of aramid fibers 314 and / or polyethylene fibers 316 are created. Additional strength can be created by laying plies of bulletproof material at 90 ° to each other and encapsulating them between layers of thermoplastic resin. Adding ceramics and plates can provide a higher level of protection. The bulletproof vest 300 shown in FIG. 7 is preferably held together by a fabric insert casing 312.

  To add further danger protection to the bulletproof vest 300 shown in FIG. 7, additional layers 320 can be inserted. This additional layer 320 can in one embodiment be a radiation protection layer. By adding such a radiation protection layer to the bulletproof vest, the bulletproof vest will achieve protection against radiation as well as bullets and shrapnel. Similarly, flame, chemical and / or biological protection could be provided by using a multilayer material of the type described in connection with FIG. In the case of radiation protection only, it will usually be desirable to place an additional layer 320 close to the user's body in order to take advantage of the excellent heat dissipation properties of the radiation protection layer. In contrast, in the case of a fabric that provides flame, chemical and / or biological protection, typically the layer is placed on the bulletproof vest to prevent such contaminants from penetrating the bulletproof vest 300. It would be desirable to add near the outside.

  Referring now to FIG. 8, there is shown a multi-piece protective garment 400 that can be used as underwear. In a particular application, there is nothing more than concealing the fact that you are wearing protective clothing. For example, a police officer or other first responder may wish to not warn others that such a danger may exist while being protected against radiation and other dangers. . Similarly, personnel operating an X-ray machine at the airport may panic aircraft passengers for accidental contact with the same X-ray machine while being protected against constant radiation exposure throughout the day. You may not want.

  In the embodiment of FIG. 8, the multi-piece protective garment includes a vest 410, two shoulder flaps 420, a posterior crotch flap 430, an anterior crotch flap 440, and two thigh flaps 450. The vest 410 is attached to the head hole 412 through the user's head so that the front vest panel 414 covers the user's chest and the back vest panel 415 covers the user's back. To fit snugly, the front vest panel 414 is attached to the rear vest panel 415 using the strap 416. The strap 416 can be tightened in a number of well-known ways, including snap buttons, VELCRO ™ fasteners, tie straps, buckles and the like. The back crotch flap 430 and the front crotch flap 440 are used to protect the user's waistline and crotch area. A rear crotch flap 430 is attached to the user's buttocks, and a front crotch flap 440 is attached to the user's crotch. Upper straps 434 and 444 are provided so that the rear crotch flap 430 and the front crotch flap 440 can be attached to the lower portion of the vest portion 410 and suspended from the vest. To fit snugly, lower straps 432, 442 are provided on both crotch flaps 430, 440 and pulled through the crotch to connect to the lower straps 432, 442 from the corresponding crotch flaps 430, 440 can do. In order to protect the user's thigh, two thigh flaps 450 are provided. These thigh flaps 450 are curved so as to be wrapped around the left and right thighs of the user. Each of these thigh flaps is provided with four straps 452, 454. The thigh flap lower strap 452 is wound around the upper leg portion of the user and is fixed to the corresponding thigh flap lower strap 452. In contrast, the upper thigh flap strap 454 can be secured to the lower portion of the front crotch flap 440 or, like the lower thigh flap strap 452, wraps around the user's upper leg and has a corresponding large It can be fixed to the upper thigh flap strap 454. The user's shoulder is protected by a shoulder flap 420. These shoulder flaps 420 are used to cover the left and right shoulders of the user while attached to the upper portion 418 of the vest portion 410. By leaving the side of the vest 410 open and using the shoulder flap 420 attachment, the multi-piece protective clothing 400 of the present invention provides free arm movement while providing vital organ protection. I am considering. Similarly, by separating the vest 410 from the crotch flaps 430, 440 and the thigh flap 450, the user can freely move the legs and torso while also gaining protection for vital organs. .

  The multi-piece protective garment 400 is constructed from the same types of radiation and hazard protection materials as previously described. In the case of radiation protection only, the radiation protective polymer film can be applied to the cloth as described in copending application No. 10 / 620,954 and then cut into the shape shown in FIG. . Or cut a multi-layer material of the type shown in FIG. 6 or a multi-layer composite of the type shown in FIG. 7 into the shape shown in FIG. 8 and include a number of radiation, chemical, biological, flame and projectile hazards. It can also provide protection against danger. In addition to underwear, these same principles apply to the manufacture of dangerous protective blankets, “dirty” or nuclear bomb control blankets, jackets, pants, shirts, drapes, X-ray apron, vests, hats, gloves and similar protective articles. It can also be applied. These same principles can also be applied to the manufacture of vehicles, walls, ships, aircraft, spacecraft, residential foundations and container liners or coatings to block a wide range of electromagnetic and ionizing radiation.

  FIG. 9 shows an alternative embodiment for constructing parts of a multi-piece protective garment 400. In this embodiment, the posterior crotch flap 530 is constructed from a standard fabric in the form of a pocket. The protective layer is then made in the form of an insert 540 that can be fitted over the pocket. In order to prevent the insert 540 from falling out of the pocket 530 after insertion, a strap 536 is sewn into the lower portion of the cloth pocket 530. This pocket 530 and insert 540 approach allows different types of inserts to be used depending on the anticipated danger. For example, if the user is likely to encounter a radiation-only hazard, an insert that protects against the radiation hazard only can be used. On the other hand, if projectiles, chemical or biological hazards are also considered, thicker inserts can be used that will provide protection against those additional hazards. This type of pocket 530 and insert 540 is also a pocket on the back of the vest 410 (see FIG. 8), for example to provide additional protection for the spine or as a belt loop to receive a belt or lumbar support brace It can also be used to form

  Furthermore, recent advances in nanotechnology can be used to create better radiation-detectable protective articles. In certain embodiments, these radiation attenuating articles may also provide protection against other types of hazards, such as flame, chemical, biological, projectile hazards and a wide range of electromagnetic radiation energy.

