EP0242294A1 - Röntgen-Strahlenschutzmaterial - Google Patents

Röntgen-Strahlenschutzmaterial Download PDF

Info

Publication number
EP0242294A1
EP0242294A1 EP87400849A EP87400849A EP0242294A1 EP 0242294 A1 EP0242294 A1 EP 0242294A1 EP 87400849 A EP87400849 A EP 87400849A EP 87400849 A EP87400849 A EP 87400849A EP 0242294 A1 EP0242294 A1 EP 0242294A1
Authority
EP
European Patent Office
Prior art keywords
metal
powder
equal
resin
rays
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.)
Granted
Application number
EP87400849A
Other languages
English (en)
French (fr)
Other versions
EP0242294B1 (de
Inventor
Yves Valy
Jean Bourcereau
Jean Sainte Luce Banchelin
Michel Puech
Jean Duphil
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Airbus Group SAS
Original Assignee
Airbus Group SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Airbus Group SAS filed Critical Airbus Group SAS
Publication of EP0242294A1 publication Critical patent/EP0242294A1/de
Application granted granted Critical
Publication of EP0242294B1 publication Critical patent/EP0242294B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G21F1/103—Dispersions in organic carriers
    • G21F1/106—Dispersions in organic carriers metallic dispersions

Definitions

  • the subject of the present invention is a material for protection against X-rays and various methods of manufacturing this material.
  • This protective material can be used to protect a large number of X-ray sensitive devices such as electronic or optical devices as well as people working under X-rays such as radiologists.
  • the invention applies more particularly to the protection against X-rays of integrated circuits and optical fibers, used in the aeronautical and space fields.
  • One of the techniques most used to protect any device against X-rays is to enclose the device in a pure metal envelope with a high atomic number.
  • the metal and the thickness of the metal sheet are chosen and adapted according to the energy of the X-ray considered and the desired filtering rate. This technique provides effective protection against high doses of X-rays but also against X-rays with high dose rate.
  • the X-ray protective metal sheet cannot be placed directly against all of the external faces of the device because of the often complex profile thereof.
  • this profile complexity is often imposed by heat dissipation constraints.
  • the volume defined by the metal protective sheet is found to be greater than the volume of the device to be protected. This leads to an increase in the weight and size of the device, an increase reinforced by mechanical devices which become necessary for keeping the metal sheet in place (spacer, bracket, screws, etc.).
  • these holding devices must be made of the same metal as that of the protective metal sheet so as not to create "holes" in the protection against X-rays.
  • dielectric ceramics such as barium titanium or neodymium titanate, titanium oxide or a complex ceramic based on lead are cited.
  • the proliferation of individual protections may prove to be more penalizing in weight than an overall protection of all the electronic components.
  • the technology for developing the various materials constituting the stacks is based on processes used for the manufacture of capacitors and in particular sintering processes. In particular, the method described does not make it possible to obtain a material for protection against X-rays having a complex shape.
  • the materials used consist mainly of a filler such as lead, dispersed in an organic binder.
  • a filler such as lead
  • Such protective materials are in particular described in document FR-A-2 190 717 filed in the name of Giken, the document FR-A-2 482 761 filed in the name A. MAURIN, and the patent US-A-3 622,432 from the HK PORTER Company.
  • lead-based materials can only be used as X-ray protective material for low dose rate radiation associated with relatively long dose distribution times.
  • materials for protection against ⁇ and neutron radiation formed from a plastic or rubberized material containing powder of a salt of lead, tungsten, barium, cadmium, bismuth or tin of a saturated fatty acid. These materials are notably described in document FR-A-2 027 514 filed in the name of F. MARYEN.
  • the subject of the present invention is precisely a material for protection against X-rays which makes it possible to remedy the various drawbacks given above.
  • this protective material of the organic material type containing a filler, allows, compared to the use of a heavy metal sheet, a gain in mass and bulk while ensuring effective protection against X-rays. at high dose rate and in particular at dose rate greater than 108 rad.s.
  • this protective material does not pose a major manufacturing problem and can be used in a greater number of applications than those of the prior art.
  • the invention relates to a material for protection against X-rays, characterized in that it is formed from a resin matrix containing in the form of a powder regularly dispersed at least one metal and / or at least one inorganic compound of a metal, the powder melting only at a temperature at least equal to 630 ° C and the metal having an atomic number at least equal to 47.
  • powder of at least one metal and / or at least one inorganic compound of a metal it is in particular necessary to understand a powder consisting of a metal and of an inorganic compound of this same metal or of another metal.
  • thermochock phenomenon within the material.
  • thermal shocks are also linked to the energy spectrum considered.
  • the thermochock generated in the protective material will be much weaker than in the corresponding metal in massive form. This induces a double favorable consequence vis-à-vis the non-degradation of the protective material of the invention against X-rays and vis-à-vis the objects to be protected.
  • the dimensions (thicknesses) and the effi cacity of the material for protection against X-rays are calculated in the energy domain of the absorption, by photoelectric effect, of the material.
