EP2798643B1 - Use of a mixture on the basis of erbium and praseodym as a radiation attenuating composition, radiation attenuating material and protection device against ionisating radiation containing such composition - Google Patents

Use of a mixture on the basis of erbium and praseodym as a radiation attenuating composition, radiation attenuating material and protection device against ionisating radiation containing such composition Download PDF

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Publication number
EP2798643B1
EP2798643B1 EP12813051.5A EP12813051A EP2798643B1 EP 2798643 B1 EP2798643 B1 EP 2798643B1 EP 12813051 A EP12813051 A EP 12813051A EP 2798643 B1 EP2798643 B1 EP 2798643B1
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EP
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Prior art keywords
mass
erbium
oxide
praseodymium
compound
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EP12813051.5A
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German (de)
French (fr)
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EP2798643A1 (en
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Noël LANTHEAUME
Marc PICHEGUT
Jacky JEHANNO
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Orano Demantelement SAS
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Areva NC SA
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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
    • G21F1/06—Ceramics; Glasses; Refractories
    • 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
    • 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
    • G21F1/08—Metals; Alloys; Cermets, i.e. sintered mixtures of ceramics and metals
    • G21F1/085—Heavy metals or alloys
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F1/00—Shielding characterised by the composition of the materials
    • G21F1/02—Selection of uniform shielding materials
    • G21F1/10—Organic substances; Dispersions in organic carriers
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F3/00—Shielding characterised by its physical form, e.g. granules, or shape of the material
    • G21F3/02—Clothing
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F3/00—Shielding characterised by its physical form, e.g. granules, or shape of the material
    • G21F3/02—Clothing
    • G21F3/035—Gloves

