Classifications

• • 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

Definitions

• the present invention is related to protective material that does not contain lead
• X-rays are high frequency and thus are formed of ionised photons comprising high energy electromagnetic waves. While passing through any kind of material, said photons lead to ionisation by interacting with the atoms or molecules that form said material. If the medium from which the photons are passing through is a live cell or a tissue and if they are subjected continuously to this ray the metabolism of the cell will be effected negatively.
• X-rays play a crucial role in the diagnosis and treatment of patients due to its characteristics that can enable imaging through radiation and due to the fact that said radiation can eliminate cells or tumours in radiation applications in the medical field.
• the protective materials that protect from radiation such as x-rays are not only used in medical technology to protect the medical staff related to such an application but also to protect the parts of the patient which are not desired to be subjected to such radiation.
• protective clothes, gloves, hats or l thyroid protectors protection for the genital area, pads, curtains and screens are used to protect medical staff and patients.
• These radiation protective products need to have special features that absorb and/or refract the beam arriving at voltage values established between 60-125 keV exiting out of the X-ray tube.
• Table- 1 shows the mass attenuation coefficients ( ⁇ / ?) of some materials in different x-ray intensities.
• Group-B those showing significant increase in N rel > 1.3 mm PbGW pro 0.1 kg/m2 60-80 kV.
• the attenuation value is defined as the attenuation factor and is determined according to the EN 61331-1 standard (Devices providing protection against X-rays used for diagnosis in Medicine, Section 1: Determination of the attenuation characteristics of Materials) as lead equivalence or as lead attenuation value.
• lead and lead compounds are used in x-ray protective materials as they are easy to obtain and they are fully protective.
• the suitable radiation attenuation materials can be the elements mentioned above or the salts and especially the oxides of these compounds or a mixture thereof.
• their usage as elastic pads or textile products that have been laminated, and that are at a certain thickness (in products that have been produced using lead as 0.1-0.6 mm/area in comparison with test reference samples) or are a unit area in practical applications have been put forward (US 4,938,233; US 5,278,219; US 6,310,355 Bl; WO 2005/023116 Al).
• polymeric structures comprising viscoelastic vinyl polymers, vinyl acetate copolymers, silicon and urethanes (polyester, polyether, polybutadiene), polychloroprene, rubber (natural and synthetic), polystyrene-butadiene block copolymers, poly(n-butyl metachrilate), PS diluted with tricresyl phosphate(polystyrene), polymethylacrilate, poly (alfa-methylstyrene), cellulase trinitrate, polyacrylonitrile, PVC (polyvinylchloride), cellulose tributyrin, cellulose nitrate, gelatine and various PS and polyisoprenes or cross linked poly(beta-hydroxyethylmetacrilate) gels, polyethylenes [LDPE, LLDPE, VLDPE, MDPE, HDPE, MPE (metalloctylene), polyethylenes [LDPE, LLDPE, VLDPE, MD
• IR polyisoprene rubber
• BR polybutadiene rubber
• SBR styrene-butadiene copolymer rubber
• plasticizers are added in order to increase the elasticity, processability, tensibility, to decrease the melting viscosity, to decrease the secondary transition temperature (glass transition temperature) and in order to be able to add further filling materials into the structure of the polymer to be used inside the protective material.
• DUP di- undecylenic phthalate
• DOP dioctyl phthalate
• DINP di-isononyl phthlalate
• DOTAP dioctyltherephthalate
• This product has the characteristics to attenuate at least 10-50% of primary X-rays of 100 keV.
• the amount of radiation attenuation material can change both the attenuation amount, and the elasticity provided by the polymer and according to various sources; it has been stated that the weight of the attenuation material must be higher than the weight of the polymeric material.
• the material is a material which provides protection in the lead equivalence of 0.25 mm, 0.35 mm, 0.50 mm, 1.00 mm, and comprises low and high atom numbered protective materials in layers.
• the material that is protected is lighter than other materials in comparison due to its porous surface. Inside the pores materials such as gas (helium etc.), and materials such as foam are present. These pores or cavities do not have any kind of negative effect in attenuating the passage of x-rays.
• This material is a protective material that can decrease a lOOkeV primary X-ray at least by 50%, that has a shore (00) rigidity of less than 100, and whose friction coefficient is less than 0.15.
• US 2005/0121631 Al describes the thin, light and elastic product developed to be used in radiation attenuation. Said product is obtained by moulding high molecule weighted metal particles and low viscosity viscous latex and casting said materials. Said material can comprise metal parts up to 89% in their structures.
