EP1512154B1 - Radiation protection material, method for production of a radiation protection material and use of the same - Google Patents
Radiation protection material, method for production of a radiation protection material and use of the same Download PDFInfo
- Publication number
- EP1512154B1 EP1512154B1 EP20030787749 EP03787749A EP1512154B1 EP 1512154 B1 EP1512154 B1 EP 1512154B1 EP 20030787749 EP20030787749 EP 20030787749 EP 03787749 A EP03787749 A EP 03787749A EP 1512154 B1 EP1512154 B1 EP 1512154B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radiation
- weight
- radiation protection
- material according
- protection material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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Images
Classifications
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/10—Organic substances; Dispersions in organic carriers
- G21F1/103—Dispersions in organic carriers
- G21F1/106—Dispersions in organic carriers metallic dispersions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
- Y10T428/257—Iron oxide or aluminum oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
Definitions
- the invention relates to a radiation protection material for the shielding of X-rays and / or gamma rays from a film-like, multilayer coating material in which radiation-absorbing particles are dispersed.
- an energy absorbing material comprising a layer consisting of a polymer composition comprising 7 to 30% by weight of a specific polar thermoplastic polymer, 0 to 15% by weight of plasticizer and 70 to 93% by weight of an inorganic composition.
- the inorganic composition consists of at least two elements, which should protect against radiation in a way that is better than lead.
- EP 0 372 758 A1 a material consisting of 4 to 19% by weight of a polar thermoplastic polymer, 0 to 10% by weight of a plasticizer and 81 to 96% by weight of an inorganic compound.
- DE 199 55 192 A1 discloses a method for producing a radiation protection material in which a thermoplastic, vulcanizable elastomer to which a metal powder is added is used.
- Another radiation protection material describes the U.S. Patent 5,908,884 in which a high-absorptivity material for radiation is embedded in a vulcanized fluororubber material.
- PVC plastisol materials are from the documents US 3,061,491 such as US 3,200,085 previously known.
- the invention has for its object to provide a radiation protection material, which with a low weight and high flexibility of the material a high Radiation protection effect over a wide application or energy range allows.
- the invention solves this object by a radiation protection material for the shielding of X-rays and gamma rays from a film-like multilayer coating material in which radiation-absorbing particles are dispersed, with the features of claim 1 and by a method according to claim 15 and a use according to claim 16
- the layer material consists of at least one support layer and at least one radiation-absorbing layer, wherein the radiation-absorbing layer comprises a curable polymer preparation which is flowable in the processing state and wherein the effective lead content ⁇ 15 wt .-% is.
- a material is provided whose radiation-absorbing layer in the state to be applied to the support layer is flowable, that is, either liquid or syrupy viscous and in particular in the range of 20,000 - 100,000 mPa s.
- the fluidity should preferably be below 80 ° C, especially at room temperature. At temperatures above 80 ° C, curing of the polymer preparation may occur.
- the curable polymer preparation comprises a PVC plastisol. This is flowable at room temperature. Furthermore, the polymer preparation comprises a liquid synthetic rubber. Such a preparation makes it possible to plasticize and vulcanize the liquid, crosslinkable and vulcanizable polymer matrix in one step and to harden it as a result. After hardening, a three-dimensional wide-mesh plastic structure with rubber-elastic behavior forms.
- Liquid synthetic rubber is a group of specialty rubbers. It has a lower viscosity than the conventional rubbers, which are uncrosslinked, but crosslinkable (vulcanizable) polymers with rubber-elastic properties at room temperature. At higher temperatures and under the influence of deforming forces, rubbers also show viscous flow and can therefore also be shaped using appropriate conditions.
- liquid rubbers make it easier to incorporate additives such as vulcanization accelerators, fillers, plasticizers or activators and are based on silicone, polyurethane, polyesters, polyethers and diene rubbers. With liquid silicone rubbers, the "cold-curing" one-component types RTV dominate.
- Liquid polyurethane rubbers usually consist of polyurethane with isocyanate end groups and are usually vulcanized with weakly basic di- and polyamines.
- Liquid diene rubbers are predominantly prepared by anionic polymerization of dienes with bifunctional starters. The resulting macro-dianions are reacted with carbon dioxide, ethylene oxide or ethylene sulfide to give polymers with carboxy, hydroxy or sulfhydryl end groups.
- the vulcanization then takes place by reaction of these end groups with, for example, polyfunctional isocyanates.
- concentration of crosslinkers must be relatively high because of the low molecular weights of the liquid rubbers. While the properties of the resulting elastomers in the liquid rubbers based on polyurethane similar to those of regular. Polyurethanes, vulcanizates of liquid diene rubbers have far lower tear strengths and elongation at break than vulcanizates of regular diene rubbers.
- the plastisols which can be used according to the invention are a dispersion of plastics, in particular of by emulsion or microemulsion polymerization polyvinyl chloride, in high-boiling organic solvents which act as a plasticizer at higher temperatures for a polymer. Upon heating, the solvents diffuse into the dispersed plastic particles, intercalating there between the macromolecules, thereby plasticizing the plastics. Upon cooling, the materials treated in this way gel into flexible, dimensionally stable and abrasion-resistant systems whose properties can be influenced by added auxiliaries, such as pigments or stabilizers.
- auxiliaries such as pigments or stabilizers.
- plasticizable polymers or copolymers or block polymers or polymer blends dissolved or mixed in one or more plasticizers, for example PVC plastisol, polyolefin plastisol and LDPE plastisol or HDPE plastisol and polymethacrylate plastisol or mixtures thereof may be used.
- plasticizers for example PVC plastisol, polyolefin plastisol and LDPE plastisol or HDPE plastisol and polymethacrylate plastisol or mixtures thereof may be used.
- synthetic rubbers all liquid rubbers such as polyurethane rubbers, silicone rubbers and other synthetic rubbers, based on polyesters, polyethers or dienes, which are flowable or liquid up to a temperature of 80 ° C, such as acrylonitrile-butadiene synthetic rubbers are used.
- a composition may be provided in which the polymer preparation contains between 20 and 40 wt .-% PVC and between 10 and 35 wt .-% of the liquid synthetic rubber, in particular an acrylonitrile-butadiene polymer and additives between 0 and 10 wt. -% such as stabilizers, anti-aging agents, starters and accelerators and residual plasticizers.
- the proportion of PVC is between 25 and 35 wt .-% and in particular between 29 and 32 wt .-%.
- the liquid rubber can be provided in particular be that between 15 and 25 wt .-% and in particular between 17 and 23 wt .-% of liquid rubber, in particular acrylonitrile-butadiene polymer is provided.
- the effective lead content is ⁇ 10% by weight, in particular ⁇ 5% by weight and in particular ⁇ 1% by weight and in particular 0% by weight, ie it is therefore a completely lead-free material where the toxic substance lead is no longer present.
- the specific lead equivalent of the material is ⁇ 30, in particular ⁇ 32 and preferably ⁇ 35 at a tube voltage in the range of 60 to 125 kV.
- the lead equivalent value of the material as a specific lead equivalent value ⁇ 30 at at least two measuring points at least 20 kV apart in a tube voltage range between 60 - 125 kV according to IEC 1331-1 / EN 61331, in particular at three or more points apart where the furthest apart points are for example 40 kV, in particular 45 kV and particularly preferably 65 kV apart.
- a measurement is carried out at, for example, 60 kV, 80 kV and 100 kV and 125 kV, and at all of these measuring points and in particular also in the areas between, the specific lead equivalent is ⁇ 30, in particular ⁇ 32 and in particular ⁇ 34.
- the determination of the lead equivalent or lead equivalent is carried out according to the specified standard on a difference measurement, that is, the amount of radiation is incident on a detector, once as empty measurement and once with a radiation-absorbing material and from the difference of these values, the transmitted radiation is determined directly ,
- the test setup is to be taken from IEC 1331-1 / EN 61331.
- the amount of transmitted radiation is used to determine the lead equivalent.
- the radiation source is an X-ray tube with a standard tungsten anode. This tube is operated at 300 - 500 mA.
- the emission of the radiation is metered in the range of 10 - 100 ms.
- the radiation quality reflects the radiation of the radiation used in the medical field. For illustration, the value as a specific lead equivalent value was referred to leadless, with the inaccuracy being +/- 1.
- the carrier layer also consists of PVC plastisol material and / or polyurethane and / or polyester and / or polyolefins and / or silicone rubbers and / or the polymer preparation of the radiation-absorbing layer.
- radiation-absorbing particles which realize a radiation-absorbing effect of the carrier layer can also be introduced into the carrier layer.
- the combination of one or more carrier layers and one or more radiation protection layers can produce a material which is extremely flexible and thin, in particular lead-free and a foil-like design having.
- the sequence of layers is freely selectable.
- the layers can be made of different materials and have different properties. In this way, the material is particularly suitable for textile applications. Due to the high flexibility and low weight, a wearer is not hindered in their activity, while a high radiation protection effect is achieved by the high specific lead equivalent at the same time.
- the carrier layer serves in particular to give strength.
- the proportion of the polymer preparation to the radiation-absorbing layer less than 20 wt .-%, but more than 0 wt .-% and the proportion of the radiation-absorbing particles is more than 80 wt .-%.