  A nanomaterial is a material having a structural feature (eg, particle size or particle size) in the range of 1 to 100 nanometers in at least one dimension. These materials exhibit unique mechanical, electrical, electronic and optical properties due to their small size and high specific surface area to volume ratio. In addition, nanomaterials, unlike conventional micron sized materials, are less likely to generate large stress concentrations, which on the other hand increase their yield strength, tensile strength and Young's modulus.

  In the present invention, nanomaterials are used in at least three different ways. In one embodiment, the nanomaterials provide radiation as disclosed above, either to enhance radiation protection or to provide additional protection, eg, flame, chemical, biological and / or projectile protection. Added to the protective polymer material. In a second aspect, nanoparticles formed from a radiopaque material (e.g., barium, bismuth, tungsten, etc.) or other dangerous protective material are replaced by a polymer instead of a bulkier form of the same or similar protective material. Used in the mixture. The use of radiopaque nanomaterials allows for a more uniform distribution of radiopaque material in the polymer mixture, which results in a higher concentration of radiopaque material before the polymer becomes brittle. It becomes possible. In a third aspect, the nanomaterial is formed as a separate nanomaterial layer. Such a separate nanomaterial layer can either be added to the product or it can be formed as an independent product.

  Nanomaterials used in the present invention include nanoparticles, nanotubes and nanoplatelets.

  The first type of nanomaterial used in the present invention is a nanoparticle. Suitable nanoparticles include nanopowders of conventional radiopaque materials, nanoceramics, nanoshells, nanospheres and other nanoparticles in the form of hemispheres and parabolics. By using radiopaque nanopowder instead of bulky radiopaque material, or by blending a mixture of both nano-sized and micron-sized radiopaque powders The relative proportion of radiopaque material in the polymer mixture can be increased. By incorporating a greater proportion of radiopaque nanopowder into the polymer mixture, the resulting product can have an enhanced electromagnetic radiation attenuation capability.

  Radiopaque material nanopowder is commercially available and can be blended into the polymer using standard blending techniques. The types of radiopaque nanopowder that can be used include: tungsten, barium, boron, lead, tin, bismuth, depleted uranium, cerium, yttrium, tantalum, lanthanum, neodymium and their compounds. Tungsten (APS: 100 nm) and tantalum (APS: 100 nm) nanopowder can be purchased, for example, from Argonide Nanomaterial Technologies, Sanford, Florida. Rare earth radiopaque nanomaterials of cerium oxide, yttrium oxide or neodymium oxide can be purchased from NanoProducts Corporation, Longmont, CO.

  Moreover, nanoparticles formed in the form of hollow nanospheres, nanohemispheres, nanoparabolas and nanoshells can be used in the present invention to achieve radiopacity and attenuation of a wide range of electromagnetic radiation. These shaped nanoparticles are believed to deflect, reflect and capture radiation in the same way that mirrors deflect, reflect and capture light waves. These shaped nanoparticles are believed to attenuate radiation differently than powdered radiopaque nanoparticles and therefore do not need to be formed from radiopaque materials, but instead are metal / semiconductor hybrids. It can also be formed from materials such as particles. For example, hybrid CdS coated gold nanoparticles have been shown to exhibit red shifted plasmon resonance absorption. This resonant absorption band of metal nanoparticles is a function of particle size. As the particle size decreases, the theoretical wavelength of maximum absorption intensity can be approached. By creating these metal nanospheres, hemispheres, and parabolic structures with specific shapes and curvatures, optical-like properties are reduced to smaller wavelengths in the electromagnetic spectrum, including radio waves, ultraviolet radiation, and ionizing radiation, such as X-rays and gamma rays. It can be used to attenuate against. These nanoparticles, unlike conventional heavy metals that absorb or scatter electromagnetic radiation, effectively redirect, shift or reflect electromagnetic radiation and then convert it to lower energy or heat.

  Referring to FIG. 5A, the deflection of radiation 132 by the concave inner surface 134 of the nano hemisphere is shown. In FIG. 5B, the radiation 142 is transmitted through the concave outer surface 144 of the nanosphere 140 but is internally reflected and thereby captured by the concave inner surface 146 of the same nanosphere 140.

  As is known in the art, parabolic or hemispherical resonant antennas have very sharp directivity characteristics. Similarly, when producing similar resonance characteristics for nano-level radiation, it is preferable to direct the nanomaterial in space to create a layer that blocks radiation coming from a specific direction (e.g., outside the garment). Would be desired. Nevertheless, shielding from all directions can be effectively achieved by depositing hundreds of layers of randomly arranged particles. For better performance, such a coating of nanomaterial should have minimal voids. As such, when making a mixture of nanomaterial and binder, it is preferred that the nanomaterial is the majority of the coating, eg, greater than 70 wt%, more preferably 85 wt% to 95 wt%.

  Ceramic nanoparticles can also be added to a radiopaque polymer mixture to increase mechanical strength, such as tensile strength and creep resistance, as well as increase heat resistance, ballistics, electromagnetic wave attenuation and neutron emission attenuation. it can. Advantageously, oxides and carbides / nitrides of aluminum, zirconium, silicon, titanium, mullite and spinel, such as boron carbide, silicon carbide, titanium carbide, tungsten carbide, boron nitride, silicon nitride, titanium diboride, diboride Ceramic nanoparticles can be incorporated into the polymer mixture to provide radiation attenuation, including, but not limited to, zirconium fluoride and other intermetallic compounds such as nickel aluminide, titanium aluminide, and molybdenum disilicate. These ceramic nanomaterials are chemical vapor deposition, pulsed laser deposition, conventional powder processing (i.e., sol-gel processing), plasma synthesis, thermal decomposition, carbothermal reduction, hydrothermal method, emulsion method, combustion synthesis, NIST method, It can be prepared by a number of methods including precipitation, electric arc and ball milling. In addition, metal second phase particles can be added to ceramics to enhance mechanical, thermal and electromagnetic wave attenuation properties. Metals such as tungsten, molybdenum, nickel, copper, cobalt and iron can be added to ceramics using conventional metallurgical techniques and solution chemistry methods such as sol-gel and coprecipitation methods.