• ⁇ -keratinize mostly carried 27-43% glycine, 23-30% alanine, 12-16% leucine or serine and 12- 17 other aminoacids.
• ⁇ -keratin type is a sample for regular proteins. Protein fibers such as sheep, goat, and black goat fibers are seen to be proteins with a structure (a-helix structure) formed of basic keratin proteins carrying 4-16% cistern.
• Angiogram computerized tomography (CT)
• heart-catheter classic radiology
• thorax- heart radiation techniques Angiogram, computerized tomography (CT), heart-catheter, classic radiology, thorax- heart radiation techniques.
• the aim of the invention is related to the preparation of a material formulation that provides protection from low intensity X-rays which does not comprise lead.
• the formulation has been planned to comprise 3 steps. 1) Matrix formulation 2) The determination of the structure and characteristics of a filler material 3) The effect of the particle size of the filler material to the ray attenuation.
• Basic composition polymers of the matrix materials carrying the filler agent can be polymers such as;
• Viscoelastic vinyl polymers vinyl acetate copolymers, silicon and urethanes (polyester, polyether, polybutadiene), polychloroprene, rubber (natural and synthetic), polystyrene-butadiene block copolymers, poly(n-butyl metacrylate), PS diluted with tricresol phosphate (polystyrene), polymethylacrilate, poly (alfa-methylstyrene), cellulase trinitrate, polyacrylonitrile, PVC (polyvinylchloride), cellulose tributyrin, cellulose nitrate, gelatine and various PS and polyisoprenes or cross linked poly(beta-hydroxyethylmetacrilate) gels, polyethylenes [LDPE, LLDPE, VLDPE, MDPE, HDPE, MPE (metallocene polyethylene), EVA, EMA (ethyl metacrylate), EEA (ethylene ethylacri
• IR polyisoprene rubber
• BR polybutadiene rubber
• NBR Nirile butadiene rubber
• SBR styrene-butadiene copolymer rubber
• Plasticizers inside the matrix material basic composition carrying the filler agent are plasticizers inside the matrix material basic composition carrying the filler agent;
• Plasticizers are added in order to increase the elasticity, processability, tensibility, to decrease the melting viscosity, to decrease the secondary transition temperature (glass transition temperature) and in order to be able to add further filling materials into the structure of the polymer to be used inside the protective material.
• di-alkyl phthalate di-undecylenic phthalate (DUP), dioctyl phthalate (DOP), di-isononyl phthlalate (DINP), di-hexyle phthalate (DHP), tributyl phosphate, and dioctyl maleate, di-n-hexyle adipate (DHA), and butyl benzyle phthalate (BBP), di-hexyle therephthalate (DHTP), dibutyl therephthalate (DBTP), dioctyl therephthalate (DOTP), disononyl cyclo hexane (DINCH- Hexamoll®), benzoates, epoxy vegetable oils (black opium poppy, canola oil and raw cotton oil etc), various sulphonamides and organophosphates are used.
• DUP di-undecylenic phthalate
• DOP dioctyl phthalate
• DINP di
• BaO, ZnO, TiO inorganics were used as activators.
• the polymer and conditioners in the matrix which are basic materials mostly are oxidized with air oxidisation and their life span decreases.
• the antioxidants released into the medium for this reason can be some inorganic antioxidants aside from organic antioxidants such as Gallic acid, benzoic acid, resorcinol, pyrogallon, hydroquinone, ascorbic acid, Polymerized 2,2,4-trimethyl-l,2-dihydroquinoline(TMQ), N-isopropyl-N'-phenyl-p- Phenylenediamine(IPPD), N-(l,3-dimethyl-butyl)-N'-phenyl-P Phenylenediamin.
• organic antioxidants such as Gallic acid, benzoic acid, resorcinol, pyrogallon, hydroquinone, ascorbic acid, Polymerized 2,2,4-trimethyl-l,2-dihydroquinoline(TMQ), N-isopropyl-N'-phenyl-p- Pheny
• Various types of supporting polymers regarded as pre filler agents in order to provide durability and polymer stabilization in the matrix can be used.
• known polymers such as cotton, cellulase etc are not suitable, proteins and polypeptides rich in sulphur and which are not soluble in water can be used.
• HSA human serum albumin
• BSA bovine serum albumin
• en-Acid glycoprotein silk, sheep's wool, wool from different types of goat such as Toros black goat, Ankara Angora goats wool and other animal type wool and carbon black, or one or more thereof can be used as strengtheners.