- the polymer preparation on the radiation-absorbing layer can be between 5 and 20% by weight and in particular between 10 and 20% by weight.
- the proportion of the radiation-absorbing particles may in particular be between 80 and 95% by weight and in particular between 80 and 90% by weight. In this case, the amount of polymer preparation must be sufficient to securely connect the particles introduced therein.
- the radiation-absorbing particles comprise tin, bismuth, barium and / or tungsten. It can be selected from the metal itself, metal oxides or metal salts.
- the effective amount of the radiation-absorbing particles in the radiation-absorbing layer should in particular 55-75 wt .-% tin powder, between 0 and 30 wt .-% bismuth, 0 - 10 wt .-% barium and / or 0 - 20 wt .-% Tungsten, the sum in each case 100 wt .-% results.
- lead components are included, pure lead as well as lead oxide and lead salts can be provided here.
- the tin powder consists of a mixture of two tin powders of different particle size distributions with approximately equal weight ratios.
- the bismuth oxide powder that can be used has a D 50 value in the range of 4-100 ⁇ m.
- the multilayer coating material preferably has a weight per unit area of 1.2 to 1.5 kg / m 2 , with a value of approximately 1.35 kg / m 2 being particularly desired.
- the multilayered layer material in particular has a film thickness of 0.3 to 1.2 mm, in particular of 0.3 to 0.5 mm, preferably 0.35 to 0.45 mm.
- the radiation protection material may be designed so that the carrier layer on its side facing away from the radiation-absorbing layer washable or abrasion resistant and / or solid to alcohols and / or disinfectants or has textile properties, for example, a flock is provided, the pleasant tactile properties when wearing ensures a product made of the material.
- abrasion resistance may be provided to extend the shelf life of a product made from the material, as well as washability, especially in the medical field to be able to easily clean manufactured objects after use.
- the material is very flexible.
- the bending stiffness which is a measure of the flexibility of the material was determined according to DIN 53121 and compared for comparison with the bending stiffness of other lead-free radiation protection films.
- the width-related bending stiffness measurement of the lead-free materials in the three-point method was carried out according to the beam method, wherein the test is carried out on a Zwick testing machine.
- the method is used to produce a radiation protection material of the type described above.
- the liquid phases are mixed before addition of the radiation-absorbing particles.
- the overall material for the radiation absorbing layer may be processed so that the particles are homogeneously distributed and then degassed prior to painting, pouring, knife coating and / or applying to the backing layer.
- the radiation-absorbing layer is subjected to ultrasound after it has been applied to the carrier layer.
- the carrier layer is not only adhesively bonded to the radiation-absorbing layer, but is integrally connected to the radiation-absorbing layer by crosslinking the two layers together during application and curing of the radiation-absorbing layer on the carrier layer.
- a physical anchor formation of the layers takes place with each other. This is done, for example, when using a PVC plastisol in the radiation-absorbing layer, provided that the material of the carrier layer is chosen so that the PVC plastisol can dissolve it.
- the invention comprises a use of the radiation protection material described above as Radiation protection clothing, in particular as a radiation protection apron or radiation protection apron or sheath or flexible barriers, such as covers or curtains.
- a radiation protection material can be easily produced, whereby a uniform, rapid and homogeneous distribution of the metal particles can be ensured in the polymer matrix, since a uniform distribution in a liquid polymer matrix is easy to implement and cumbersome kneading or walking as in the conventional radiation protection film materials can be omitted.
- the resulting radiation protection material of several layers is very flexible and uniformly radiation-absorbing over a wide energy range.
- FIG. 1 shows a cross-section through the lead-free foil-like radiation protection material, which is applied to a silicone-coated release paper 4.
- the release paper 4 can be structured to produce a structure, for example a leather grain, on a carrier layer 2.
- the carrier layer 2 of a PVC plastisol film is by knife coating on a silicone-coated release paper 4 and through subsequent gelling at 190-200 ° C formed.
- the carrier layer 2 gives the radiation protection material sufficient strength.
- a paste of the radiation-absorbing layer 3 is doctored onto this carrier layer 2 with a weight per unit area of 70-80 g / m 3 and then crosslinked or vulcanized in the drying oven at about 200 °.
- the total thickness of the film-like layer material is then about 0.35-0.45 mm and has a total basis weight of about 1.35 kg / m 2 .
- the paste from which the radiation-absorbing layer is formed consists of a PVC plastisol and a solvent-free and water-free acrylonitrile-butadiene liquid rubber and the metallic additives of tin powder and bismuth oxide powder.
- the polymer mixture of the radiation absorbing layer 3 has 13 parts by weight of polymer material, 65 parts by weight of tin powder and 22 parts by weight of bismuth powder.
- the tin powder consists of two different types with different grain size distribution (product name: TEGO-Zinngr imagine, TEGO 30 BG, TEGO 60 BG - Fa. Ecka Granules).
- the tin powders with different particle size distribution are mixed in a ratio of 1: 1.
- the bismuth oxide powder is also referred to in the nomenclature as yellow bismuth (Bi 2 O 3 ).
- the D 50 value is a maximum of 10 ⁇ m with a typical value of 5.5 ⁇ m.
- the lead-free radiation protection material may initially remain on the silicone-coated release paper layer 4 until it is made up into a radiation protection apron, for example.
- polymer mixture 13% by weight Tin powder TEGO 60 BG (metallic) 35% by weight Tin powder TEGO 30 BG (metallic) 30% by weight Bismuth trioxide (Bi 2 O 3 ) 22% by weight
- a polymer blend is given below. Parts by weight [g] DINP (plasticizer) 3400 TXIB (plasticizer) 600 Tin oxide (ZnO) 100 Sulfur (S) 100 Vulkazit D (vulcanization accelerator) 60 Vulkazit M (vulcanization accelerator) 60 Vestolit 1415 K 80 (PVC) 2800 Tegoprene (dispersing agent / anti-tack) 200 Nipol 1312 LV (liquid rubber) 1600 Total 8820
- This polymer mixture enters the initially pasty radiation-absorbing layer at a weight fraction of about 13% by weight.
- the proportion of PVC is about 31 wt .-%, the proportion of liquid rubber about 18 wt .-% and the amount of plasticizer about 45 wt .-% of the polymer composition.
- the carrier layer 2 has the following composition: PVC 40-70% by weight Plasticizer (DINP) 30-50% by weight Aggregates for aging protection, ozone resistance, color pigments 0.1-0.5% by weight
- the viscosity can be adjusted by changing the proportion of the plasticizer TXIB.
- the radiation protection material described does not show a collapse of the shielding efficiency at tube voltage over 100 kV, but is within a voltage range of 60-150 kV within the prescribed tolerance limits of the international standard IEC 1331-1 / EN 61331.
- the second figure now shows a table in which the sample number, the recipe number, the basis weight, the bending stiffness, the material thickness and then the shielding effects at a given x-ray tube voltage for 60 kV, 80 kV, 100 kV and 125 kV respectively for the specific as well the general lead equivalent.
- the sample numbers 1-14 relate to radiation protection materials according to the invention. Sample Nos. 15 - 19 Xenolite lead-free and Suprasine are marketed products for lead-free radiation protection materials.
- the specific lead equivalent of the x-ray tube voltage is defined as the lead equivalent at x-ray tube voltage x 100 / material thickness.
- the lead equivalent was determined according to IEC 1331-1 / EN 61331.
- compositions for the radiation protection layer are as follows: Recipe 1: 13% by weight of polymer preparation, 65% by weight of tin powder, 22% by weight of bismuth trioxide. Recipe 2: 11% by weight of polymer preparation, 62-66% by weight of tin powder, 27-23% by weight of bismuth powder. Recipe 3: 10-11% by weight of polymer preparation, 60-64% by weight of tin powder, 18-20% by weight of bismuth powder, 8-10% by weight of tungsten powder. Recipe 4: 12% by weight of polymer preparation, 65% by weight of tin powder, 10% by weight of barium fluoride, 13% by weight of tungsten powder.
- composition of the polymer preparation is as follows in the formulations 1 - 4: composition Wt .-% Di-isononyl phthalate (DINP) - Vestolit 38 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB) - Kran Chemie 6 Zinc oxide active - Rheinchemie Rheinau GmbH 1 Grinding sulfur - Solveig 1 N, N'-diphenylguanidine (Vulkacit D) - Rheinchemie Rheinau GmbH 0.5 2-mercaptobenzothiazole (MBT, Vulkacit Merkapto) - Rheinchemie Rheinau GmbH 0.5 PVC (Vestolit P 1415 K 80) - Vestolit 31 Ba / Zn stabilizer for PVC (Mark BZ 505) - Compton Vinyl Additive GmbH 1 Vulkanox DDA, (anti-aging agent) - Rheinchemie Rheinau GmbH 1 Acrylonitrile-butadiene polymer (Nipol 1312 LV
- the samples made, in particular according to formulation 2 have a particularly good specific lead equivalent, in comparison with the known products, in particular via a Tube voltage range of at least 20 kV difference, where the absolute voltage values are between 60 and 125 kV.
- the thickness of the xenolite material is 0.6 mm and this results in a bending stiffness for the material of 1.28 cN.
- Suprasine needs a thickness of 0.65 mm to achieve this shielding performance and then has a flexural stiffness of 1.11 cN.