Alternatively, the nanoparticles can be synthesized by several additional techniques. One such technique can coat inner removable template particles, such as silica or polymer beads, with a metal material to a multi-stage colloid or gas phase assembly, which can then be removed to create an empty metal shell. Colloid template method. Creating a uniform coating on a particle template by colloidal self-assembly is based on the concept of self-assembled organic molecular species. The two ends of the molecule to be conjugated have specific functional groups (i.e. thiol, amine, carboxyl groups) that can be targeted for specific interaction with the clusters used to make templates and coatings. Have. Uniform and dense packing of molecules around the template leads to a dense packing of clusters that form a porous but space-filled shell around the template. Non-interactive metal-coated magnetic materials including SiO ₂ / Au, Fe ₃ O ₄ / Au, NiO / Co, silver, platinum, tantalum, tungsten, aluminum and copper or coated semiconductor particles such as PbS / CdS Particles are an example of such a composite particle structure. Alternatively, PbS-coated CdS nanocomposite particles with a diameter of a few nanometers can be synthesized by ion substitution in a reverse microemulsion. Refractive nonlinearity in these nanocomposite particles can be attributed to the optical Stark effect and strong interfacial and nanoparticle interactions.

  Hollow nanospheres can also be synthesized by utilizing the nanoscale Kirkendall effect. When nanocrystals such as cobalt are exposed to sulfur, there is a difference in diffusion and the cobalt atoms move outward faster than the sulfur atoms, thereby creating hollow nanospheres of cobalt sulfide. Cobalt oxide and cobalt selenide can also be synthesized by this technique. Similarly, it may be possible to synthesize other metals such as silver, gold, platinum, aluminum, copper and tungsten using this technique.

Nanoparticles can also be made by in situ particle formation / in situ polymerization. In this method, a stable suspension of metal particles is prepared in the presence of a polymer. Once in solution, the composite can be cast or additional monomers of the same or different polymer types can be added to form the nanocomposite. The reaction takes place in the presence of the protective polymer, limiting the size of the nanocomposite from which it is obtained. The particle size is also controlled by the choice of metal precursor and the metal / polymer interaction. For example, when comparing PdCl ₂ with (NH ₄ ) ₂ PdCl ₄ , the former shows a tendency to form halogen-bridged complexes, and thus a tendency to form aggregates of nanoparticles, whereas the latter It does not show such a tendency. The interaction between the metal precursor and the polymer is also important to control the particle size. If the polymer has a stronger interaction with the precursor, the particle size tends to decrease because the metal precursor is prevented from phase separation. Using this technique, nanoparticles can also be formed by the use of micelles formed from amphiphilic block polymers or cross-linked gelling matrices. While using a copolymer to form micelles, any metal salt is introduced that can penetrate the micelles or is stable in the micelle corona. When a reducing agent is added, metal particles form in micelles or in the corona, giving rise to some morphology.

  In general, the nanoparticle size is controlled in several ways depending on the synthesis technique used. For example, in the gas phase, the synthetic particle size is controlled by changing system parameters such as temperature, gas flow rate and system pressure. In other methods, such as sol-gel technology, the particle size can be changed by changing the concentration and temperature of the solution. In mechanical grinding, the particle size is rather dependent on the speed of the grinding media and the grinding time.

  Hollow nanocrystals can be purchased from Molecular Foundry of Berkeley National Laboratory, Berkeley California, which specializes in the synthesis of hollow metal, metal oxide / sulfide nanocrystals.

The second type of nanomaterial used in the present invention is a nanotube. Nanotubes are typically formed from carbon. When added to a polymer mixture, nanotubes represent another way to increase the mechanical properties of the mixture, such as modulus, chemical resistance, flame resistance, strength and electrical conductivity. Carbon nanotubes have unique electrical properties because the electron conduction process in the nanotubes is confined in the radial direction, and as a result, can also be used to attenuate electromagnetic radiation. Methods for producing these nanotubes include chemical vapor deposition techniques in which the nanotubes are grown using a catalyst and a hydrocarbon precursor. Nanotubes can also be made by electric arc, laser ablation, chemical vapor deposition and high pressure carbon monoxide conversion (HiPCO). HiPCO produces large quantities of 80% pure nanotubes using high pressure disproportionation of carbon monoxide gas in the presence of iron carbonyl catalyst vapor. Other types of nanotubes include hexagonal boron nitride nanotubes, dichalcogenide nanotubes (ie MoS ₂ , WS ₂ ), oxide nanotubes (ie V ₂ O, MoO ₃ ), gold nanotubes and organic nanotubes . Nanotubes can be purchased from Materials and Electrochemical Research Corporation of Tucson, Arizona.

  Once manufactured, the nanotubes should undergo a purification process before being incorporated into the radiopaque polymer mixture of the present invention. Purification and processing methods include prefiltration, dissolution, microfiltration, sedimentation and chromatography. The resulting nanotube product is then preferably dispersed in a polymer mixture with a surfactant, such as sodium dodecyl sulfate.

  A third type of nanomaterial that can be added to a radiopaque polymer mixture is a nanoplatelet (ie, a plate-like nanofiller). Nanoplatelets are layered materials that typically have a high aspect ratio and a thickness on the order of about 1 nm.

  Nanoplatelets will increase the chemical, ballistic, flame, electromagnetic radiation and neutron resistance of the mixture when added in large amounts to the polymer mixture. Nanoplatelets include nanoclays such as montmorillonite clay. Montmorillonite clay belongs to the smectite group, which also includes clays such as bentonite, hectorite, pyrophyllite, talc, vermiculite, soconite, saponite and nontronite, layered silicic acid (i.e. ) As well as layered double hydroxides. Other family clays such as kaolinite and chlorite and other phyllosilicates such as mica can also be used. Also, the transition metal dichalcogenide (i.e., tantalum dichalcogenide intercalated with lithium) is dispersed in the polymer mixture to provide a mixture with nanoclay-like properties (thanks to its similar layered structure). ) And can also increase the attenuation of electromagnetic radiation.