• Sn and SnO, BaO are not used as they are characterised to be intensively basic, BaS0 4 , W, W 2 0 3 , WI 3 , WC, Bi, Bi 2 0 3 , BilO, Bil 3 , Bismuthsubnitrate, Bismuth subcarbonate have been taken into consideration and have been added to the matrix as filler agents. In the present invention all of these elements and compositions have been each examined and also they have been examined as multiple mixtures.
• the mixture of the matrix and the filler agent is not constituted with a chemical reaction but is constituted more with a physical and mechanical mixture.
• this physical mixture the effective structural characteristic has been observed in two ways as shown below;
• Another aim of the invention is to carry our basic formulations in order to be able to produce non lead, protective gear, providing protection from low intensity x-rays suitable to prepare protective chambers for dentistry, such as protective garments, gloves, hats, thyroid protectors, genital region protectors, pads, curtains, screens, comprising Sn and SnO, BaO, BaS0 4/ W, W 2 0 3 , WI 3 , WC, Bi, Bi 2 0 3 , BilO, Bil 3 , Bismuthsubnitrate, Bismuth subcarbonate and organic materials such as "ovomucoid, gelatine, human serum albumin (HSA), bovine serum albumin (BSA), Oi-Acid glycoprotein, silk, sheep's wool, different types of goat's wool (Toros black goat, Ankara Angora goat) and other animal type wool" which can be converted into a layer in a dough machine by a homogenously mixing procedure conducted via a mixer/Banbury/kneader.
• Figure la Shows the images of W(2-5 pm) filler agents in the scanning electron microscopes
• Figure lb Shows the images of Bi (10-13 pm) filler agents in a scanning electron microscope
• Figure lc Shows the images of BilO (11-16 pm) filler agents in a scanning electron microscope
• Figure Id Shows the images of Sn (2-5 pm) filler agents in a scanning electron microscope Figure le. Shows the images of Bi203 filler agents in a scanning electron microscope
• Figure 2 Show the ionised x-ray intensity attenuation characteristic of the material prepared.
• Iyonised chamber (at a 60 cm lateral 60 cm vertical distance)
• the non lead protective material comprises one or more inorganic active fillers such as Sn and SnO, BaO, BaS0 4 , W, W 2 0 3 , WI 3 , WC, Bi, Bi 2 0 3/ BilO, Bil 3 , Bismuthsubnitrate, Bismuth subcarbonate.
• Bismuthsubcarbonate has been used to prepare BilO aside from Bi 2 0 3 and Bismuthsubnitrate filler agent, but BaO was only used at the rate of 0-1.0% as a catalyst in order to achieve an attenuation filler agent.
• the particle size of the attenuation material is important in terms of the distribution inside the polymer matrix. It is recorded in the literature that the attenuation per unit mass with the combination of the elements which are compatible to each other in the structure that has been established is higher than those elements that are used on its own.
• the attenuation size of the BilO which has a particle size smaller than 16pm established in this invention is 11% higher when compared with the crystal shaped BilO mentioned in the patent numbered WO 2004/099078.
• one or more of the organic materials such as ovomucoid, gelatine, human serum albumin (HSA), bovine serum albumin (BSA), or Acid glycoprotein, silk, sheep's wool, different goat type wools (Toros black goat, Ankara Angora goat) and other wools with animal origin are used.
• HSA human serum albumin
• BSA bovine serum albumin
• Acid glycoprotein silk, sheep's wool, different goat type wools (Toros black goat, Ankara Angora goat) and other wools with animal origin are used.
• the matrix in the non lead protective material subject to the invention comprises one or more polymeric binders defined under the title "Basic composition polymers of the matrix materials carrying the filler agent" as a binder.
• the matrix in the non lead protective material subject to the invention comprises one or more plasticizers defined under the title "Plasticizers inside the matrix material basic composition, carrying the filler agent" as plasticizers.
• BilO is a crystallized structure
• the BilO synthesis having a particle size smaller than 16 pm using a different synthesis process; is dissolved in 120.0 g (6.0 part/weight) KI or (5.4 part/weight Nal) 300.0 ml de-ionised water, 700.0 ml de-ionized water is added to 200.0 g (10 part/weight) Bismuthsubnitrate, and the mixture is mixed in a mechanical mixture (1200 cycle/minute), and the mixture is heated at 85 °C temperature. KI (or Nal) solution is slowly (2-10 minutes) added on top. The mixture is mixed for a further 30 minutes and left to cool.