- the composition according to the invention for example according to recipe 2, only needs a thickness of 0.45 mm to achieve this shielding value and achieves a bending stiffness of 0.43 cN. In this way, particularly light and flexible, comfortable for the wearer materials, especially for the production of textiles, such as clothing and barriers, created.
Abstract
Description
Die Erfindung betrifft ein Strahlenschutzmaterial für die Abschirmung von Röntgen- und/oder Gammastrahlen aus einem folienartigen, mehrschichtigen Schichtmaterial, in dem strahlenabsorbierende Partikel dispergiert sind.The invention relates to a radiation protection material for the shielding of X-rays and / or gamma rays from a film-like, multilayer coating material in which radiation-absorbing particles are dispersed.
Aus dem Stand der Technik ist es bekannt, folienartige Materialien zur Herstellung von Röntgenschutzschürzen und anderen strahlenabsorbierenden Anwendungen unter Zusätzen von metallischem Bleipulver oder auch Bleisalzen wie Oxiden oder Sulfiden und Polymeren wie zum Beispiel PVC-Plastisol, EVA-Copolymeren oder Kautschuk herzustellen. Dabei ist Blei als toxische Substanz einzustufen. Sogenannte Bleischürzen haben darüber hinaus ein Gewicht, das den Träger in seiner Tätigkeit behindert.From the prior art it is known to produce film-like materials for the production of X-ray protective aprons and other radiation-absorbing applications with additions of metallic lead powder or lead salts such as oxides or sulfides and polymers such as PVC plastisol, EVA copolymers or rubber. Lead is to be classified as a toxic substance. So-called lead aprons also have a weight that hinders the wearer in his job.
Zur Vermeidung dieser Nachteile sind aus dem Stand der Technik eine Reihe von Produkten bekannt. So zeigt beispielsweise die
Des Weiteren ist aus
Des Weiteren zeigt die
Weitere mehrschichtige flexible Röntgenschutzmaterialen sind aus
Weiterhin ist aus der
Ein weiteres Strahlenschutzmaterial beschreibt die
Weitere PVC-Plastisolmaterialien sind aus den Dokumenten
Schließlich ist aus
Der Erfindung liegt die Aufgabe zugrunde, ein Strahlenschutzmaterial zu schaffen, das bei einem geringen Gewicht und hoher Flexibilität des Materials eine hohe Strahlenschutzwirkung über einen weiten Einsatz- bzw. Energiebereich ermöglicht.The invention has for its object to provide a radiation protection material, which with a low weight and high flexibility of the material a high Radiation protection effect over a wide application or energy range allows.
Die Erfindung löst diese Aufgabe durch ein Strahlenschutzmaterial für die Abschirmung von Röntgen- und Gammastrahlen aus einem folienartigen mehrschichtigen Schichtmaterial, in dem strahlenabsorbierende Partikel dispergiert sind, mit den Merkmalen des Anspruchs 1 sowie durch ein Verfahren nach Anspruch 15 und eine Verwendung nach Anspruch 16. Beim erfindungsgemäßen Strahlenschutzmaterial besteht das Schichtmaterial aus mindestens einer Trägerschicht und mindestens einer strahlenabsorbierenden Schicht, wobei die strahlenabsorbierende Schicht eine aushärtbare Polymerzubereitung umfasst, die im Verarbeitungszustand fließfähig ist und wobei der wirksame Bleigehalt ≤ 15 Gew.-% beträgt.The invention solves this object by a radiation protection material for the shielding of X-rays and gamma rays from a film-like multilayer coating material in which radiation-absorbing particles are dispersed, with the features of
Auf diese Weise wird ein Material bereitgestellt, dessen strahlenabsorbierende Schicht im aufzubringenden Zustand auf die Trägerschicht fließfähig ist, das heißt entweder flüssig oder sirupartig viskos und insbesondere im Bereich von 20.000 - 100.000 mPa s liegt. Die Fließfähigkeit soll dabei vorzugsweise unterhalb 80° C insbesondere bei Raumtemperatur gegeben sein. Bei Temperaturen über 80° C kann es zu einem Aushärten der Polymerzubereitung kommen.In this way, a material is provided whose radiation-absorbing layer in the state to be applied to the support layer is flowable, that is, either liquid or syrupy viscous and in particular in the range of 20,000 - 100,000 mPa s. The fluidity should preferably be below 80 ° C, especially at room temperature. At temperatures above 80 ° C, curing of the polymer preparation may occur.
Dabei ist vorgesehen, dass die härtbare Polymerzubereitung ein PVC-Plastisol umfasst. Dieses ist bei Raumtemperatur fließfähig. Des Weiteren umfasst die Polymerzubereitung einen flüssigen Synthesekautschuk. Eine solche Zubereitung erlaubt es, in einem Schritt die flüssige, vernetzbare und vulkanisierbare Polymermatrix zu plastifizieren und zu vulkanisieren und hierdurch zu erhärten. Nach Härten bildet sich ein dreidimensionales weitmaschiges Kunststoffgebilde mit gummmielastischem Verhalten.It is envisaged that the curable polymer preparation comprises a PVC plastisol. This is flowable at room temperature. Furthermore, the polymer preparation comprises a liquid synthetic rubber. Such a preparation makes it possible to plasticize and vulcanize the liquid, crosslinkable and vulcanizable polymer matrix in one step and to harden it as a result. After hardening, a three-dimensional wide-mesh plastic structure with rubber-elastic behavior forms.
Bei flüssigem Synthesekautschuk handelt es sich um eine Gruppe der Spezialkautschuke. Sie besitzt eine niedrigere Viskosität als die klassischen Kautschuke, bei denen es sich um unvernetzte, aber vernetzbare (vulkanisierbare) Polymere mit gummielastischen Eigenschaften bei Raumtemperatur handelt. Bei höheren Temperaturen und bei Einfluss deformierender Kräfte zeigen zwar auch Kautschuke viskoses Fließen und können daher bei geeigneten Bedingungen auch formgebend verarbeitet werden. Flüssige Kautschuke erlauben dahingegen ein leichteres Einarbeiten von Additiven wie Vulkanisationsbeschleunigern, Füllstoffen, Weichmachern oder Aktivatoren und basieren auf Silikon, Polyurethan, Polyestern, Polyethern und Dienkautschuken. Bei flüssigen Silikon-Kautschuken dominieren die "kalthärtenden" Einkompohententypen RTV. Bei ihnen handelt es sich um verzweige Poly-Dimethylsiloxane mit Silanol-Endgruppen, die zum Beispiel mit Tetrabutyltitanat oder Triacetoxymethylsilan versetzt werden und bei Zutritt von Luftfeuchtigkeit vulkanisieren. Flüssige Polyurethankautschuke bestehen meist aus Polyurethan mit Isocyanat-Endgruppen und werden in der Regel mit schwach basischen Di- und Polyaminen vulkanisiert. Flüssige Dien-Kautschuke werden vorwiegend durch anionische Polymerisation von Dienen mit bifunktionellen Startern hergestellt. Die entstehenden Makro-Dianionen werden mit Kohlendioxid, Ethylenoxid oder Ethylensulfid zu Polymeren mit Caboxy-, Hydroxy- oder Sulfhydryl-Endgruppen umgesetzt.
Die Vulkanisation erfolgt dann durch Reaktion dieser Endgruppen mit zum Beispiel polyfunktionellen Isocyanaten. Die Konzentration der Vernetzer muss wegen der niedrigen Molmassen der flüssigen Kautschuke relativ hoch gewählt werden. Während die Eigenschaften der resultierenden Elastomere bei den flüssigen Kautschuken auf Polyurethanbasis ähnlich denen regulärer. Polyurethane sind, weisen Vulkanisate flüssiger Dien-Kautschuke weit niedrigere Reißfestigkeiten und Reißdehnungen auf als Vulkanisate regulärer Dien-Kautschuke.Liquid synthetic rubber is a group of specialty rubbers. It has a lower viscosity than the conventional rubbers, which are uncrosslinked, but crosslinkable (vulcanizable) polymers with rubber-elastic properties at room temperature. At higher temperatures and under the influence of deforming forces, rubbers also show viscous flow and can therefore also be shaped using appropriate conditions. On the other hand, liquid rubbers make it easier to incorporate additives such as vulcanization accelerators, fillers, plasticizers or activators and are based on silicone, polyurethane, polyesters, polyethers and diene rubbers. With liquid silicone rubbers, the "cold-curing" one-component types RTV dominate. These are branched poly-dimethylsiloxanes with silanol end groups, which are admixed with, for example, tetrabutyl titanate or triacetoxymethylsilane and vulcanized on ingress of atmospheric moisture. Liquid polyurethane rubbers usually consist of polyurethane with isocyanate end groups and are usually vulcanized with weakly basic di- and polyamines. Liquid diene rubbers are predominantly prepared by anionic polymerization of dienes with bifunctional starters. The resulting macro-dianions are reacted with carbon dioxide, ethylene oxide or ethylene sulfide to give polymers with carboxy, hydroxy or sulfhydryl end groups.
The vulcanization then takes place by reaction of these end groups with, for example, polyfunctional isocyanates. The concentration of crosslinkers must be relatively high because of the low molecular weights of the liquid rubbers. While the properties of the resulting elastomers in the liquid rubbers based on polyurethane similar to those of regular. Polyurethanes, vulcanizates of liquid diene rubbers have far lower tear strengths and elongation at break than vulcanizates of regular diene rubbers.