Definitions

  • the invention relates to the use of an erbium-praseodymium-based mixture as a radio-attenuating composition, that is to say as a composition having the property of attenuating ionizing radiation, in particular electromagnetic radiation of gamma and X type.
  • radio-attenuator material comprising a radio-attenuator composition based on erbium and praseodymium, and to an article of protection, individually or collectively, against ionizing radiation comprising this material.
  • the invention finds application in all fields in which a protection against ionizing radiation can be sought and, in particular, in the fields of nuclear medicine (scintigraphy, radiotherapy, etc. ) , radiology, medical imaging , and the nuclear industry.
  • radio-attenuator composition composed of elemental salt of barium, tungsten and bismuth.
  • the patent application US 2008/0128658 [2] discloses the use of a composition comprising gadolinium oxide Gd 2 O 3 , tungsten and one or more non-gadolinium rare earth oxides, such as LaO 3 , CeO 2 , Nd 2 O 3 , Pr 6 O 11 , Eu 2 O 3 and Sm 2 O 3 .
  • the patent application FR 2 948 672 [3] advocates the use of a composition composed of oxides of tungsten, bismuth and lanthanum.
  • a mixture comprising erbium or a compound thereof and praseodymium or a compound thereof has radiation properties. attenuation particularly advantageous, and that these properties can advantageously be used to produce materials and protective articles suitable for providing highly effective protection against ionizing radiation, in particular gamma and X electromagnetic radiation.
  • radio-attenuation implemented in the context of the invention is based on an interaction which takes place between, on the one hand, the photons resulting from an ionizing radiation, and on the other hand, at least one element radio-attenuator, the latter absorbing part of the energy of these photons.
  • This ionizing radiation may be an electromagnetic radiation of the gamma type, when the latter is emitted by one or more radioactive atoms during their disintegration.
  • This ionizing radiation may also be X-type electromagnetic radiation when it is produced by an X-ray generator, in which a potential difference usually ranging from several tens to several hundred kilovolts (kV) is applied.
  • kV kilovolts
  • the probability and the intensity of this interaction are closely related to various parameters, such as the nature of the radio-attenuator chemical element, the binding forces between the atomic nucleus of this element and the different layers of its electronic procession, or still the energy of the ionizing radiation.
  • the ability of a chemical element to attenuate radiation can be measured by a mass attenuation coefficient, which is proportional to this interaction probability, which is again referred to as an "effective cross-section ".
  • the attenuation is all the more important that the cross section is high.
  • the cross section has discontinuities related to the binding energies of the different electronic layers of this element.
  • the phenomenon of absorption of a photon (gamma or X) by the radio-attenuator chemical element is observed when the energy of the photon is substantially greater than the binding energy of one of the electrons of this chemical element. This phenomenon increases significantly when the energy of this photon is large enough to expel an electron from a deeper electronic layer of the radio-attenuator chemical element.
  • the interaction between the photons resulting from the ionizing radiation and the radio-attenuator chemical element, as described above, can occur according to several effects, such as the photoelectric effect, the Compton effect or the effect of materialization.
  • the predominant effects are closely related to the atomic number of the chemical element which carries out the absorption, but also to the energy of the absorbed radiation.
  • these photons constitute the base of a secondary radiation of type X, of energy mainly centered on 52 keV.
  • erbium and its compounds, in particular its oxides prove to be particularly effective in the field of radio-attenuation, when they are subjected to ionizing radiation, for example an electromagnetic radiation of the type gamma or X, of energy mainly centered on 60 keV.
  • ionizing radiation for example an electromagnetic radiation of the type gamma or X, of energy mainly centered on 60 keV.
  • Mostly centered energy on 60 keV means energy for which a proportion greater than or equal to 80% of the photon distribution of an energy spectrum, which corresponds to this radiation, has an energy of 60 keV.
  • This type of radiation can, for example, come from X-ray generators in which a potential difference, for example ranging from 80 to 150 kV, is applied.
  • This type of radiation may still be the main radiation emitted by a nuclear fuel, for example MOX (consisting of a mixture of plutonium and uranium oxides), for which this main radiation corresponds to the emission of a photon gamma americium-241, itself obtained by ⁇ decay - radioactive plutonium-241.
  • MOX consisting of a mixture of plutonium and uranium oxides
  • the erbium or erbium compound is used in the radio-attenuating composition in combination with praseodymium or a compound thereof.
  • the erbium compound is preferably an erbium oxide and, even more so, erbium sesquioxide (III), of the formula Er 2 O 3