  • the parameters influencing the level of protection i.e. filtering, are defined to offer the same protection efficiency as a solid metal taken as a reference.
  • the filtering efficiency of the reference solid metal is expressed in g / cm2.
  • filtering equivalent to n g / cm2 of the reference metal n being a function of the efficiency requirement.
  • any of the protective materials which are the subject of the invention may be used.
  • the possible level of protection being a function, in part, of the thickness available to accommodate materials for protection against X-rays, the nature of the powder and its quantity in the resin matrix will be imposed.
  • the loss of efficiency is all the smaller the higher the quantity of powder and the smaller the particle size.
  • the value of dispersion of the granulometry of the powders in the matrix is linked to the average value of the granulometry chosen for the application considered. This dispersion value can be up to five times the average value of the particle size.
  • the particle size parameter guaranteeing the best compromise "cost-performance-ease of implementation" is for a particle size powder with an average value of 4 ⁇ m with a dispersion coefficient of 2.5.
  • the powder can therefore advantageously contain grains having dimensions ranging from 1.6 ⁇ m to 10 ⁇ m.
  • the amount of powder in the binder can be up to 50% by volume of the finished X-ray protection material. As with particle size, the higher the amount of powder, the more effective the protection. However, an amount of powder greater than 50% by volume is contrary to good mechanical strength of the material and good homogeneity of the latter. Furthermore, the minimum quantity of powder allowing effective protection against X-rays is 25% by volume of the finished protective material.
  • the doping rate is a function of the envisaged application, and in particular a function of the flexibility desired for the protective material.
  • thermoplastic or thermosetting resin may be used.
  • resin which can be used mention may be made of polyamides, poly ethers, polyesters, phenoplasts or phenolic resins, polyolefins, epoxides, polyimides, silicones and furan resins.
  • a silicone resin such as a mixture of RTV1502 and RTV141 from Rhône Poulenc, a phenolic resin such as bakelite or a polyetherblockamide or polyetherblockester resin is used.
  • the metallic powder dispersed in the organic binder can be a powder of silver, antimony, barium, rare earth, tantalum, tungsten, rhenium, irridium, platinum, gold, d 'uranium, hafnium or a mixture of these metals. Silver, tantalum, tungsten or uranium is preferably used as the metal powder.
  • the powder consisting of an inorganic compound, dispersed in the organic binder may be an oxide, a nitride, a carbide of a heavy metal whose atomic number is at least equal to 47 or a mixture of these compounds.
  • metals used in the composition of the inorganic compound use may be made of those mentioned above.
  • the inorganic compound is an oxide, a nitride or a carbide of silver, tantalum, tungsten or uranium when this compound actually exists.
  • the X-ray filtering efficiency is a relationship between the irradiation spectrum and the energy levels of the electron bands of the reference metal. These energy levels have discontinuities which mean that, for a given X-ray energy, a metal "A”, and therefore an inorganic compound of this metal, filters more than a metal "B” and therefore that a inorganic compound of the latter. At a different energy, this metal "B” will be able to filter more than metal "A"; the same is true for the inorganic compounds of these metals.
  • metals and / or of one or more inorganic compounds of a metal makes it possible to optimize protection against X-rays over a very wide energy spectrum.
  • the choice of metals and / or inorganic compounds to be mixed takes into account the specific intended use.
  • metals and / or compounds having complementary absorption spectra are associated in particular in order to obtain the desired protection X.
  • the invention also relates to methods of manufacturing a material for protection against X-rays as defined above.
  • These methods all consist of a premixing of the resin and of the powder and then of a polymerization according to the desired shape.
  • the premixing stage ensures good distribution of the powder in the organic binder, and therefore homogeneity of the opacity of the material for protection against X-rays.
  • a first method consists in melting granules of a thermoplastic resin, in intimately mixing this molten resin with powder of at least one metal and / or at least one inorganic compound of a metal, the powder melting only 'at a temperature at least equal to 630 ° C and the metal having an atomic number at least equal to 47, to extrude the mixture to form granules of said mixture and to polymerize these granules.
  • This process has the advantage of simple implementation and gives very good results as to the homogeneity of the protective material. It can be used, taking into account the flexibility of the material obtained, to produce an X-ray protective sheath of an optical fiber made of plastic, glass or silica or of an electrical conductor.
  • the extrusion of the resin-powder mixture can be obtained with conventional devices and in particular with a WERNER ZSK 30 extruder-granulator.
  • Thermoplastic resins and powders usable are those mentioned above.
  • the polymerization is obtained by the introduction into the mixture of a catalyst or a hardener associated with a temperature cycle.
  • the specific shape of the finished material can be obtained by injection molding or by compression molding, a technique well known to those skilled in the art.
  • a second manufacturing method consists in intimately mixing a first powder of a resin and a second powder of at least one metal and / or at least one inorganic compound of a metal, the second powder not melting that at a temperature at least equal to 630 ° C and the metal having an atomic number at least equal to 47, and to polymerize the mixture obtained.