  Natural nanoclay such as smectite clay is a substance with high layering and weak bonding. Each layer consists of two silica tetrahedron sheets and an edge shared octahedron sheet of either alumina or magnesia. Each unit cell has a negative charge due to isomorphous replacement of aluminum with alumina or magnesium into the silicate layer. Natural nanoclay layers are held together by layers of charge-compensating cations such as lithium (Li +), sodium (Na +), potassium (K +) and calcium (Ca +). These charge-compensating cations provide a route to the rich intercalation chemistry and surface modification required to disperse nanoclays in polymers. Synthetic clays such as hydrotalcite carry positive charges to the platelets. In order for these layered nanoclays to be useful in a radiopaque polymer mixture, the layers should be separated and properly dispersed in the mixture. In the case of nanoclays such as silicate clays, they are inherently hydrophilic, but the polymers tend to be hydrophobic. In order to obtain intercalation and exfoliation of these clays, the passages or layers of these clays must be opened and the resulting clay polarity matches that of the polymer so that the polymer is intercalated between the layers. You have to do that. This is done by exchanging inorganic cations with organic cations. Larger organic cations swell the layer and increase the hydrophobicity of the clay. The organically modified clay can then be intercalated with the polymer by several routes. In the case of clays having a positive charge, such as hydrotalcite, anionic surfactants can be used. Other types of clay modification can be used depending on the choice of polymer. Such include ionic dipole interactions, the use of silane coupling agents, and the use of block polymers. An example of an interaction between ionic dipoles is the intercalation of small molecules such as dodecylpyrrolidone into clay. Undesirable interactions between the clay edge and the polymer can be eliminated by modifying the edge using a silane coupling agent. Alternatively, the copolymerization of clay and polymer can be carried out by using the copolymer so that one component of the copolymer is compatible with the clay and the other component of the copolymer is compatible with the polymer.

  By incorporating a small amount (about 2-5% by weight) of nanoclay into the polymer mixture, the resistance of the polymer mixture to harmful chemicals can also be substantially improved. However, the level of chemical resistance improvement depends on many factors such as the degree of exfoliation of the nanoplatelets in the polymer mixture, the proportion of nanomaterial filler, its aspect ratio, and the way the platelets are arranged. By incorporating nanoclays in the polymer mixture, the oxygen permeation in the mixture is particularly reduced, which reduces polymer degradation by reducing the oxidation of the resin and thus increasing its flame retardancy. In addition, the inorganic phase can act as a sink to prevent the polymer chains from breaking down.

  To increase the flame retardancy of the polymer mixture of the present invention, traditional flame retardant additives such as alumina trihydrate (ATH), magnesium hydroxide or organic brominated and chlorinated compounds are often added. It is done. Nevertheless, in order to achieve an acceptable level of flame retardancy (eg in the case of cables or wires), these flame retardant additives are usually required at very high levels. These high additive levels make the manufacturing process more difficult and thus weaken the polymer end product.

  In the present invention, this flame retardant embrittlement problem can be eliminated by using nanomaterials in the polymer mixture. More specifically, the addition of a small weight percent (e.g. 2-10%) of nanoclay together with traditional bulky flame retardant additives such as ATH or magnesium hydroxide results in the same or improved levels in the polymer mixture. The additive amount required to achieve the fire resistance of can be greatly reduced. Other nano-sized flame retardant additives that can be added to the polymer mixture are nano / micron sized oxides, such as nano / micron sized compounds of antimony oxide, molybdenum, titanium, zirconium and zinc. Silicon carbide, silicon nitrate, aluminum nitride, silicon nanotubes, carbon nanotubes, and boron nitride nanotubes may also be used to increase the fire resistance of the polymer. In addition, conventional refractory additives, such as ATH or magnesium hydroxide, can be added in the nanosize range to achieve fire resistance more effectively in the polymer mixture. By using these nanomaterials, the resulting polymer mixture will be stronger, lighter and more flexible.

  One of the major limitations in the use of nanomaterials in polymer compositions is processing. More specifically, nanomaterials tend to agglomerate and reduce their surface area, and therefore the desired properties of the resulting nanocomposite cannot be achieved unless properly dispersed and distributed in the polymer matrix. . In order to effectively disperse the nanomaterial in the polymer and process the resulting mixture by standard manufacturing techniques, the nanomaterial should be surface modified. For example, in the case of nanoclays, the clay surface can be modified by a method known as compatibilization so that the nanoclay is attracted to the polymer resin matrix and thus thoroughly dispersed. The two most common compatibilization methods are onium ion modification and ion-dipole interaction.

  Once the nanomaterial aggregation problem is resolved, there are three general ways to disperse the nanomaterial in the polymer mixture. The first method is direct mixing of the polymer and nanomaterial either as a separate phase or in solution. The second method is in situ polymerization in the presence of nanomaterials, and the third method is in situ particle processing including in situ formation of nanomaterials and in situ polymerization.

  For example, to prepare chemical flame resistant nanocomposites, polymers such as ethyl vinyl acetate (EVA) can be mixed directly with nanoplatelets such as nanoclay, silicic acid or transition metal dichalcogenides. . Such mixtures can be made with or without conventional flame retardants such as ATH and magnesium hydroxide. The resulting polymer mixture can then be processed with a twin screw extruder and formed into the desired product using blow molding or injection molding. Compounding using a twin screw extruder generates a large amount of shear that helps exfoliate the nanomaterial in the polymer mixture. The addition of nanoclays or nanotubes will increase the viscosity of the polymer mixture. Therefore, the rheology of the mixture should be closely monitored and controlled by adding flowable additives that are compatible with the polymer and filler used (ie, nanoclay or nanotube).

  The nanomaterial can also be coated on several different substrates, including polymer substrates, to produce the protective product of the present invention. Nanocomposites are well-known techniques such as evaporation, sputtering (glow discharge / ion and beam / laser), ion plating, chemical vapor deposition (CVD), plasma enhanced CVD, thermal spraying, dip coating, fluidized bed and spray spraying. It can be used to coat several different substrates. Nanomaterials can also be applied to various substrates by other techniques such as spraying alone, liquid coating by existing techniques such as spraying with high voltage electric field, rollstock, extrusion, coating and coextrusion. It can also be applied as a coat.