  • the praseodymium compound is preferably an oxide of praseodymium and, more importantly, a chosen oxide from praseodymium (III) oxide, praseodymium (IV) oxide and praseodymium oxide (III-IV), of the formulas Pr 2 O 3 , PrO 2 and Pr 6 O 11 respectively .
  • Praseodymium (III-IV) oxide is particularly preferred.
  • the radio-attenuator composition according to the invention comprises such erbium and praseodymium oxides, this preferably comprises from 55 to 65% by weight of erbium oxide and from 35 to 45% by weight.
  • praseodymium oxide mass more preferably, the radio-attenuator composition comprises (60 ⁇ 2)% by weight of erbium oxide and (40 ⁇ 2)% by weight of praseodymium oxide.
  • a radio-attenuator composition which comprises erbium or a compound thereof and praseodymium or a compound thereof, can be further expanded. using them together with bismuth or a compound thereof.
  • the erbium or the erbium compound and the praseodymium or the praseodymium compound are used within the radio-attenuator composition, together with at least bismuth, introduced in elemental form or in the form of a compound, for example bismuth sesquioxide (III), of formula Bi 2 O 3 , in proportions which depend in particular on the energy of the ionizing radiation received by the radio-attenuator composition and incorporated.
  • bismuth introduced in elemental form or in the form of a compound, for example bismuth sesquioxide (III), of formula Bi 2 O 3
  • composition combining erbium or a compound thereof, praseodymium or a compound thereof and bismuth or a compound thereof allows the attenuation ionizing radiation having a wide energy range, for example between 0 and 100 keV, the radio-attenuation properties of each of these three elements are not discrete but continuous.
  • the bismuth is used in elemental form.
  • bismuth when present in the radio-attenuator composition, it comprises from 30 to 45% by weight of erbium oxide, from 20 to 30% by weight of praseodymium oxide and from 30 to 30% by weight. 45% by weight of bismuth; more preferably, it comprises from 33 to 42% and, particularly preferably, (36 ⁇ 2)% by weight of erbium oxide, from 22 to 28% and, particularly preferably, (24 ⁇ 2)% in weight of praseodymium oxide, and 30 to 45% and particularly preferably (40 ⁇ 2)% by weight of bismuth.
  • erbium or the compound thereof and praseodymium or the compound thereof with antimony, barium, tin, tantalum, tungsten, uranium, one of their compounds and mixtures thereof.
  • erbium or its compound, praseodymium or its compound and, where appropriate, bismuth or its compound are preferably used in the form of powders dispersed in a matrix.
  • the erbium compound is typically an oxide and, in particular, erbium (III) sesquioxide of formula Er 2 O 3 .
  • the praseodymium compound is typically an oxide, which is preferably chosen from praseodymium (III) oxide, praseodymium (IV) oxide and praseodymium (III-IV) oxide, from respective formulas Pr 2 O 3 , PrO 2 and Pr 6 O 11 , praseodymium oxide (III-IV) being very particularly preferred.
  • the radio-attenuator composition according to the invention comprises such erbium and praseodymium oxides, this preferably comprises from 55 to 65% by weight of erbium oxide and from 35 to 45% by weight.
  • praseodymium oxide mass more preferably, this composition comprises (60 ⁇ 2)% by weight of erbium oxide and (40 ⁇ 2)% by weight of praseodymium oxide.
  • the radio attenuator composition according to the invention comprises an erbium oxide, a praseodymium oxide and bismuth
  • the latter preferably comprises from 30 to 45% by weight of erbium oxide, 30% by weight of praseodymium oxide and 30 to 45% by weight of bismuth; more preferably, it comprises from 33 to 42% and, particularly preferably, (36 ⁇ 2)% by weight of erbium oxide, from 22 to 28% and, particularly preferably, (24 ⁇ 2)% in weight of praseodymium oxide, and 30 to 45% and particularly preferably (40 ⁇ 2)% by weight of bismuth.
  • the respective proportions of the matrix and the radio-attenuator composition in the material can vary to a large extent according to the use for which this material is intended and, in particular, the desired level of radio-attenuation. as part of this usage.
  • the matrix represents from 10 to 25% by weight of the mass of the material and that the radio-attenuator composition represents from 75 to 90% by weight of the mass of the material.
  • the matrix represents (15 ⁇ 2)% by mass of the mass of the material and that the radio composition attenuator represents (85 ⁇ 2)% by weight of the mass of the material.
  • the radio-attenuator composition is preferably composed of particles of which at least 90% in number have a lower average particle size. or equal to 20 microns and, more preferably, less than or equal to 1 micron.
  • the matrix it is also chosen according to the use for which the radio-attenuator material is intended.
  • the mechanical properties sought, the characteristics of flexibility and comfort of this article preferably orient towards a matrix based on a thermoplastic material, in particular, polyvinyl chloride, or based on an elastomeric material, chosen in particular from natural rubber, synthetic polyisoprenes, polybutadienes, polychloroprenes, chlorosulfonated polyethylenes, elastomeric polyurethanes, fluoroelastomers (fluoroelastomers), isoprene- iso- butylene copolymers (or butyl rubbers), ethylene-propylene-diene copolymers (or EPDM), block copolymers of styrene-isoprene-s tyrene (or SIS),