  • the resin powder has a particle size ranging from 1 to 50 ⁇ m, thus ensuring good distribution of the resin and of the filler in the finished material.
  • This process has the advantage of being able to be used both with thermoplastic resins and with thermosetting resins.
  • the resins and powders that can be used are those given above.
  • thermosetting resins polymerization can be obtained by heating the mold into which the powders are introduced.
  • a third manufacturing process consists in dispersing in a liquid resin a powder of at least one metal and / or at least one inorganic compound of a metal, the powder melting only at a temperature at less equal to 630 ° C and the metal having an atomic number at least equal to 47, and to polymerize the resin thus charged.
  • thermosetting resins such as silicones.
  • This process can be used in particular to cover a protective case, in particular with electronic devices.
  • the casing is covered by overmolding, in particular hot, the charged liquid resin being introduced into the mold by injection.
  • the metal powders or inorganic compounds of a metal used advantageously have a purity greater than 99.9% to allow homogeneity of the opacity with X-rays.
  • a resin sold under the reference PA11 from ATOCHEM are melted at a temperature of 220 ° C.
  • This resin is a thermoplastic polyamide resin, the polymerization of which is obtained by ambient cooling.
  • tungsten is added representing 30% by volume of the finished product.
  • This powder has an average particle size of 4 ⁇ m and a dispersion of 2.5.
  • the purity of tungsten is 99.9%.
  • This mixture is then introduced into a ZSK30 extruder-granulator from the company WERNER in order to obtain mixture granules of 3 to 5mm in diameter which can be polymerized in any form.
  • These mixture granules are in particular introduced into a mold containing a box, intended to contain electronic circuits and to be protected against X-rays.
  • the thickness of the protective coating depends on the efficiency of the desired X-ray filtering and on the energy spectrum of these rays can be adapted in each case. However, a thickness of 1.5 mm may be sufficient in the majority of cases.
  • the casing is coated by injection molding or by compression of the X-ray protective material on the casing to be protected, housed in the mold.
  • an X-ray protective material is produced with the PA11 resin containing 6% by volume of tungsten and 24% by volume of uranium oxide UO2.
  • the powders of W and UO2 have a particle size of 4 ⁇ m and a dispersion of 2.5.
  • the material obtained by injection molding on a housing, provides effective protection against X-rays of energy ranging from 4 to 70 KeV. A thickness greater than 2 mm of this material is sufficient to ensure effective protection of electronic circuits housed in the housing.
  • an X-ray protective material was produced formed from a DINYL resin from RHONE-POULENC containing 30% by volume of a tungsten powder of 99.9% of purity.
  • This resin is a polyetherblockamide, thermoplastic.
  • the average particle size of this powder was 4 ⁇ m with a dispersion coefficient of 2.5.
  • This material was used to coat optical fibers with silica.
  • the outer diameter of the fiber cladding was 2.5 mm.
  • a similar material can be obtained by replacing the DINYL resin with the HYTREL resin from DUPONT de NEMOURS, the latter being a polyether blocker (thermoplastic).
  • An X-ray protective material was formed formed from a silicone matrix (RTV1502 + RTV141) containing a tungsten powder with 40% by volume of the finished material.
  • the tungsten powder has the same characteristics as above.
  • the material obtained is flexible and has an elongation at break greater than 50%. This material is particularly well suited for coating electrical conductors or optical fibers, given its flexibility.
  • the homogeneity of the opacity of the X-ray protective material was checked by a microdensitometric analysis of a photograph of the part obtained in X-ray radiography.
  • the fineness of measurement reaches dimensions 2 ⁇ 5 ⁇ m.
  • the materials obtained according to the invention have a distribution of the opacity values which always falls within the distribution of the opacity of the equivalent protection of the pure metal taken as a reference as a function of the state.
  • metallurgical surface condition, flatness, scratch, edge effect
  • the resin matrix of the protective material according to the invention is a thermoplastic resin
  • the material will be mainly used as a coating material; it may cover a rigid housing or a flat or curved panel made of plastic or metal, an electrical conductor or an optical conductor of plastic or glass.
  • the resin used must have a coefficient of expansion compatible with that of the material constituting the surface to be covered.
  • a protective material according to the invention this can be produced directly in the form of a housing or a protective panel, rigid or flexible depending on the resin used.
  • the material according to the invention finds its application wherever any device must be protected against X-rays and more particularly in the event of a severe mechanical and climatic environment.
  • the invention applies when minimum mass conditions are required.
  • the material according to the invention allows filtering efficiency equivalent to that of a sheet of solid material, a gain in mass, size and a reduction in manufacturing costs.
  • the material according to the invention can be used advantageously to protect the electronic devices on board an aircraft.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • X-Ray Techniques (AREA)
EP19870400849 1986-04-16 1987-04-14 Röntgen-Strahlenschutzmaterial Expired - Lifetime EP0242294B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8605441 1986-04-16
FR8605441A FR2597651B1 (fr) 1986-04-16 1986-04-16 Materiau de protection contre les rayons x et procedes de fabrication de ce materiau