  Alternatively, after the nanomaterial is attached to a flexible film, the film can be coated with a pressure-sensitive adhesive to produce an adhesive material having shielding properties. In the case of protecting a human skin from the sun's ultraviolet rays, for example, the nanomaterial can be mixed with a binder to form a spray or ointment that is applied directly to the skin. Furthermore, because the thickness of several hundred rows of nanomaterials is on the order of 1 micrometer, the nanoshielding material of the present invention is transparent to visible light, thereby providing goggles and other having excellent optical properties. Can be used in the manufacture of transparent shields.

  Referring now to FIG. 10, a bomb storage container 760 including a bomb storage ball 762, a front hatch 764, a wheel assembly 766 and a bomb tray 768 is shown. The ball portion 762 and the front hatch 764 of the bomb containment vessel 760 are constructed of a hard explosion-resistant material, such as hardened steel. The existing bomb containment 760 is constructed to contain conventional bomb explosions, but is not designed to contain or attenuate nuclear radiation, such as gamma and neutron emissions or rays. However, using the principles of the present invention, the bomb containment 760 can be reconstructed to protect against nuclear hazards caused by, for example, “dirty bombs” or radiation bombs.

  In a preferred embodiment, a radiation protective polymer layer 770 is applied to the outside of the bomb containment vessel 760. As before, the radiation protection polymer layer 770 is formed from a mixture comprising one or more of the foregoing radiopaque materials and one or more of the aforementioned polymers. In the preferred embodiment shown in FIG. 10, a radiopaque polymer mixture is used to form a curved radiopaque tile 772. These radiopaque tiles 772 can be formed by any number of known manufacturing methods including injection molding, extrusion, vacuum molding, drape molding, pressure molding, and plug assist molding. The radiopaque tiles 772 are then applied to the outer surface of the bomb storage container 760 and to each other. A smooth decorative layer (not shown) can then be deposited on the radiopaque tile 772 to improve the appearance of the bomb containment vessel 760. Alternatively, the radiopaque polymer layer can be formed in one piece, or bomb storage by adhesive spraying, rotational molding, injection molding, immersion in liquid bath, painting or other known coating and injection molding methods It is also possible to uniformly coat the outside or inside of the container.

  In operation, the hardened material of the bomb containment vessel 760 contains the explosive power of the bomb, and the radiation protection layer 770 of the present invention contains the radiation emitted by the bomb. Although the radiation protection layer of the present invention can also be applied to the inside of the bomb containment vessel 760, the inventors have found that the damage that the explosion causes to the radiation protection layer 770 is much more effective. I think it should not be.

  In the foregoing specification, the invention has been described with reference to specific preferred embodiments and methods. However, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the broader spirit and scope of the claimed invention. For example, those skilled in the art will recognize that the principles of the present invention apply to many types of articles in addition to the toys, tableware, weapons and medical devices described above. More specifically, the relatively lightweight radiopaque material of the present invention can be incorporated into virtually any type of plastic product (e.g., automotive parts, telephones, storage containers, etc.) Allows presence and / or attributes to be evaluated by X-ray. Furthermore, the principles of the present invention may be applied to virtually any type of manufacturing method for plastic products. Although X-ray examination has been described in the preferred embodiment, other types of radiation, such as alpha, beta or gamma radiation, can alternatively be used to detect radiopaque polymeric articles. In the case of nanomaterials, many nanomaterials have been found to have minimal toxicity, which is enhanced when nanocomposites are added intravenously or orally to the human body for use in radiography. Tissue contrast can also be provided. The specification and drawings are, accordingly, to be regarded in an illustrative sense rather than a restrictive sense, and the present invention is limited only by the claims.

It is a front view of the radiopaque polymer article of the present invention. 1 is a side view of an injection molding apparatus for making a radiopaque polymer article of the present invention. 1 is a perspective view of an apparatus for detecting the presence and attributes of radiopaque polymer articles on a high speed assembly line. FIG. It is a front view of a radiation protection whole body suit. It is a side view of the nano hemisphere for attenuating radiation. It is a side view of the nanosphere for attenuating radiation. 1 is a cross-sectional view of a composite material that can provide multiple forms of hazard protection. FIG. It is a figure which shows the vest formed with many danger protection layers. It is an exploded view of protective clothing that can be worn as underwear. FIG. 2 shows a pocket and a hazard protection insert for the pocket. It is a perspective view of a radiation attenuating bomb storage container.

Claims (81)