  • the search for characteristics of durability and resistance to wear of the material preferably orient towards siliceous matrices, in particular glass, matrices based on a thermosetting resin, chosen in particular from unsaturated epoxy, vinyl ester and polyester resins, or a material based on a thermoplastic, chosen in particular from polyethylene, polypropylene, polycarbonate, for example, bisphenol A polycarbonate, acrylonitrile-butadiene-styrene (or ABS) and products obtained by coextrusion of ABS with (meth) acrylate type compounds , such as polymethylmethacrylate (or PMMA).
  • a thermosetting resin chosen in particular from unsaturated epoxy, vinyl ester and polyester resins
  • a material based on a thermoplastic chosen in particular from polyethylene, polypropylene, polycarbonate, for example, bisphenol A polycarbonate, acrylonitrile-butadiene-styrene (or ABS) and products obtained by coextrusion of ABS with (meth) acrylate type
  • the invention also relates to a protection article against ionizing radiation, comprising a radio-attenuator material as defined above.
  • the protective article is an individual protective article such as a glove, an apron, a chasuble, a jacket, a skirt, a cuff, a thyroid protector, a gonad shield, a protective clothing of the an axillary hollow, an eye protection strip, an operative field, a curtain, a sheet, or a collective protective article such as a mattress, panel, or shield.
  • an individual protective article such as a glove, an apron, a chasuble, a jacket, a skirt, a cuff, a thyroid protector, a gonad shield, a protective clothing of the an axillary hollow, an eye protection strip, an operative field, a curtain, a sheet, or a collective protective article such as a mattress, panel, or shield.
  • the invention has many advantages.
  • Samples E1, E2 and E3 correspond to materials that comprise a radio-attenuator composition composed of Er 2 O 3 and Pr 6 O 11 while samples E4 and E5 correspond to materials that comprise a radio-attenuator composition composed of Er 2 O 3 , Pr 6 O 11 , and bismuth in elemental form.
  • these samples use a radio-attenuator composition in the form of powders of which at least 90% of the particles constituting these powders have an average particle size of less than or equal to 20 ⁇ m.
  • Example 1 The samples obtained in Example 1 above were subjected to tests to evaluate their ability to attenuate ionizing radiation type X, which originates from X-ray generators in which a particular potential difference is applied, or of the gamma type, which are for example emitted by powders used in the manufacture of nuclear fuels.
  • ionizing radiation type X which originates from X-ray generators in which a particular potential difference is applied, or of the gamma type, which are for example emitted by powders used in the manufacture of nuclear fuels.
  • the attenuation properties of type X ionizing radiation by materials according to the invention are evaluated by applying the prescriptions of the standard NF EN 61331-1, entitled "Radiological protection devices against X-rays for medical diagnosis. - Part 1: Determination of the attenuation properties of materials .
  • a gain factor, denoted F X , for a potential difference and specific proportions of Er 2 O 3 / Pr 6 O 11 / Bi in the radio attenuator composition, is also defined as being the ratio of e exp (X) to e theo (X) .
  • the efficiency of a material is equivalent, in terms of radio-attenuation, to that of a material of the same surface mass but consisting solely of lead.
  • Gain factors between 1.14 and 1.63 are obtained with the materials according to the invention, which means that these materials have increased radio attenuating properties compared to materials containing a radio-attenuator agent consisting only of lead.
  • the attenuation properties of a gamma-type ionizing radiation by materials in accordance with the invention are evaluated by means of a device using these materials, placed at a distance between, on the one hand, a a radioactive source consisting of americium-241, which emits ionizing radiation of gamma type energy 59 keV, and secondly, a spectrometer on which is assembled a germanium gamma detector.
  • the method used is to determine the attenuation of gamma-type radiation from americium-241, by measuring the area of the photoelectric absorption peaks recorded by the detector. This surface is compared, by the same method, to surfaces obtained with lead screens of known thickness.
  • e theo ( ⁇ ) an equivalent theoretical lead thickness, denoted e theo ( ⁇ ) , calculated from the mass per unit area of the tested materials, and the density of the lead in metallic form.
  • this thickness corresponds to the thickness of a material of the same mass as the materials tested, but composed only of lead.
  • Gain factors greater than 2 are obtained with the materials according to the invention, which thus have increased radio-attenuating properties compared to materials containing a radio-attenuator agent consisting solely of lead.
  • FIG. Figure 7 A graphical representation of the effective cross-section, denoted n, as a function of the photonic energy, denoted E, is shown on FIG. Figure 7 .
  • the thick line curve which represents the effective cross-section of photons resulting from gamma-type ionizing radiation emitted by americium-241, as a function of the photon energy, has a maximum corresponding to a high distribution of photons having an energy mainly centered on 59.6 keV.
  • such a material according to the invention can be used for attenuation of radiation from the MOX fuel.
  • this ionizing radiation of the type gamma represents a proportion ranging from 75 to 85% of all gamma radiation and X from the latter.