Bei dem erfindungsgemäß einsetzbaren Plastisolen handelt es sich um eine Dispersion von Kunststoffen, insbesondere von durch Emulsions- oder Mikroemulsionspolymerisation dargestelltem Polyvinylchlorid, in hoch siedenden organischen Lösungsmittel, die bei höheren Temperaturen als Weichmacher für ein Polymer fungieren. Beim Erwärmen diffundieren die Lösungmittel in die dispergierten Kunststoffpartikel, lagern sich dort zwischen den Makromolekülen ein und bewirken dadurch ein Plastifizieren der Kunststoffe. Beim Abkühlen gelieren die so behandelten Stoffe zu flexiblen, formstabilen und abriebfesten Systemen, deren Eigenschaften durch zugesetzte Hilfsstoffe wie Pigmente oder Stabilisatoren beeinflusst werden können.The plastisols which can be used according to the invention are a dispersion of plastics, in particular of by emulsion or microemulsion polymerization polyvinyl chloride, in high-boiling organic solvents which act as a plasticizer at higher temperatures for a polymer. Upon heating, the solvents diffuse into the dispersed plastic particles, intercalating there between the macromolecules, thereby plasticizing the plastics. Upon cooling, the materials treated in this way gel into flexible, dimensionally stable and abrasion-resistant systems whose properties can be influenced by added auxiliaries, such as pigments or stabilizers.
Als Plastisole können insbesondere alle plastifizierbaren Polymere oder Copolymere oder Blockpolymere oder Polymergemische, gelöst oder vermischt in einem oder mehreren Weichmachern, zum Beispiel PVC-Plastisol, Polyolefin-Plastisol sowie LDPE-Plastisol oder HDPE-Plastisol sowie Polymetacrylat-Plastisol oder Mischungen hiervon verwandt werden.As plastisols in particular, all plasticizable polymers or copolymers or block polymers or polymer blends, dissolved or mixed in one or more plasticizers, for example PVC plastisol, polyolefin plastisol and LDPE plastisol or HDPE plastisol and polymethacrylate plastisol or mixtures thereof may be used.
Als Synthesekautschuke können alle Flüssigkautschuke wie Polyurethan-Kautschuke, Silikonkautschuke sowie weitere Synthesekautschuke, auf Basis von Polyestern, Polyether oder Dienen, die bis zu einer Temperatur von 80° C fließfähig oder flüssig sind, wie zum Beispiel Acrylnitril-Butadien-Synthesekautschuke verwandt werden.As synthetic rubbers, all liquid rubbers such as polyurethane rubbers, silicone rubbers and other synthetic rubbers, based on polyesters, polyethers or dienes, which are flowable or liquid up to a temperature of 80 ° C, such as acrylonitrile-butadiene synthetic rubbers are used.
Dabei kann insbesondere eine Zusammensetzung vorgesehen sein, bei der die Polymerzubereitung zwischen 20 und 40 Gew.-% PVC enthält sowie zwischen 10 und 35 Gew.-% des flüssigen Synthesekautschuks, insbesondere eines Acrylonitril-Butadien-Polymers sowie Zuschlagstoffe zwischen 0 und 10 Gew.-% wie beispielsweise Stabilisatoren, Alterungsschutzmittel, Starter sowie Beschleuniger und Rest Weichmacher.In this case, in particular, a composition may be provided in which the polymer preparation contains between 20 and 40 wt .-% PVC and between 10 and 35 wt .-% of the liquid synthetic rubber, in particular an acrylonitrile-butadiene polymer and additives between 0 and 10 wt. -% such as stabilizers, anti-aging agents, starters and accelerators and residual plasticizers.
Insbesondere ist vorgesehen, dass der Anteil an PVC zwischen 25 und 35 Gew.-% und insbesondere zwischen 29 und 32 Gew.-% liegt. Für den Flüssigkautschuk kann insbesondere vorgesehen sein, dass zwischen 15 und 25 Gew.-% und insbesondere zwischen 17 und 23 Gew.-% an Flüssigkautschuk, insbesondere Acrylonitril-Butadien-Polymer vorgesehen ist.In particular, it is provided that the proportion of PVC is between 25 and 35 wt .-% and in particular between 29 and 32 wt .-%. For the liquid rubber can be provided in particular be that between 15 and 25 wt .-% and in particular between 17 and 23 wt .-% of liquid rubber, in particular acrylonitrile-butadiene polymer is provided.
Insbesondere kann vorgesehen sein, dass der wirksame Bleigehalt ≤ 10 Gew.-%, insbesondere ≤ 5 Gew.-% und insbesondere ≤ 1 Gew.-% sowie insbesondere 0 Gew.-% beträgt, das heißt es sich also um ein vollständig bleifreies Material handelt, in dem der als toxisch einzustufende Stoff Blei nicht länger enthalten ist.In particular, it can be provided that the effective lead content is ≦ 10% by weight, in particular ≦ 5% by weight and in particular ≦ 1% by weight and in particular 0% by weight, ie it is therefore a completely lead-free material where the toxic substance lead is no longer present.
Es kann dabei vorgesehen sein, dass der spezifische Bleigleichwert des Materials ≥ 30, insbesondere ≥ 32 sowie vorzugsweise ≥ 35 bei einer Röhrenspannung im Bereich von 60 - 125 kV beträgt. Insbesondere kann vorgesehen sein, dass der Bleigleichwert des Materials als spezifischer Bleigleichwert ≥ 30 an mindestens zwei mindestens 20 kV auseinander liegenden Messpunkten in einem Röhrenspannungsbereich zwischen 60 - 125 kV nach IEC 1331-1/EN 61331 beträgt, insbesondere an drei oder mehr auseinander liegenden Punkten, wobei die am weitesten auseinander liegenden Punkte beispielsweise 40 kV, insbesondere 45 kV und besonders bevorzugt 65 kV auseinander liegen. Insbesondere erfolgt eine Messung bei zum Beispiel 60 kV, 80 kV und 100 kV sowie 125 kV, und an sämtlichen dieser Messpunkte sowie insbesondere auch in den Bereichen dazwischen liegt der spezifische Bleigleichwert bei ≥ 30, insbesondere ≥ 32 und insbesondere ≥ 34.It may be provided that the specific lead equivalent of the material is ≥ 30, in particular ≥ 32 and preferably ≥ 35 at a tube voltage in the range of 60 to 125 kV. In particular, it can be provided that the lead equivalent value of the material as a specific lead equivalent value ≥ 30 at at least two measuring points at least 20 kV apart in a tube voltage range between 60 - 125 kV according to IEC 1331-1 / EN 61331, in particular at three or more points apart where the furthest apart points are for example 40 kV, in particular 45 kV and particularly preferably 65 kV apart. In particular, a measurement is carried out at, for example, 60 kV, 80 kV and 100 kV and 125 kV, and at all of these measuring points and in particular also in the areas between, the specific lead equivalent is ≥ 30, in particular ≥ 32 and in particular ≥ 34.
Bei dem spezifischen Bleigleichwert handelt es sich um eine Messung zur Bestimmung der Abschirmwerte und damit des Bleigleichwerts nach IEC 1331-1/EN 61331, wobei die Werte auf die Dicke der Probe normiert wurden und die Dickenmessung durch mechanisches Abtasten nach DIN 53370 vorgenommen wurde. Die Dickenmessung erfolgte dabei unter Zugrundelegung folgender Größen:
- Messfläche: rund,
Durchmesser 10 cm - Messkraft: 0,8 N
- Anpressdruck: 10 kPa +/- 2 kPa
- Skaleneinteilung: 0,01 mm
- Messgenauigkeit: +/- 0,01 mm.
- Flächengewicht: Messungenauigkeit +/- 0,02 kg/m2.
- Measuring area: round,
diameter 10 cm - Measuring force: 0.8 N
- Contact pressure: 10 kPa +/- 2 kPa
- Scale graduation: 0.01 mm
- Measuring accuracy: +/- 0.01 mm.
- Basis weight: measurement inaccuracy +/- 0,02 kg / m 2 .
Die Bestimmung des Bleigleichwertes oder Bleiäquivalentes erfolgt nach der angegebenen Norm über eine Differenzmessung, das heißt es wird die Strahlenmenge gemessen, die auf einen Detektor auftrifft, einmal als Leermessung und einmal mit einem strahlenabsorbierenden Material und aus der Differenz dieser Werte wird direkt die durchgelassene Strahlung bestimmt. Der Versuchsaufbau ist dabei der IEC 1331-1/EN 61331 zu entnehmen. Über die Menge der durchgelassenen Strahlung erfolgt die Bestimmung des Bleigleichwerts. Die Strahlenquelle ist dabei eine Röntgenröhre mit einer Standard-Wolfram-Anode. Diese Röhre wird mit 300 - 500 mA betrieben. Die Abgabe der Strahlung erfolgt dosiert im Bereich von 10 - 100 ms. Die Strahlenqualität spiegelt dabei die Strahlung der im medizinischen Bereich eingesetzten Strahlung wieder. Zur Darstellung wurde der Wert als spezifischer Bleigleichwert dimensionslos auf Blei bezogen, wobei die Ungenauigkeit +/- 1 beträgt.The determination of the lead equivalent or lead equivalent is carried out according to the specified standard on a difference measurement, that is, the amount of radiation is incident on a detector, once as empty measurement and once with a radiation-absorbing material and from the difference of these values, the transmitted radiation is determined directly , The test setup is to be taken from IEC 1331-1 / EN 61331. The amount of transmitted radiation is used to determine the lead equivalent. The radiation source is an X-ray tube with a standard tungsten anode. This tube is operated at 300 - 500 mA. The emission of the radiation is metered in the range of 10 - 100 ms. The radiation quality reflects the radiation of the radiation used in the medical field. For illustration, the value as a specific lead equivalent value was referred to leadless, with the inaccuracy being +/- 1.