Publications (2)

Publication Number Publication Date
EP0242294A1 true EP0242294A1 (de) 1987-10-21
EP0242294B1 EP0242294B1 (de) 1991-06-19

Family

ID=9334292

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870400849 Expired - Lifetime EP0242294B1 (de) 1986-04-16 1987-04-14 Röntgen-Strahlenschutzmaterial

Country Status (6)

Country Link
EP (1) EP0242294B1 (de)
JP (1) JPS62250399A (de)
CA (1) CA1298698C (de)
DE (1) DE3770857D1 (de)
ES (1) ES2023425B3 (de)
FR (1) FR2597651B1 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0371699A1 (de) * 1988-11-25 1990-06-06 Du Pont Canada Inc. Strahlungsschutzmaterial
EP0372758A1 (de) * 1988-11-25 1990-06-13 Du Pont Canada Inc. Hochgefüllte Zusammensetzungen
WO1994016448A1 (en) * 1993-01-12 1994-07-21 Smith & Nephew Plc Antimicrobial articles
US5548125A (en) * 1991-07-16 1996-08-20 Smith & Nephew Plc Radiation protective glove
FR2755440A1 (fr) * 1996-11-07 1998-05-07 Tuffet Sophie Procede de conservation de longue duree de molecules d'adn et conditionnement pour sa mise en oeuvre
WO1999057264A1 (fr) * 1998-05-06 1999-11-11 Sophie Tuffet Procede de conservation de longue duree de molecules d'adn et conditionnement pour sa mise en oeuvre
FR2969016A1 (fr) * 2010-12-21 2012-06-22 Commissariat Energie Atomique Agencement pour le moulage d'un melange a base de poudre metallique autour d'un noyau ceramique
US20230386690A1 (en) * 2022-05-24 2023-11-30 Stark Street Materials Company Silicon enhanced ionizing radiation shielding and its method of manufacture

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2138865C1 (ru) * 1995-06-29 1999-09-27 Российский Федеральный Ядерный Центр - Всероссийский Научно-Исследовательский Институт Экспериментальной Физики Рентгенозащитная композиция
UA59493C2 (uk) * 2001-12-26 2003-09-15 Юрій Сергійович Алексеєв Радіаційнозахисний матеріал
UA64033C2 (en) * 2002-03-06 2004-02-16 Yurii Sergiiovych Aleksieiev Composite material for radiation protection and the method for producing the material
RU2294030C2 (ru) * 2002-10-02 2007-02-20 Российский федеральный ядерный центр - Всероссийский научно-исследовательский институт экспериментальной физики - РФЯЦ ВНИИЭФ Рентгенозащитная композиция
WO2004051670A1 (fr) * 2002-12-03 2004-06-17 Yuri Sergeyevich Alexeyev Materiau composite de protection contre le rayonnement et procede de production de ce dernier (2 variantes)
RU2326905C2 (ru) * 2006-01-10 2008-06-20 Федеральное государственное унитарное предприятие "Комбинат "Электрохимприбор" Полимерная композиция
RU2325998C2 (ru) * 2006-01-10 2008-06-10 Федеральное государственное унитарное предприятие "Комбинат "Электрохимприбор" Способ изготовления крупногабаритных толстостенных деталей
RU2415485C1 (ru) * 2009-06-30 2011-03-27 Открытое Акционерное Общество "Государственный Ракетный Центр Имени Академика В.П. Макеева" Рентгенозащитная композиция