Description

DOMAINE TECHNIQUETECHNICAL AREA

L'invention se rapporte à l'utilisation d'un mélange à base d'erbium et de praséodyme en tant que composition radio-atténuatrice, c'est-à-dire en tant que composition possédant la propriété d'atténuer les rayonnements ionisants, en particulier les rayonnements électromagnétiques de type gamma et X.The invention relates to the use of an erbium-praseodymium-based mixture as a radio-attenuating composition, that is to say as a composition having the property of attenuating ionizing radiation, in particular electromagnetic radiation of gamma and X type.

Elle se rapporte également à un matériau radio-atténuateur comprenant une composition radio-atténuatrice à base d'erbium et de praséodyme, ainsi qu'à un article de protection, individuelle ou collective, contre les rayonnements ionisants comprenant ce matériau.It also relates to a radio-attenuator material comprising a radio-attenuator composition based on erbium and praseodymium, and to an article of protection, individually or collectively, against ionizing radiation comprising this material.

L'invention trouve application dans tous les domaines dans lesquels une protection contre les rayonnements ionisants peut être recherchée et, en particulier, dans les domaines de la médecine nucléaire (scintigraphie, radiothérapie, etc.), de la radiologie, de l'imagerie médicale, et de l'industrie nucléaire.The invention finds application in all fields in which a protection against ionizing radiation can be sought and, in particular, in the fields of nuclear medicine (scintigraphy, radiotherapy, etc. ) , radiology, medical imaging , and the nuclear industry.

ÉTAT DE LA TECHNIQUE ANTÉRIEURESTATE OF THE PRIOR ART

Dans un certain nombre de professions, il est usuel d'utiliser des vêtements et autres articles de protection contre les rayonnements ionisants.In a number of occupations, it is common practice to use clothing and other protective items against ionizing radiation.

C'est notamment le cas dans les domaines de la médecine, de la radiologie, ou encore de l'imagerie médicale, où les rayonnements ionisants sont utilisés à des fins diagnostiques et thérapeutiques.This is particularly the case in the fields of medicine, radiology, or even medical imaging, where ionizing radiation is used for diagnostic and therapeutic purposes.

C'est également le cas dans l'industrie des matières plastiques où des irradiations sont utilisées pour obtenir des effets chimiques de polymérisation, de greffage, de réticulation ou de dégradation de polymères ; dans l'industrie nucléaire, où des opérateurs sont exposés à un risque d'irradiation, notamment lors de la manipulation de poudres de combustibles nucléaires ou du démantèlement d'installations ; ou encore dans les laboratoires d'inspection et de contrôle, par exemple de pièces manufacturées, où des techniques analytiques basées sur l'utilisation de rayonnements ionisants sont employées.This is also the case in the plastics industry where irradiations are used to obtain chemical effects of polymerization, grafting, crosslinking or polymer degradation; in the nuclear industry, where operators are exposed to the risk of irradiation, especially when handling nuclear fuel powders or dismantling of facilities; or in inspection and control laboratories, for example of manufactured parts, where analytical techniques based on the use of ionizing radiation are employed.

La plupart des articles de radioprotection actuellement disponibles sur le marché comprennent une matrice dont la nature dépend de la destination de ces articles et qui renferme du plomb, soit sous la forme de feuilles, soit sous la forme de fines particules, le plomb pouvant alors être à l'état de métal, d'oxyde ou de sel.Most of the radiation protection products currently available on the market include a matrix whose nature depends on the destination of these articles and which contains lead, either in the form of leaves or in the form of fine particles, the lead can then be in the state of metal, oxide or salt.

Compte tenu de la toxicité du plomb et de ses composés, la fabrication de tels articles de protection nécessite un équipement lourd et coûteux pour prévenir toute contamination du personnel en charge de cette fabrication.Given the toxicity of lead and its compounds, the manufacture of such protective articles requires heavy equipment and expensive to prevent contamination of personnel in charge of this manufacture.

De plus, l'élimination des déchets issus de la fabrication de ces articles ainsi que celle des articles de protection après usage nécessite des filières spécifiques de collecte et de traitement, à défaut de quoi ils sont tout simplement éliminés dans des décharges avec toutes les conséquences néfastes sur l'environnement que cela peut impliquer.In addition, the disposal of waste from the manufacture of these articles as well as that of post-use protection articles requires specific collection and treatment channels, otherwise they are simply disposed of in landfills with all the consequences. harmful to the environment that this may imply.

Aussi a-t-il été récemment proposé de remplacer l'utilisation du plomb en tant qu'agent radio-atténuateur par celle d'autres métaux qui sont également capables d'atténuer les rayonnements ionisants mais qui ne sont pas toxiques ou, en tout cas, présentent une toxicité moindre que celle du plomb.It has recently been proposed to replace the use of lead as a radio-attenuator with other metals which are also capable of reducing ionizing radiation but which are not toxic or, at all In this case, the toxicity is lower than that of lead.

Ainsi, par exemple, la demande internationale PCT WO 2006/069007 [1] préconise d'utiliser une composition radio-atténuatrice composée d'un sel de baryum, de tungstène et de bismuth élémentaires.For example, international demand PCT WO 2006/069007 [1] recommends the use of a radio-attenuator composition composed of elemental salt of barium, tungsten and bismuth.

La demande de brevet US 2008/0128658 [2] décrit l'utilisation d'une composition comprenant de l'oxyde de gadolinium Gd2O3, du tungstène et un ou plusieurs oxydes de terres-rares autres que de gadolinium, tels que LaO3, CeO2, Nd2O3, Pr6O11, Eu2O3 et Sm2O3.The patent application US 2008/0128658 [2] discloses the use of a composition comprising gadolinium oxide Gd 2 O 3 , tungsten and one or more non-gadolinium rare earth oxides, such as LaO 3 , CeO 2 , Nd 2 O 3 , Pr 6 O 11 , Eu 2 O 3 and Sm 2 O 3 .