• SnCI 2 is mixed with 500.0 ml de-ionized water up to 80 °C temperature and is mixed and dissolved. 80.0 g NaOH is dissolved in 500.0 ml de-ionized water and SnCI 2 precipitation is added to NaOH solvent and mixed (1250 cycle/minute) slowly (in 5-15 minutes). The mixture is mixed for 45 minutes and is left to cool. It is washed with 300 ml de-ionized water each time and after it has been drained it is dried at 90 °C/10 3 Pa and grey SnO with a particle size smaller than 16pm is obtained (Yield %89).
• sample which comprises 50 part weight (70 part/weight DOP and 30 part/weight latex) is taken from sample- 2.1, 50part weight Bismuthsubnitrate is added and mixed, lamination is carried out in a lamination machine
• sample which comprises 50 part/weight (70 part/weight DOP and 30 part/weight latex) is taken from sample- 2.1, 50 part/weight BaC0 3 is added and mixed, lamination is carried out in a lamination machine (However BaC0 3 was not suitable for mass lamination due to its base)
• the sample which comprises 50 part/weight (70 part/weight Hexamoll (DINCH) and 30 part/weight latex) is taken from sample- 2.1, 50 part/weight Bismuthsubnitrate is mixed, lamination is carried out in a lamination machine.
• the sample which comprises 40 part/weight is taken from Sample -2.4, and is mixed with 60 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.
• 36 part/weight is taken from sample 2.4 (79 part/weight natural rubber and 21 part weight Ankara Angora goats wool), and is mixed with 56.8 part weight Bismuthsubnitrate and 7.2 part/weight Tungsten. The mixture is laminated in a lamination machine.
• 38.6 part/weight is taken from sample 2.4 (79 part/weight natural rubber and 21 part/weight Ankara Angora goats wool), and is mixed with 52.8 part/weight Bismuthsubnitrate and 8.6 part/weight Tungsten carbide. The mixture is laminated in a lamination machine.
• 39.8 part/weight is taken from sample 2.4 (83.4 part/weight natural rubber and 16.6 part/weight Ankara Angora goats wool), and is mixed with 17.2 part weight BaS0 4/ 39.2 part/weight Bismuthsubnitrate and 3.8 part/weight BilO. The mixture is laminated in a lamination machine.
• 36.2 part/weight is taken from sample 2.4 (83.4 part/weight natural rubber and 16.6 part/weight Ankara Angora goats wool), and is mixed with 15.6 part/weight BaS0 4 , 35.6 part weight Bismuthsubnitrate and 9.2 part weight Tungsten and 3.4 part weight BilO. The mixture is laminated in a lamination machine.
• 36.3 part/weight is taken from sample 2.4 (83.4 part/weight natural rubber and 16.6 part weight Ankara Angora goats wool), and is mixed with 15.6 par weight BaS0 4 , 35.7 part/weight Bismuthsubnitrate and 8.9 part/weight Tungsten carbide and 3.4 part weight BilO. The mixture is laminated in a lamination machine.
• 44.8 ' part/weight is taken from Sample-2.5, and is mixed with 55.2 part weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.
• 45.6 part/weight is taken from Sample-2.5, (96.5 part weight PVC/NBR and 3.5 part/weight silk) and is mixed with 54.4 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.
• 40.6 part/weight is taken from Sample-2.5, (96.5 part weight PVC/NBR and 3.5 part weight silk) and is mixed with 48.3 part/weight Bismuthsubnitrate and 11.1 part/weight Bil 3 . The mixture is laminated in a lamination machine.
• Sample 3.21. 52.6 part/weight is taken from Sample-2.5, (72.5 part/weight PVC/NBR and 2.5 part/weight Ankara Angora goats wool and 25 part/weight gelatine) and is mixed with 47.4 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.
• 55.6 part/weight is taken from Sample-2.6, (65.3 part/weight natural rubber and 18.5 part/weight Ankara Angora goats wool and 16.2 part/weight PVC) and is mixed with 32.5 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.
• 56.8 part/weight is taken from Sample-2.4, and is mixed with 29.4 part weight Bismuthsubnitrate and 13.8 part/weight BilO. The mixture is laminated in a lamination machine.
• 46.4 part weight is taken from Sample-2.4, and is mixed with 24.1 part/weight Bismuthsubnitrate and 18.2 part/weight Bismuthsubcarbonate and 11.3 part/weight BilO. The mixture is laminated in a lamination machine.
• 50.7 part/weight is taken from Sample-2.6, (85 part/weight natural rubber and 15 part/weight PVC) and is mixed with 22.3 part/weight Bismuthsubnitrate, 10 part/weight BilO and 22.3 part/weight Bismuthsubcarbonate. The mixture is laminated in a lamination machine.