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE639424A (de) *
FR1168251A (fr) * 1955-12-23 1958-12-05 Everglades Ltd Matériau protecteur pour substances radioactives et récipients constitués par ce matériau
US3114721A (en) * 1961-01-23 1963-12-17 Gen Electric Radiation shielding compositions
FR2212613A1 (de) * 1972-12-28 1974-07-26 Flaugnatti Richard
FR2406870A1 (fr) * 1977-10-20 1979-05-18 Lintott Eng Ltd Ecran antiradiations
FR2439460A1 (fr) * 1978-10-19 1980-05-16 Serole Michelle Materiau de protection radiologique a haut coefficient d'attenuation
FR2570001A1 (fr) * 1984-09-07 1986-03-14 Tech Milieu Ionisant Procede de depot d'un materiau constitue en majeure partie par un metal, un alliage, du bore et/ou une substance ceramique, utilisable pour la realisation de blindages ou d'ecrans biologiques

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE639424A (de) *
FR1168251A (fr) * 1955-12-23 1958-12-05 Everglades Ltd Matériau protecteur pour substances radioactives et récipients constitués par ce matériau
US3114721A (en) * 1961-01-23 1963-12-17 Gen Electric Radiation shielding compositions
FR2212613A1 (de) * 1972-12-28 1974-07-26 Flaugnatti Richard
FR2406870A1 (fr) * 1977-10-20 1979-05-18 Lintott Eng Ltd Ecran antiradiations
FR2439460A1 (fr) * 1978-10-19 1980-05-16 Serole Michelle Materiau de protection radiologique a haut coefficient d'attenuation
FR2570001A1 (fr) * 1984-09-07 1986-03-14 Tech Milieu Ionisant Procede de depot d'un materiau constitue en majeure partie par un metal, un alliage, du bore et/ou une substance ceramique, utilisable pour la realisation de blindages ou d'ecrans biologiques

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0371699A1 (de) * 1988-11-25 1990-06-06 Du Pont Canada Inc. Strahlungsschutzmaterial
EP0372758A1 (de) * 1988-11-25 1990-06-13 Du Pont Canada Inc. Hochgefüllte Zusammensetzungen
AU626944B2 (en) * 1988-11-25 1992-08-13 Du Pont Canada Inc. Radiation protection material
US5548125A (en) * 1991-07-16 1996-08-20 Smith & Nephew Plc Radiation protective glove
WO1994016448A1 (en) * 1993-01-12 1994-07-21 Smith & Nephew Plc Antimicrobial articles
FR2755440A1 (fr) * 1996-11-07 1998-05-07 Tuffet Sophie Procede de conservation de longue duree de molecules d'adn et conditionnement pour sa mise en oeuvre
WO1999057264A1 (fr) * 1998-05-06 1999-11-11 Sophie Tuffet Procede de conservation de longue duree de molecules d'adn et conditionnement pour sa mise en oeuvre
FR2969016A1 (fr) * 2010-12-21 2012-06-22 Commissariat Energie Atomique Agencement pour le moulage d'un melange a base de poudre metallique autour d'un noyau ceramique
WO2012084803A1 (fr) * 2010-12-21 2012-06-28 Commissariat à l'énergie atomique et aux énergies alternatives Agencement pour le moulage d'un melange a base de poudre metallique autour d'un noyau ceramique
US8714955B2 (en) 2010-12-21 2014-05-06 Commissariat à l'énergie atomique et aux énergies alternatives Configuration for moulding a blend made of metal powder around a ceramic core
US20230386690A1 (en) * 2022-05-24 2023-11-30 Stark Street Materials Company Silicon enhanced ionizing radiation shielding and its method of manufacture

Also Published As

Publication number Publication date
EP0242294B1 (de) 1991-06-19
DE3770857D1 (de) 1991-07-25
FR2597651B1 (fr) 1989-12-08
ES2023425B3 (es) 1992-01-16
JPS62250399A (ja) 1987-10-31
CA1298698C (en) 1992-04-14
FR2597651A1 (fr) 1987-10-23

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