Creating a radiopaque polymer mixture by mixing the polymer with a radiopaque material;
Using the radiopaque polymer mixture to form a radiopaque polymer article;
Exposing the radiopaque polymer article to a radiation source;
Detecting how much of the radiation is transmitted through the radiopaque polymer article;
Determining the presence and / or attributes of the radiopaque polymer article using the detected radiation.
A method of detecting a radiopaque polymeric article.   The polymer is polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, polyisoprene, polystyrene, polysulfone, ethylene vinyl acetate, polyester, acrylonitrile-butadiene-styrene, acrylic, polycarbonate, polyoxymethylene, acetal, 2. The detection method according to claim 1, wherein the detection method is selected from the group consisting of polytetrafluoroethylene, ionomer, cellulose, polyether ketone, silicone, epoxy, elastomer and polymer foam.   Radiopaque materials are barium, barium sulfate, barium chloride, other barium compounds, tungsten, tungsten carbide, tungsten oxide, other tungsten compounds, bismuth, bismuth compounds, tantalum, tantalum compounds, titanium, titanium compounds, diato Diatrizoate Meglumine (for injection) USP, Acetrizoate Sodium, boron, boric acid, boron oxide, boron salts, other boron compounds, beryllium, beryllium compounds, bunamiosyl sodium, diatrizo Ate sodium, etiozido oil, iobenzamic acid, iocarmic acid, iosetamic acid, iodidipamide, iodixanol, iodized oil, iodoalphionic acid, o-iodohyperate sodium, iodo Sodium phthalein, iodopyracet, ioglycic acid, iohexol, iomegramic acid, iopamidol, iopanoic acid, iopentol, iophendylate, iophenoxic acid, iopromide, ioproic acid, iopidol, iopidone, iotalamic acid, Iotrolan, ioversol, ioxagric acid, ioxirane, ipodate, meglumine acetolizoate, meglumine ditrizoate methiodal sodium, metrizamide, metrizoic acid, fenobuthiozil, phentetiothalein sodium, propioliodone , Sodium Iodomethamate, Sozoiodolic Acid, Thorium Oxide and Trypanoate Sodium That is selected from the group, the detection method of claim 1, wherein.   The polymer mixture further comprises one or more additives selected from the group consisting of plasticizers, emulsifiers, surfactants, suspending agents, leveling agents, drying accelerators, adhesives and flow improvers. Item 2. The detection method according to Item 1.   2. The detection method according to claim 1, wherein the polymer mixture further comprises a flame retardant.   6. The detection method according to claim 5, wherein the flame retardant is selected from the group consisting of aluminum trihydrate, magnesium hydroxide, an organic brominated compound and an organic chlorinated compound.   2. The detection method according to claim 1, wherein the polymer mixture further comprises a nanomaterial.   8. The detection method according to claim 7, wherein the nanomaterial is selected from the group consisting of nanoparticles, nanotubes and nanoplatelets.   2. The detection method according to claim 1, wherein the radiopaque material contains lead.   2. The detection method according to claim 1, wherein the radiopaque material contains tin.   The detection method according to claim 1, wherein the radiopaque polymer article is formed by extrusion and injection molding.   The detection method of claim 1, wherein the radiopaque polymer article is formed by extrusion and vacuum forming.   The detection method of claim 1, wherein the radiopaque polymer article is formed by applying a radiopaque coating to an existing article.   2. The detection method according to claim 1, wherein the radiation source generates X-rays.   2. The detection method according to claim 1, wherein the presence of the radiopaque polymer article is confirmed by measuring the level of blocked radiation.   2. The detection method according to claim 1, further comprising a plurality of radiation detectors arranged in a pattern of pixels.   17. The detection method of claim 16, wherein the contour of the radiopaque polymer article is determined by evaluating the amount of radiation detected by each pixel.   2. The detection method according to claim 1, wherein the presence or absence of a contaminant is further detected.   17. The detection method of claim 16, wherein a break, crack or other defect in the radiopaque polymer article is identified by evaluating the amount of radiation detected by each pixel.   2. The detection method according to claim 1, wherein the radiopaque polymer article is a premium.   2. The detection method according to claim 1, wherein the radiopaque polymer article is a weapon or an explosive.   The detection method according to claim 1, wherein the radiopaque polymer article is a straw or other tableware.   2. The detection method according to claim 1, wherein the radiopaque polymer article is a medical device.   24. The detection method according to claim 23, wherein the medical device is a catheter.   2. The detection method according to claim 1, wherein the radiopaque polymer article is contained in a box or other container. Creating a radiopaque polymer mixture by mixing the polymer with a radiopaque material;
Forming a polymer article using the radiopaque polymer mixture;
Placing the article in a box;
Exposing the box to a radiation source;
Detecting how much of the radiation is transmitted through the box;
Determining whether the radiopaque article is contained in the box using the detected radiation.
A method for detecting the presence of a polymer article contained in a box.   The polymer is polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate, polyester, acrylonitrile-butadiene-styrene, acrylic, polycarbonate, polyisoprene, polystyrene, polysulfone, polyoxymethylene, acetal, 27. The detection method according to claim 26, selected from the group consisting of polytetrafluoroethylene, ionomer, cellulose, polyetherketone, silicone, epoxy, elastomer and polymer foam.   Radiopaque materials are barium, barium sulfate, barium chloride, other barium compounds, tungsten, tungsten carbide, tungsten oxide, other tungsten compounds, bismuth, bismuth compounds, tantalum, tantalum compounds, titanium, titanium compounds, diato Lysoate meglumine (injectable) USP, acetolysoate sodium, boron, boric acid, boron oxide, boron salts, other boron compounds, beryllium, beryllium compounds, bunamiosyl sodium, diatrizoate sodium, etiozido oil, iobenzam acid , Iocalumic acid, iosetamic acid, iodipamide, iodixanol, iodo oil, iodoalfionic acid, sodium iodohyperate, sodium iodophthalein, iodopyracet, ioglic acid, iohexol, iodo Megramic acid, iopamidol, iopanoic acid, iopentol, iofendilate, iophenoxylic acid, iopromide, ioproic acid, iopidol, iopidone, iotalamic acid, iotrolan, ioversol, ioxagric acid, ioxirane, ipodate, meglumine acetolyzoate, meglumine ditrizoate 27. Detection according to claim 26, selected from the group consisting of tometiodar sodium, metrizamide, metrizoic acid, fenobuthizyl, fentethiothalein sodium, propiodone, sodium iodometamate, sozoiodic acid, thorium oxide and trypanoate sodium. Method.   