Nach einer weiteren Ausgestaltung kann vorgesehen sein, dass die Trägerschicht ebenfalls aus PVC-Plastisol-Material und/oder Polyurethan und/oder Polyester und/oder Polyolefinen und/oder Silikonkautschuken und/oder der Polymerzubereitung der strahlenabsorbierenden Schicht besteht. Grundsätzlich können auch in die Trägerschicht strahlenabsorbierende Teilchen eingebracht werden, die eine strahlenabsorbierende Wirkung der Trägerschicht realisieren. Durch die Zusammenstellung von einer oder mehreren Trägerschichten sowie von einer oder mehreren Strahlenschutzschichten kann ein Material erzeugt werden, das äußerst flexibel sowie dünn ist, insbesondere bleifrei und eine folienartige Gestaltung aufweist. Die Abfolge der Schichten ist dabei frei wählbar. Die Schichten können aus verschiedenen Materialien bestehen und unterschiedliche Eigenschaften besitzen. Auf diese Weise ist das Material insbesondere für textile Anwendungen geeignet. Aufgrund der hohen Flexibilität und des geringen Gewichts wird eine Trägerperson bei ihrer Tätigkeit nicht behindert, wobei gleichzeitig eine hohe Strahlenschutzwirkung durch den hohen spezifischen Bleigleichwert erzielt wird. Dabei dient die Trägerschicht insbesondere dazu Festigkeit zu geben.According to a further embodiment it can be provided that the carrier layer also consists of PVC plastisol material and / or polyurethane and / or polyester and / or polyolefins and / or silicone rubbers and / or the polymer preparation of the radiation-absorbing layer. In principle, radiation-absorbing particles which realize a radiation-absorbing effect of the carrier layer can also be introduced into the carrier layer. The combination of one or more carrier layers and one or more radiation protection layers can produce a material which is extremely flexible and thin, in particular lead-free and a foil-like design having. The sequence of layers is freely selectable. The layers can be made of different materials and have different properties. In this way, the material is particularly suitable for textile applications. Due to the high flexibility and low weight, a wearer is not hindered in their activity, while a high radiation protection effect is achieved by the high specific lead equivalent at the same time. The carrier layer serves in particular to give strength.
Es kann dabei vorgesehen sein, dass der Anteil der Polymerzubereitung an der strahlenabsorbierenden Schicht weniger als 20 Gew.-%, aber mehr als 0 Gew.-% und der Anteil der strahlenabsorbierenden Teilchen mehr als 80 Gew.-% beträgt. Insbesondere kann die Polymerzubereitung an der strahlenabsorbierenden Schicht zwischen 5 und 20 Gew.-% und insbesondere zwischen 10 und 20 Gew.-% liegen. Der Anteil der strahlenabsorbierenden Teilchen kann insbesondere zwischen 80 und 95 Gew.-% und insbesondere zwischen 80 und 90 Gew.-% betragen. Dabei muss die Menge der Polymerzubereitung ausreichen, die darin eingebrachten Teilchen sicher zu verbinden.It may be provided that the proportion of the polymer preparation to the radiation-absorbing layer less than 20 wt .-%, but more than 0 wt .-% and the proportion of the radiation-absorbing particles is more than 80 wt .-%. In particular, the polymer preparation on the radiation-absorbing layer can be between 5 and 20% by weight and in particular between 10 and 20% by weight. The proportion of the radiation-absorbing particles may in particular be between 80 and 95% by weight and in particular between 80 and 90% by weight. In this case, the amount of polymer preparation must be sufficient to securely connect the particles introduced therein.
Nach einem ersten Ausführungsbeispiel kann vorgesehen sein, dass die strahlenabsorbierenden Teilchen Zinn, Wismut, Barium und/oder Wolfram umfassen. Dabei kann ausgewählt werden aus dem Metall selbst, Metalloxiden oder Metallsalzen. Die wirksame Menge der strahlenabsorbierenden Teilchen in der strahlenabsorbierenden Schicht soll dabei insbesondere 55 - 75 Gew.-% Zinnpulver, zwischen 0 und 30 Gew.-% Wismut, 0 - 10 Gew.-% Barium und/oder 0 - 20 Gew.-% Wolfram enthalten, wobei die Summe jeweils 100 Gew.-% ergibt. Durch eine derartige Polymerzubereitung mit eingefügten strahlenabsorbierenden Teilchen, lassen sich das Abschirmverhalten, aber auch Gewicht, Flexibilität und Strahlenschutzwirkung optimieren. So wirkt sich die Verwendung der Metalle anstelle der Oxide oder Salze stets positiv auf das Gewicht des Materials aus, sofern dieses mit einem Metallsalz oder Metalloxid des gleichen Metalls verglichen wird bei gleicher Abschirmwirkung.According to a first embodiment it can be provided that the radiation-absorbing particles comprise tin, bismuth, barium and / or tungsten. It can be selected from the metal itself, metal oxides or metal salts. The effective amount of the radiation-absorbing particles in the radiation-absorbing layer should in particular 55-75 wt .-% tin powder, between 0 and 30 wt .-% bismuth, 0 - 10 wt .-% barium and / or 0 - 20 wt .-% Tungsten, the sum in each
Sofern Bleianteile enthalten sind, können hierbei sowohl reines Blei als auch Bleioxid und Bleisalze vorgesehen sein.If lead components are included, pure lead as well as lead oxide and lead salts can be provided here.
Bei einer Weiterbildung der Erfindung ist vorgesehen, dass das Zinnpulver aus einem Gemisch zweier Zinnpulver unterschiedlicher Korngrößenverteilungen mit etwa gleichen Gewichtsverhältnissen besteht.In a development of the invention, it is provided that the tin powder consists of a mixture of two tin powders of different particle size distributions with approximately equal weight ratios.
Dabei sind ca. 90 % der Teilchen des ersten Zinnpulvers (TEGO 30) kleiner 125 µm und ca. 90 % der Teilchen des zweiten Zinnpulvers (TEGO 60) kleiner 75 µm. Das Wismut-Oxid-Pulver, das verwendet werden kann, weist ein D50-Wert im Bereich von 4 - 100 µm auf.About 90% of the particles of the first tin powder (TEGO 30) are smaller than 125 μm and about 90% of the particles of the second tin powder (TEGO 60) are smaller than 75 μm. The bismuth oxide powder that can be used has a D 50 value in the range of 4-100 μm.
Das mehrschichtige Schichtmaterial weist vorzugsweise ein Flächengewicht von 1,2 - 1,5 kg/m2 auf, wobei insbesondere ein Wert von ca. 1,35 kg/m2 angestrebt ist. Das mehrschichtige Schichtmaterial besitzt dabei insbesondere eine Folienstärke von 0,3 bis 1,2 mm, insbesondere von 0,3 - 0,5 mm, vorzugsweise 0,35 - 0,45 mm.The multilayer coating material preferably has a weight per unit area of 1.2 to 1.5 kg / m 2 , with a value of approximately 1.35 kg / m 2 being particularly desired. The multilayered layer material in particular has a film thickness of 0.3 to 1.2 mm, in particular of 0.3 to 0.5 mm, preferably 0.35 to 0.45 mm.
Das Strahlenschutzmaterial kann dabei so gestaltet sein, dass die Trägerschicht auf ihrer der strahlenabsorbierenden Schicht abgewandten Seite abwaschbar oder abriebfest und/oder fest gegenüber Alkoholen und/oder Desinfektionsmitteln ist oder textile Eigenschaften aufweist, wobei beispielsweise eine Beflockung vorgesehen ist, die angenehme taktile Eigenschaften beim Tragen eines aus dem Material hergestellten Produktes sicherstellt. Darüber hinaus kann eine Abriebfestigkeit vorgesehen sein, um die Haltbarkeit eines aus dem Material hergestellten Produktes zu verlängern sowie eine Abwaschbarkeit, um gerade im medizinischen Bereich daraus hergestellte Gegenstände nach Gebrauch problemlos reinigen zu können.The radiation protection material may be designed so that the carrier layer on its side facing away from the radiation-absorbing layer washable or abrasion resistant and / or solid to alcohols and / or disinfectants or has textile properties, for example, a flock is provided, the pleasant tactile properties when wearing ensures a product made of the material. In addition, abrasion resistance may be provided to extend the shelf life of a product made from the material, as well as washability, especially in the medical field to be able to easily clean manufactured objects after use.