• 44.5 part/weight is taken from Sample-2.6, (85 part/weight natural rubber and 15 part/weight PVC) and is mixed with 19.8 part/weight Bismuthsubnitrate, 9.1 partyweight BilO and 14.7 part weight Bismuthsubcarbonate and 11.9 part weight Tungsten. The mixture is laminated in a lamination machine.
• 43.3 part/weight is taken from Sample-2.6, (76 part/weight natural rubber and 24 part/weight PVC) and is mixed with 56.7 part weight BilO. The mixture is laminated in a lamination machine.
• the mixture is laminated in a lamination machine.
• 29.4 part/weight is taken from Sample-2.5, and is mixed with 70.6 part/weight Tungsten. The mixture is laminated in a lamination machine.
• 56 part/weight is taken from Sample-2.5, and is mixed with 44 part/weight BilO. The mixture is laminated in a lamination machine.
• 34.6 part weight is taken from Sample-2.7, (78.6 part/weight natural rubber and 21.4 part/weight PVC/NBR), and is mixed with 65.4 part/weight BilO. The mixture is laminated in a lamination machine.
• 29.4 part weight is taken from Sample-2.5, and is mixed with 70.6 part/weight PbO. The mixture is laminated in a lamination machine.
• 47 part/weight is taken from Sample-2.7, (46.8 part/weight natural rubber and 40.4 part/weight Ankara Angora goats wool and 12.8 part weight PVC/NBR), and is mixed with 53 part/weight BilO. The mixture is laminated in a lamination machine.
• 20 part/weight is taken from Sample-2.6, (76 part/weight natural rubber and 24 part weight PVC), and is mixed with 80 part/weight BilO. The mixture is laminated in a lamination machine.
• 15 part/weight is taken from Sample-2.7, (46.8 part/weight natural rubber and 40.4 part/weight Ankara Angora goats wool and 12.8 part/weight PVC/NBR) and is mixed with 85 part/weight BilO. The mixture is laminated in a lamination machine.
• 20 part/weight is taken from Sample-2.8, (60 part/weight PVC/NBR and 1 part/weight Ankara Angora goats' wool) and is mixed with 80 part/weight Bismuth. The mixture is laminated in a lamination machine.
• 25 part/weight is taken from Sample-2.8, (44 part/weight PVC/NBR and 26 part/weight Ankara Angora goats' wool) and is mixed with 75 part weight PbO. The mixture is laminated in a lamination machine.
• 20 part/weight is taken from Sample-2.8, and is mixed with 60 part/weight Bismuth, 20 part/weight Tungsten. The mixture is laminated in a lamination machine.
• 64.6 part/weight is taken from Sample-2.5, (85.6 part/weight PVC/NBR and 14.4 part/weight Toros black goat's wool) and is mixed with 35.4 part/weight BilO. The mixture is laminated in a lamination machine.
• 33,34 part/weight is taken from Sample-2.8, and is mixed with 33,33 part/weight tin oxide, 33,33 part/weight tin. The mixture is laminated in a lamination machine.
• 31,5 part/weight is taken from Sample-2.8, and is mixed with 27,2 part/weight BaS0 4 , 29,1 part/weight BilO, 12,2 part/weight Tungsten carbide. The mixture is laminated in a lamination machine. Sample 3.53.
• 50 part/weight is taken from Sample-2.8, and is mixed with 25 part/weight Bismuth, 25 part/weight BilO. The mixture is laminated in a lamination machine.
• 50 part/weight is taken from Sample-2.8, and is mixed with 25 part/weight Bismuth,
• 50 part/weight is taken from Sample-2.8, and is mixed with 56 part weight Bismuth, 24 part/weight tin. The mixture is laminated in a lamination machine.
• the attenuation characteristics of the ionised rays have been explained in detail above and said samples showing attenuation characteristics have been obtained according to the system given below schematically ( Figure 2).
• the sample material range which will be measured with a x-ray source has been taken as 60cm as a standard.
• the ray intensity (a) distributed and refracted with an electrometer emanating from a 60 to lOOkeV source has been measured with an b) electrometer.
• the a) ray intensity passing through the electrometer following the submission of the rays to the material at the same ray intensities have been b) measured with the reflection of the rays to an electrometer; and
• Table 5 The lamination thickness of the samples and the ionized x-ray at a 60cm distance and the % decrease values of the rays arriving at a 90kvP X-ray dose.

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