The polymer mixture further comprises one or more additives selected from the group consisting of plasticizers, emulsifiers, surfactants, suspending agents, leveling agents, drying accelerators, adhesives and flow improvers. Item 26. The detection method according to Item 26.   27. The detection method of claim 26, wherein the polymer mixture further comprises a flame retardant.   27. The detection method according to claim 26, wherein the flame retardant is selected from the group consisting of alumina trihydrate, magnesium hydroxide, an organic brominated compound and an organic chlorinated compound.   27. The detection method of claim 26, wherein the polymer mixture further comprises a nanomaterial.   27. The detection method according to claim 26, wherein the nanomaterial is selected from the group consisting of nanoparticles, nanotubes and nanoplatelets. A hollow explosion-proof container;
A hatch on the container for allowing a bomb to be inserted into the container and sealing the container after the bomb has been inserted;
A radiopaque polymer layer on the container comprising a polymer and a radiopaque material;
Radiation protection bomb containment vessel.   The polymer is polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate, polyester, acrylonitrile-butadiene-styrene, acrylic, polycarbonate, polyisoprene, polystyrene, polysulfone, polyoxymethylene, acetal, 35. The containment vessel of claim 34, selected from the group consisting of polytetrafluoroethylene, ionomer, cellulose, polyetherketone, silicone, epoxy, elastomer and polymer foam.   Radiopaque materials are barium, barium sulfate, barium chloride, other barium compounds, tungsten, tungsten carbide, tungsten oxide, other tungsten compounds, bismuth, bismuth compounds, tantalum, tantalum compounds, titanium, titanium compounds, diato Lysoate meglumine (injectable) USP, acetolysoate sodium, boron, boric acid, boron oxide, boron salts, other boron compounds, beryllium, beryllium compounds, bunamiosyl sodium, diatrizoate sodium, etiozido oil, iobenzam acid , Iocalumic acid, iosetamic acid, iodipamide, iodixanol, iodo oil, iodoalfionic acid, sodium iodohyperate, sodium iodophthalein, iodopyracet, ioglic acid, iohexol, iodo Megramic acid, iopamidol, iopanoic acid, iopentol, iofendilate, iophenoxylic acid, iopromide, ioproic acid, iopidol, iopidone, iotalamic acid, iotrolan, ioversol, ioxagric acid, ioxirane, ipodate, meglumine acetolyzoate, meglumine ditrizoate 35. Storage according to claim 34, selected from the group consisting of tomethiodal sodium, metrizamide, metrizoic acid, fenobuthizyl, fentethiothalein sodium, propiodonone, sodium iodomethamate, sozoiodoic acid, thorium oxide and trypanoate sodium. container.   The polymer layer further comprises one or more additives selected from the group consisting of plasticizers, emulsifiers, surfactants, suspending agents, leveling agents, drying accelerators, adhesives and flow improvers. Item 34. The containment vessel according to Item 34.   35. The containment vessel of claim 34, wherein the polymer layer further comprises a flame retardant.   39. The containment vessel of claim 38, wherein the flame retardant is selected from the group consisting of alumina trihydrate, magnesium hydroxide, organic brominated compounds and organic chlorinated compounds.   35. The containment vessel of claim 34, wherein the polymer layer further comprises a nanomaterial.   41. The containment vessel of claim 40, wherein the nanomaterial is selected from the group consisting of nanoparticles, nanotubes and nanoplatelets.   A radiopaque polymer mixture comprising a polymer and a radiopaque nanomaterial.   43. The radiopaque polymer mixture of claim 42, wherein the nanomaterial is selected from the group consisting of nanoparticles, nanotubes and nanoplatelets. Radiopaque nanomaterials include tungsten, barium, boron, tantalum, bismuth, depleted uranium, cerium oxide (CeO ₂ ), yttrium oxide (Y ₂ O ₃ ), lanthanum oxide (La ₂ O ₃ ) and neodymium oxide (Nd ₂ O ₃₎ is formed from a material selected from the group of claim 42 radiopaque polymer mixture according.   43. The radiopaque polymer mixture according to claim 42, wherein the radiopaque nanomaterial is formed from a substance comprising lead or tin.   43. The radiopaque polymer mixture of claim 42, wherein the radiopaque nanomaterial is formed from a material comprising a transition metal dichalcogenide.   43. The radiopaque polymer mixture of claim 42, wherein the nanomaterial is selected from the group consisting of nanospheres, nanohemispheres and nanoparabolas.   The polymer is polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate, polyester, acrylonitrile-butadiene-styrene, acrylic, polyisoprene, polystyrene, polysulfone, polycarbonate, polyoxymethylene, acetal, 43. The radiopaque polymer mixture of claim 42, selected from the group consisting of polytetrafluoroethylene, ionomer, cellulose, polyetherketone, silicone, epoxy, elastomer and polymer foam.   43. The radiopaque polymer mixture of claim 42, further comprising a flame retardant.   Flame retardant is antimony oxide, antimony pentoxite, molybdenum compound, titanium, zirconium, zinc, silicon carbide, silicon nitrate, aluminum nitride, alumina trihydrate, magnesium hydroxide, organic Selected from the group consisting of brominated compounds, organochlorinated compounds, natural and synthetic nanoclays, pyrophyllite, chlorite, smectite, montmorillonite, palygorskite, talc, vermiculite, soconite, saponite, nontronite and mica, 50. A radiopaque polymer mixture according to claim 49.   43. The radiopaque polymer mixture of claim 42, further comprising an additive to impart enhanced chemical, biological or projectile protection.   The additive is selected from the group consisting of alumina oxide, aironia oxide, ferrite oxide, tianate oxide, mixed composite oxide, carbide powder, nitride powder and boride powder. Item 52. A radiopaque polymer mixture according to Item 51.   43. The radiopaque polymer mixture of claim 42, wherein the nanomaterial is selected from the group consisting of natural nanoclay, synthetic nanoclay, layered silicic acid and nanotubes.   43. The radiopaque polymer mixture of claim 42, wherein the nanomaterial is widely dispersed in the polymer mixture. A polymer,