Schließlich kann vorgesehen sein, dass das Material sehr flexibel ist. Die Biegesteifigkeit, die ein Maß für die Flexibilität des Materials ist, wurde nach DIN 53121 bestimmt und zum Vergleich mit der Biegesteifigkeit anderer bleifreier Strahlenschutzfolien verglichen. Dabei erfolgte die breitenbezogenen Biegesteifigkeitsmessung der bleifreien Materialien im Dreipunkt-Verfahren nach der Balkenmethode, wobei die Prüfung an einer Zwick-Prüfmaschine erfolgt. Die Formel zur Berechnung beträgt nach DIN 53121 dabei:
Dabei ist die Breite der Probe: b = 35 mm
Messlänge: 1 = 30 mm
maximale Durchbiegung: f = 5 mm.Finally, it can be provided that the material is very flexible. The bending stiffness, which is a measure of the flexibility of the material was determined according to DIN 53121 and compared for comparison with the bending stiffness of other lead-free radiation protection films. In this case, the width-related bending stiffness measurement of the lead-free materials in the three-point method was carried out according to the beam method, wherein the test is carried out on a Zwick testing machine. The formula for calculation is according to DIN 53121:
The width of the sample is: b = 35 mm
Measuring length: 1 = 30 mm
maximum deflection: f = 5 mm.
Besonders bevorzugt sind Materialien insbesondere mit einer Biegesteifigkeit von kleiner 1 cN. Besonders bevorzugt ist, wenn gleichzeitig eine Abschirmwirkung im zuvor genannten Bereich beziehungsweise bei Einzelpunkten ≥ 30, insbesondere ≥ 32 und insbesondere ≥ 34 bezüglich des spezifischen Bleigleichwertes erzielt wird.Particularly preferred are materials, in particular with a bending stiffness of less than 1 cN. It is particularly preferred if at the same time a shielding effect in the aforementioned range or at individual points ≥ 30, in particular ≥ 32 and in particular ≥ 34 with respect to the specific lead equivalent is achieved.
Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung eines Strahlenschutzmaterials, das folgende Schritte umfasst:
- Bereitstellen einer Trägerschicht, insbesondere Herstellen durch Aufrakeln und Trocknen auf ein Substrat,
- Herstellen des Materials für die strahlenabsorbierende Schicht aus einer flüssigen, gießfähigen Polymermatrix und kontinuierlichem oder diskontinuierlichem Zugeben von strahlenabsorbierenden Metallpartikeln,
- Aufstreichen, Aufgießen, Aufrakeln und/oder Auftragen des Materials für die strahlenabsorbierende Schicht auf die Trägerschicht,
- thermische, chemisches, und/oder physikalisches Vernetzen beziehungsweise Aushärten der Polymermatrix.
- Providing a carrier layer, in particular production by knife coating and drying on a substrate,
- Producing the material for the radiation-absorbing layer from a liquid, pourable polymer matrix and continuously or discontinuously adding radiation-absorbing metal particles,
- Spreading, pouring, knife coating and / or applying the material for the radiation-absorbing layer on the support layer,
- thermal, chemical, and / or physical crosslinking or curing of the polymer matrix.
Dabei kann vorgesehen sein, dass das Verfahren zur Herstellung eines Strahlenschutzmaterials der vorstehend beschriebenen Art dient.It can be provided that the method is used to produce a radiation protection material of the type described above.
Des Weiteren kann vorgesehen sein, dass nach Herstellen der flüssigen gießfähigen Polymermatrix eine Durchmischung der flüssigen Phasen vor Zugeben der strahlenabsorbierenden Partikel erfolgt. Das Gesamtmaterial für die strahlenabsorbierende Schicht kann so bearbeitet werden, dass die Partikel homogen verteilt sind und dann entgast werden vor dem Aufstreichen, Aufgießen, Aufrakeln und/oder Auftragen auf die Trägerschicht. Darüber hinaus kann vorgesehen sein, dass zur Verdichtung der Feststoffpartikel in der Polymermatrix die strahlenabsorbierende Schicht mit Ultraschall beaufschlagt wird, nachdem sie auf die Trägerschicht aufgebracht wurde.Furthermore, it can be provided that, after the liquid pourable polymer matrix has been produced, the liquid phases are mixed before addition of the radiation-absorbing particles. The overall material for the radiation absorbing layer may be processed so that the particles are homogeneously distributed and then degassed prior to painting, pouring, knife coating and / or applying to the backing layer. In addition, it can be provided that, for compacting the solid particles in the polymer matrix, the radiation-absorbing layer is subjected to ultrasound after it has been applied to the carrier layer.
Schließlich kann nach einem besonders bevorzugten Ausführungsbeispiel vorgesehen sein, dass die Trägerschicht mit der strahlenabsorbierenden Schicht nicht lediglich adhäsiv verbunden ist, sondern mit der strahlenabsorbierenden Schicht integral verbunden ist, durch Vernetzung der beiden Schichten miteinander beim Aufbringen und Aushärten der strahlenabsorbierenden Schicht auf der Trägerschicht. Dabei erfolgt eine physikalische Ankerbildung der Schichten untereinander. Dies erfolgt zum Beispiel bei Einsatz eines PVC-Plastisols in der strahlenabsorbierenden Schicht, sofern das Material der Trägerschicht so gewählt ist, dass das PVC-Plastisol es anlösen kann.Finally, according to a particularly preferred embodiment, it may be provided that the carrier layer is not only adhesively bonded to the radiation-absorbing layer, but is integrally connected to the radiation-absorbing layer by crosslinking the two layers together during application and curing of the radiation-absorbing layer on the carrier layer. In this case, a physical anchor formation of the layers takes place with each other. This is done, for example, when using a PVC plastisol in the radiation-absorbing layer, provided that the material of the carrier layer is chosen so that the PVC plastisol can dissolve it.
Weiterhin umfasst die Erfindung eine Verwendung des vorstehend beschriebenen Strahlenschutzmaterials als Strahlenschutzkleidung, insbesondere als Strahlenschutzschürze oder Strahlenschutzschurz oder -mantel oder flexible Barrieren, wie Abdeckungen oder Vorhänge.Furthermore, the invention comprises a use of the radiation protection material described above as Radiation protection clothing, in particular as a radiation protection apron or radiation protection apron or sheath or flexible barriers, such as covers or curtains.
Auf diese Weise kann einfach ein Strahlenschutzmaterial hergestellt werden, wobei eine gleichmäßige, schnelle und homogene Verteilung der Metallpartikel in der Polymermatrix sichergestellt werden kann, da eine gleichmäßige Verteilung in einer flüssigen Polymermatrix leicht zu realisieren ist und ein umständliches Kneten oder Walken wie bei den herkömmlichen Strahlenschutzfolienmaterialien entfallen kann. Das entstehende Strahlenschutzmaterial aus mehreren Schichten ist sehr flexibel und über einen weiten Energiebereich gleichmäßig strahlenabsorbierend.In this way, a radiation protection material can be easily produced, whereby a uniform, rapid and homogeneous distribution of the metal particles can be ensured in the polymer matrix, since a uniform distribution in a liquid polymer matrix is easy to implement and cumbersome kneading or walking as in the conventional radiation protection film materials can be omitted. The resulting radiation protection material of several layers is very flexible and uniformly radiation-absorbing over a wide energy range.
Weitere Vorteile und Merkmale ergeben sich aus den übrigen Unterlagen.Further advantages and features emerge from the other documents.
Die Erfindung soll im Folgenden anhand einer Zeichnung näher erläutert werden.The invention will be explained in more detail below with reference to a drawing.
Dabei zeigen:
Figur 1- Schnitt durch ein erfindungsgemäßes Strahlenschutzmaterial;
Figur 2- Tabelle der verschiedenen Materialparameter.
- FIG. 1
- Section through a radiation protection material according to the invention;
- FIG. 2
- Table of the different material parameters.
Die Trägerschicht 2 aus einem PVC-Plastisolfilm wird durch Aufrakeln auf ein silikonbeschichtete Trennpapier 4 und durch anschließendes Gelieren bei 190 - 200 ° C gebildet. Die Trägerschicht 2 gibt dem Strahlenschutzmaterial eine ausreichende Festigkeit. Auf dieser Trägerschicht 2 mit einem Flächengewicht von 70 - 80 g/m3 wird nachfolgend eine Paste der strahlenabsorbierenden Schicht 3 aufgerakelt und dann im Trockenofen bei ca. 200 ° vernetzt beziehungsweise vulkanisiert. Die Gesamtdicke des folienartigen Schichtmaterials beträgt dann ca. 0,35 - 0,45 mm und hat ein Gesamtflächengewicht von ca. 1,35 kg/m2. Die Paste, aus der die strahlenabsorbierende Schicht gebildet ist, besteht aus einem PVC-Plastisol und einem lösungsmittelfreien und wasserfreien Acryl-Nitril-Butadien-Flüssigkautschuk sowie den metallischen Zuschlagstoffen aus Zinnpulver und Wismutoxidpulver. Die Polymermischung der strahlenabsorbierenden Schicht 3 weist 13 Gewichtsanteile Polymermaterial, 65 Gewichtsanteile Zinnpulver und 22 Gewichtsanteile Wismutpulver auf. Das Zinnpulver besteht aus zwei verschiedenen Typen mit unterschiedlicher Korngrößenverteilung (Produktbezeichnung: TEGO-Zinngrieß, TEGO 30 BG, TEGO 60 BG - Fa. Ecka Granules).The
Die Zinnpulver mit unterschiedlicher Korngrößenverteilung sind im Verhältnis 1 : 1 gemischt. Das Wismutoxidpulver wird in der Nomenklatur auch als gelber Wismut (Bi2O3) bezeichnet. Der D50-Wert (Korngrößenverteilung) liegt maximal bei 10 µm mit einem typischen Wert von 5,5 µm.The tin powders with different particle size distribution are mixed in a ratio of 1: 1. The bismuth oxide powder is also referred to in the nomenclature as yellow bismuth (Bi 2 O 3 ). The D 50 value (particle size distribution) is a maximum of 10 μm with a typical value of 5.5 μm.
Das bleifreie Strahlenschutzmaterial kann nach seiner Herstellung zunächst auf der silikonbeschichteten Trennpapierschicht 4 verbleiben, bis es zum Beispiel zu einer Strahlenschutzschürze konfektioniert wird.After its preparation, the lead-free radiation protection material may initially remain on the silicone-coated
Eine bevorzugte bleifreie Rezeptur wird nachstehend angegeben.
(metallisch)
(metallic)
Ein Beispiel einer Polymermischung ist nachstehend angegeben.
Diese Polymermischung geht mit einem Gewichtsanteil von ca. 13 Gew.-% in die zunächst pastenförmige strahlenabsorbierende Schicht ein. Dabei beträgt der Anteil des PVC ca. 31 Gew.-%, der Anteil Flüssigkautschuk ca. 18 Gew.-% und der Anteil Weichmacher ca. 45 Gew.-% an der Polymerzusammensetzung.This polymer mixture enters the initially pasty radiation-absorbing layer at a weight fraction of about 13% by weight. The proportion of PVC is about 31 wt .-%, the proportion of liquid rubber about 18 wt .-% and the amount of plasticizer about 45 wt .-% of the polymer composition.
Die Trägerschicht 2 hat dabei folgende Zusammensetzung:
Die Viskosität lässt sich durch Verändern des Anteils des Weichmachers TXIB einstellen.The viscosity can be adjusted by changing the proportion of the plasticizer TXIB.
Ein derartiges Strahlenschutzmaterial mit einer Folienstärke von 0,35 - 0,45 mm und einem Gesamtflächengewicht von 1,35 kg/m2 erreicht nach der Prüfmethode IEC 1331-1/EN 61331 folgende Bleigleichwerte in Abhängigkeit von der Röhrenspannung einer Röntgenquelle:
- 0,14 mm Pb bei 60 kV
- 0,15 mm Pb bei 80 kV
- 0,15 mm Pb bei 100 kV
- 0,13 mm Pb bei 150 kV,
- 0.14 mm Pb at 60 kV
- 0.15 mm Pb at 80 kV
- 0.15 mm Pb at 100 kV
- 0.13 mm Pb at 150 kV,
Im Gegensatz zu bekannten Strahlenschutzmaterialien zeigt das beschriebene Strahlenschutzmaterial keinen Einbruch des Abschirmwirkungsgrades bei Röhrenspannung über 100 kV, sondern ist über eine Spannungsbreite von 60 - 150 kV innerhalb der vorgeschriebenen Toleranzgrenzen des internationalen Standards IEC 1331-1/EN 61331.In contrast to known radiation protection materials, the radiation protection material described does not show a collapse of the shielding efficiency at tube voltage over 100 kV, but is within a voltage range of 60-150 kV within the prescribed tolerance limits of the international standard IEC 1331-1 / EN 61331.
Die zweite Figur zeigt nun eine Tabelle, in der die Probennummer, die Rezepturnummer, das Flächengewicht, die Biegesteifigkeit, die Materialstärke sowie dann folgend die Abschirmwirkungen bei gegebener Röntgenröhrenspannung für 60 kV, 80 kV, 100 kV und 125 kV jeweils für den spezifischen wie auch den allgemeinen Bleigleichwert angegeben sind. Die Probennummern 1 - 14 beziehen sich auf erfindungsgemäße Strahlenschutzmaterialien. Bei den Proben Nr. 15 - 19 Xenolite bleifrei sowie Suprasine handelt es sich um auf dem Markt befindliche Produkte für bleifreie Strahlenschutzmaterialien. Der spezifische Bleigleichwert der Röntgenröhrenspannung definiert sich als der Bleigleichwert bei Röntgenröhrenspannung x 100/Materialstärke.The second figure now shows a table in which the sample number, the recipe number, the basis weight, the bending stiffness, the material thickness and then the shielding effects at a given x-ray tube voltage for 60 kV, 80 kV, 100 kV and 125 kV respectively for the specific as well the general lead equivalent. The sample numbers 1-14 relate to radiation protection materials according to the invention. Sample Nos. 15 - 19 Xenolite lead-free and Suprasine are marketed products for lead-free radiation protection materials. The specific lead equivalent of the x-ray tube voltage is defined as the lead equivalent at x-ray tube voltage x 100 / material thickness.
Der Bleigleichwert wurde nach IEC 1331-1/EN 61331 ermittelt.The lead equivalent was determined according to IEC 1331-1 / EN 61331.
Die Zusammensetzungen für die Strahlenschutzschicht sind dabei wie folgt:
Die Zusammensetzung der Polymerzubereitung ist dabei wie folgt bei den Rezepturen 1 - 4 :
Aus der Tabelle ergibt sich, dass die vorgenommenen Proben insbesondere nach der Rezeptur 2 einen besonders guten spezifischen Bleigleichwert, im Vergleich zu den bekannten Produkten aufweisen, insbesondere über einen Röhrenspannungsbereich von mindestens 20 kV Differenz, wobei die absoluten Spannungswerte zwischen 60 und 125 kV liegen.From the table it follows that the samples made, in particular according to
Daraus ergibt sich, dass, sofern man einen Abschirmwert von 0,175 Pb erzielen will, bei dem Xenolitematerial eine Dicke von 0,6 mm notwendig ist und sich hieraus eine Biegesteifigkeit für das Material von 1,28 cN ergibt. Suprasine benötigt eine Dicke von 0,65 mm zur Erzielung dieser Abschirmleistung und weist dann eine Biegesteifigkeit von 1,11 cN auf. Die erfindungsgemäße Zusammensetzung beispielsweise gemäß Rezeptur 2 benötigt zur Erreichung dieses Abschirmwerts lediglich eine Dicke von 0,45 mm und erreicht eine Biegesteifigkeit von 0,43 cN. Auf diese Weise können besonders leichte und flexible, für den Träger angenehme Materialien, insbesondere für die Herstellung von Textilien, wie Bekleidung und Barrieren, geschaffen werden.It follows that, if one wants to achieve a shielding value of 0.175 Pb, the thickness of the xenolite material is 0.6 mm and this results in a bending stiffness for the material of 1.28 cN. Suprasine needs a thickness of 0.65 mm to achieve this shielding performance and then has a flexural stiffness of 1.11 cN. The composition according to the invention, for example according to
Claims (16)
- Radiation protection material for shielding X-rays and/or gamma rays from a foil-like, multi-layer material in which radiation-absorbing particles are dispersed, wherein the layer material consists of at least one carrier layer and one radiation absorbing layer, characterized in that the radiation-absorbing layer comprises a hardenable polymer preparation which is flowable in the processing state and wherein the effective lead portion is ≤ 15 weight% characterized in that the polymer preparation of the radiation absorbing layer comprises a PVC-plastisol and a liquid caoutchouc component, in particular a mixture of PVC-plastisol and a liquid caoutchouc component.
- Radiation protection material according to claim 1, characterized in that the polymer material comprises softeners and/or cross-linking agents and/or further additional auxiliary substances.
- Radiation protection material according to claim 1 or 2, characterized in that the polymer preparation contains between 20 and 40 weight% PVC and 10 to 35 weight% liquid caoutchouc, 0 to 10 weight% additional and auxiliary substances, the rest being softener.
- Radiation protection material according to claim 3, characterized in that the polymer preparation contains 25 to 35 weight%, in particular 30 weight% PVC, 15 to 25 weight%, in particular 20 weight% liquid caoutchouc, 0 to 7 weight% additional substances and auxiliary means, the rest being softener.
- Radiation protection material according to any one of the preceding claims, characterized in that the effective lead content is ≤ 10 weight%, in particular ≤ 5 weight% and in particular 0 weight%.
- Radiation protection material according to any one of the preceding claims, characterized in that the specific lead equivalent is ≥ 30, in particular ≥ 32 and in particular ≥ 34 at at least a tube voltage within a tube voltage range of between 60 and 125 kV in accordance with IEC 1331-1/EN 61331.
- Radiation protection material according to claim 6, characterized in that the specific lead equivalent is ≥ 30 at at least two tube voltages having a difference of at least 20 kV within a tube voltage range of between 60 and 125 kV in accordance with IEC 1331-1/EN 61331 and in particular ≥ 32 and in particular ≥ 34 and in particular the tube voltages differ by 40 kV, 45 kV and in particular 65 kV.
- Radiation protection material according to any one of the preceding claims, characterized in that the carrier layer consists of PVC-plastisol material and/or polyurethane and/or polyester.