Fireproof materials,
A radiopaque material,
A polymer mixture that can protect against both radiation and flame hazards.   Radiopaque materials include barium, barium sulfate, barium chloride, other barium compounds, lead, tungsten, tungsten carbide, tungsten oxide, other tungsten compounds, bismuth, bismuth compounds, tantalum, tantalum compounds, titanium, titanium compounds, Diatrizoate meglumine (injectable) USP, sodium acetorizate, boron, boric acid, boron oxide, boron salts, other boron compounds, beryllium, beryllium compounds, bunamiosyl sodium, diatrizoate sodium, etiozido oil, Iobenzamic acid, iocarmic acid, iosetamic acid, iodipamide, iodixanol, iodo oil, iodoalfionic acid, sodium iodophthalate, iodophthalein sodium, iodopyracet, ioglic acid, iohexol, Iomegramic acid, iopamidol, iopanoic acid, iopentol, iofendilate, iofenoxylic acid, iopromide, ioproic acid, iopidol, iopidone, iotaramic acid, iotrolan, ioversol, ioxagric acid, ioxirane, ipodate, meglumine acetolyzoate, meglumine ditrizoe 56. The polymer of claim 55, wherein the polymer is selected from the group consisting of tometiodar sodium, metrizamide, metrizoic acid, fenobuthizyl, fentethiothalein sodium, propioridone, sodium iodometamate, sozoiodic acid, thorium oxide and trypanoate sodium. blend. Radiopaque materials are lead, tin, tungsten, barium, boron, tantalum, bismuth, depleted uranium, barium, cerium oxide (CeO ₂ ), yttrium oxide (Y ₂ O ₃ ), lanthanum oxide (La ₂ O ₃ ) 56. The polymer mixture of claim 55, comprising a nanomaterial selected from the group consisting of and neodymium oxide (Nd ₂ O ₃ ).   56. The polymer mixture of claim 55, wherein the radiopaque material comprises a nanomaterial formed in the shape of a nanosphere, nanohemisphere, nanotube or nanoparabolic.   Flame retardant is nano clay, nano zeolite, sol-gel derived metal oxide, silicon carbide (SiC), silicon nitrate (SiN), silicon nanotube, fluoropolymer, alumina trihydrate, magnesium hydroxide, brominated compound , Antimony oxide, antimony pentoxite, molybdenum compound, titanium, zirconium, zinc, silicon carbide, silicon nitrate, chlorinated compound, pyrophyllite, chlorite, smectite, montmorillonite, palygorskite, talc, vermiculite, soconite, saponite, 56. The polymer mixture of claim 55, comprising a nanomaterial selected from the group consisting of nontronite and mica.   43. An article formed from the polymer mixture of claim 42.   61. The article of claim 60, wherein the article is clothing.   62. The article of claim 61, wherein the garment is an underwear, vest, hat, glove, full body suit, apron, shirt, trousers, pocket or groin protector.   61. The article of claim 60, wherein the article is a bomb suppression blanket.   61. The article of claim 60, wherein the article is a vehicle, wall, ship, aircraft, spacecraft or container liner or coating.   56. An article formed from the polymer mixture of claim 55.   68. The article of claim 65, wherein the article is clothing.   68. The article of claim 66, wherein the garment is underwear, a vest, a hat, a glove, a full body suit, an apron, a shirt, trousers, a pocket or a crotch protector.   66. The article of claim 65, wherein the article is a bomb suppression blanket.   68. The article of claim 65, wherein the article is a vehicle, wall, ship, aircraft, spacecraft or container liner or coating. Injecting into the human body a composition of radiopaque nanomaterials;
Detecting the morphology of cells in the human body using radiation.
A method for increasing the contrast of human cells for radiological detection. A polymer,
Chemically or biologically resistant materials,
A radiopaque material,
A polymer mixture that can protect against both radiation and chemical or biological hazards.   Radiopaque materials include lead, tin, barium, barium sulfate, barium chloride, other barium compounds, tungsten, tungsten carbide, tungsten oxide, other tungsten compounds, bismuth, bismuth compounds, tantalum, tantalum compounds, titanium, titanium Compound, diatrizoate meglumine (injectable) USP, sodium acetolizoate, boron, boric acid, boron oxide, boron salts, other boron compounds, beryllium, beryllium compounds, bunamiosyl sodium, diatrizoate sodium, etiozide Oil, iobenzamic acid, iocarmic acid, iosetamic acid, iodipamide, iodixanol, iodo oil, iodoalphionic acid, sodium iodophthalate, iodophthalein sodium, iodopyracet, ioglic acid, iohexo , Iomegramic acid, iopamidol, iopanoic acid, iopentol, iofendilate, iophenoxy acid, iopromide, ioproic acid, iopidol, iopidone, iotalamic acid, iotrolan, ioversol, ioxagric acid, ioxirane, ipodate, meglumine acetolyzoate, meglumine 72. Selected from the group consisting of ditrizoate sodium methiodar, metrizamide, metrizoic acid, fenobuthizyl, sodium fentethiotalein, propiodone, sodium iodomethamate, sozoiodic acid, thorium oxide and trypanoate sodium. The polymer mixture described. Radiopaque materials are lead, tin, tungsten, barium, boron, tantalum, bismuth, depleted uranium, barium, cerium oxide (CeO ₂ ), yttrium oxide (Y ₂ O ₃ ), lanthanum oxide (La ₂ O ₃ ) 72. The polymer mixture of claim 71, comprising a nanomaterial selected from the group consisting of and neodymium oxide (Nd ₂ O ₃ ).   72. The polymer mixture of claim 71, wherein the chemically or biologically resistant material comprises a nanomaterial selected from the group consisting of nanoceramics, natural nanoclays, synthetic nanoclays, nanotubes and layered silicic acid.   75. The polymer mixture of claim 74, wherein the natural nanoclay is selected from the group consisting of montmorillonite, kaolin, smectite, palygorskite, mica, talc, chlorite and vermiculite.   The polymer is polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate, polyisoprene, polystyrene, polysulfone, polyester, acrylonitrile-butadiene-styrene, acrylic, polycarbonate, polyoxymethylene, acetal, 72. The polymer mixture of claim 71, selected from the group consisting of polytetrafluoroethylene, ionomer, cellulose, polyetherketone, silicone, epoxy, elastomer and polymer foam.   72. An article formed from the polymer mixture of claim 71.   78. The article of claim 77, wherein the article is clothing.   79. The article of claim 78, wherein the garment is an undergarment, vest, hat, glove, full body suit, apron, shirt, trousers, pocket or groin protector.   78. The article of claim 77, wherein the article is a bomb suppression blanket.   78. The article of claim 77, wherein the article is a vehicle, wall, ship, aircraft, spacecraft or container liner or coating.

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