- Radiation protection material according to any one of the preceding claims, characterized in that the portion of the polymer preparation of the radiation-absorbing layer is > 0 and ≤ 20 weight% and the portion of radiation absorbing particles is ≥ 80 weight% and < 100 weight% and in particular the portion of the polymer preparation is 10 to 20 weight% and the portion of radiation absorbing particles is 80 to 90 weight%.
- Radiation protection material according to any one of the preceding claims, characterized in that the radiation absorbing particles contain tin, bismuth, barium and/or tungsten and oxides and salts of the metals and mixtures thereof.
- Radiation protection material according to any one of the preceding claims, characterized in that the multi-layer material has a thickness of 0.3 to 1.2 mm, in particular 0.3 to 0.5 mm, preferably 0.35 to 0.45 mm.
- Radiation protection material according to any one of the preceding claims, characterized in that radiation absorbing particles are contained in the at least one carrier layer.
- Radiation protection material according to any one of the preceding claims, characterized in that the at least one carrier layer can be washed and/or is abrasion-resistant and/or has textile properties on its side facing away from the radiation absorbing layer.
- Radiation absorbing material according to any one of the preceding claims, characterized in that the carrier layer is integrally connected with the radiation absorbing layer.
- Method for producing a radiation protection material according to any one of the preceding claims, characterized in that a carrier layer is provided, in particular produced through doctoring and drying on a substrate, a material for a radiation absorbing layer is produced from of a pourable liquid polymer preparation through adding radiation absorbing particles and the material for the radiation-absorbing layer is disposed, poured, doctored or applied onto the carrier layer and the material of the radiation absorbing layer is hardened through thermal and/or chemical and/or physical cross-linking.
- Use of a radiation protection material according to any one of the preceding claims, as radiation protection clothes, in particular as a radiation protection apron or radiation protection loincloth.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2002208918 DE20208918U1 (en) | 2002-06-08 | 2002-06-08 | Lead-free radiation protection material |
DE20208918U | 2002-06-08 | ||
PCT/EP2003/006085 WO2004017333A1 (en) | 2002-06-08 | 2003-06-10 | Radiation protection material, method for production of a radiation protection material and use of the same |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1512154A1 EP1512154A1 (en) | 2005-03-09 |
EP1512154B1 true EP1512154B1 (en) | 2010-03-31 |
Family
ID=29285776
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20030787749 Expired - Lifetime EP1512154B1 (en) | 2002-06-08 | 2003-06-10 | Radiation protection material, method for production of a radiation protection material and use of the same |
Country Status (7)
Country | Link |
---|---|
US (2) | US20060151749A1 (en) |
EP (1) | EP1512154B1 (en) |
JP (1) | JP4620460B2 (en) |
AT (1) | ATE463035T1 (en) |
AU (1) | AU2003285657A1 (en) |
DE (2) | DE20208918U1 (en) |
WO (1) | WO2004017333A1 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4268162B2 (en) * | 2005-10-18 | 2009-05-27 | 日本特装株式会社 | Radiation protection equipment for vehicles |
US20110165373A1 (en) * | 2010-01-07 | 2011-07-07 | BIoXR, LLC | Radio-opaque films of laminate construction |
US20140151584A1 (en) * | 2012-10-29 | 2014-06-05 | Bloxr Corporation | Nuclear radiation shields, shielding systems and associated methods |
US9114121B2 (en) * | 2010-01-07 | 2015-08-25 | Bloxr Solutions, Llc | Radiation protection system |
US8754389B2 (en) * | 2010-01-07 | 2014-06-17 | Bloxr Corporation | Apparatuses and methods employing multiple layers for attenuating ionizing radiation |
JP5791281B2 (en) * | 2010-02-18 | 2015-10-07 | キヤノン株式会社 | Radiation detection apparatus and radiation detection system |
DE112011105651T5 (en) * | 2011-09-23 | 2014-08-28 | Planideia Confecção De Vestuário De Proteção Ltda. -Epp | Radiopake elastomeric materials with carbon-carbon bonds, process for their preparation and use thereof |
CN102496396B (en) * | 2011-11-16 | 2013-11-06 | 哈尔滨工业大学 | Rare earth/ tungsten/ polyethylene composite gradient nuclear radiation prevention material and production method thereof |
CN102648783A (en) * | 2012-05-19 | 2012-08-29 | 扬州锦江有色金属有限公司 | Shielding shoe with nuclear-radiation-prevention alloy cellosilk woven layer |
CN102664050B (en) * | 2012-05-28 | 2014-10-29 | 丁俊 | Radiation protection material |
USD751256S1 (en) | 2013-08-22 | 2016-03-08 | Gonaprons Llc | Radiation shielding device |
US9534089B2 (en) * | 2014-07-11 | 2017-01-03 | The Boeing Company | Temperature-resistant silicone resins |
US10128010B2 (en) | 2014-12-15 | 2018-11-13 | Tokuyama Corporation | Radiation shielding material and production method therefor |
CN108586777A (en) * | 2018-04-19 | 2018-09-28 | 孙海 | A kind of preparation method of unleaded anti-ray radiation rubber composite material |
JP7092302B2 (en) | 2018-05-31 | 2022-06-28 | 早川ゴム株式会社 | Radiation shielding finger cot |
RU2709596C1 (en) * | 2019-02-15 | 2019-12-18 | Акционерное общество "Научно-исследовательский институт резиновых покрытий и изделий" (АО "НИИРПИ") | Thermoradiation-resistant elastomer composition |
CN113674888A (en) * | 2021-08-20 | 2021-11-19 | 山东双鹰医疗器械有限公司 | X-ray and gamma-ray protective hard material and preparation method thereof |
CN113696369A (en) * | 2021-09-08 | 2021-11-26 | 西安工程大学 | Preparation method of X-ray and gamma-ray protective body based on thermoplastic elastomer |
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US3200085A (en) * | 1959-03-02 | 1965-08-10 | Arthur L Barber Jr | Radiation barrier material and method of making the same |
US3061491A (en) * | 1959-07-24 | 1962-10-30 | Cordo Chemical Corp | Laminated structures |
US3627707A (en) * | 1968-12-31 | 1971-12-14 | Ball Corp | Thixotropic polyvinyl chloride plastisol composition |
US4056161A (en) * | 1975-10-30 | 1977-11-01 | Tillotson Corporation | Sound attenuation material |
JPS56131649A (en) * | 1980-03-21 | 1981-10-15 | Showa Denko Kk | Neutron shield |
US4938233A (en) * | 1987-08-03 | 1990-07-03 | Techton, Inc. | Radiation shield |
GB9300564D0 (en) | 1993-01-12 | 1993-03-03 | Smith & Nephew | Protective articles |
JP3557864B2 (en) * | 1996-09-24 | 2004-08-25 | 住友電気工業株式会社 | Radiation shielding material and its manufacturing method |
US6153666A (en) * | 1998-07-16 | 2000-11-28 | Bar-Ray Products, Inc. | Radiation-attenuating sheet material |
US6232383B1 (en) * | 1998-11-06 | 2001-05-15 | Nurescell, Inc. | Nuclear resistance cell and methods for making same |
US6828578B2 (en) * | 1998-12-07 | 2004-12-07 | Meridian Research And Development | Lightweight radiation protective articles and methods for making them |
DE20100267U1 (en) * | 2001-01-08 | 2001-06-28 | Thiess Axel | Lead-free X-ray protective material |
DE10234159C1 (en) * | 2002-07-26 | 2003-11-06 | Heinrich Eder | Lead substitute for protection from radiation from x-ray tube, e.g. for protective clothing such as apron, contains tin, bismuth and optionally tungsten or their compounds in matrix |
US7196023B2 (en) * | 2003-04-10 | 2007-03-27 | Kappler, Inc. | Chemically resistant radiation attenuation barrier |
-
2002
- 2002-06-08 DE DE2002208918 patent/DE20208918U1/en not_active Expired - Lifetime
-
2003
- 2003-06-10 AU AU2003285657A patent/AU2003285657A1/en not_active Abandoned
- 2003-06-10 WO PCT/EP2003/006085 patent/WO2004017333A1/en active Application Filing
- 2003-06-10 US US10/516,916 patent/US20060151749A1/en not_active Abandoned
- 2003-06-10 DE DE50312570T patent/DE50312570D1/en not_active Expired - Lifetime
- 2003-06-10 AT AT03787749T patent/ATE463035T1/en not_active IP Right Cessation
- 2003-06-10 EP EP20030787749 patent/EP1512154B1/en not_active Expired - Lifetime
- 2003-06-10 JP JP2004528446A patent/JP4620460B2/en not_active Expired - Fee Related
-
2008
- 2008-01-24 US US12/018,811 patent/US7645506B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US20060151749A1 (en) | 2006-07-13 |
US7645506B2 (en) | 2010-01-12 |
EP1512154A1 (en) | 2005-03-09 |
DE50312570D1 (en) | 2010-05-12 |
ATE463035T1 (en) | 2010-04-15 |
JP2005529352A (en) | 2005-09-29 |
AU2003285657A1 (en) | 2004-03-03 |
WO2004017333A1 (en) | 2004-02-26 |
JP4620460B2 (en) | 2011-01-26 |
US20080128660A1 (en) | 2008-06-05 |
DE20208918U1 (en) | 2003-10-23 |
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