La demande de brevet FR 2 948 672 [3] préconise l'utilisation d'une composition composée d'oxydes de tungstène, de bismuth et de lanthane.The patent application FR 2 948 672 [3] advocates the use of a composition composed of oxides of tungsten, bismuth and lanthanum.

La demande internationale PCT WO 2005/017556 [4] propose d'utiliser une composition comprenant au moins deux éléments choisis parmi l'antimoine, le bismuth, l'iode, le tungstène, l'étain, le tantale, l'erbium, le baryum, les sels, les composés et les alliages de ceux-ci, tandis que la demande de brevet DE 10 2006 958 [5] décrit un matériau multicouche de radioprotection dont certaines couches comprennent un élément radio-atténuateur choisi parmi l'étain, l'antimoine, l'iode, le césium, le baryum, le lanthane, le cérium, le praséodyme et le néodyme, éventuellement associé à un deuxième élément radio-atténuateur ayant, lui, un nombre atomique allant de 60 à 70.International demand PCT WO 2005/017556 [4] proposes to use a composition comprising at least two elements chosen from antimony, bismuth, iodine, tungsten, tin, tantalum, erbium, barium, salts, compounds and alloys thereof, while the patent application DE 10 2006 958 [5] describes a multilayer radioprotection material some of whose layers comprise a radio-attenuator element chosen from tin, antimony, iodine, cesium, barium, lanthanum, cerium, praseodymium and neodymium, possibly associated with a second radio-attenuator element having an atomic number ranging from 60 to 70.

S'il n'est pas contestable que l'erbium et le praséodyme font partie des éléments chimiques qui sont cités, dans les références [2], [4] et [5] précitées, comme étant susceptibles d'être utilisés dans des compositions radio-atténuatrices, il s'avère que rien n'est dit dans ces références sur les capacités réelles de ces deux éléments, pris séparément ou en combinaison, à atténuer les rayonnements ionisants.While it is undeniable that erbium and praseodymium are part of the chemical elements which are cited in references [2], [4] and [5] above, as being capable of being used in compositions radio-attenuators, it turns out that nothing is said in these references about the real capabilities of these two elements, taken separately or in combination, to attenuate ionizing radiation.

Or, il se trouve que, dans le cadre de leurs travaux, les inventeurs ont constaté qu'un mélange comprenant de l'erbium ou un composé de celui-ci et du praséodyme ou un composé de celui-ci présente des propriétés de radio-atténuation particulièrement intéressantes, et que ces propriétés peuvent avantageusement être mises à profit pour réaliser des matériaux et des articles de protection propres à assurer une protection très efficace contre les rayonnements ionisants, en particulier les rayonnements électromagnétiques de type gamma et X.However, it is found that, in the course of their work, the inventors have found that a mixture comprising erbium or a compound thereof and praseodymium or a compound thereof has radiation properties. attenuation particularly advantageous, and that these properties can advantageously be used to produce materials and protective articles suitable for providing highly effective protection against ionizing radiation, in particular gamma and X electromagnetic radiation.

Et c'est sur la base de cette constatation qu'est basée l'invention.And it is on the basis of this observation that the invention is based.

EXPOSÉ DE L'INVENTIONSTATEMENT OF THE INVENTION

L'invention a donc, en premier lieu, pour objet l'utilisation d'un mélange comprenant :

  • de 30 à 70% en masse d'erbium ou d'un composé de celui-ci ;
  • de 20 à 50% en masse de praséodyme ou d'un composé de celui-ci ; et
  • de 0 à 50% en masse de bismuth ou d'un composé de celui-ci ; en tant que composition radio-atténuatrice.
The invention therefore, in the first place, relates to the use of a mixture comprising:
  • from 30 to 70% by weight of erbium or a compound thereof;
  • from 20 to 50% by weight of praseodymium or a compound thereof; and
  • from 0 to 50% by weight of bismuth or a compound thereof; as a radio-attenuator composition.

Le principe de radio-atténuation mis en oeuvre dans le cadre de l'invention a pour base une interaction qui a lieu entre, d'une part, les photons issus d'un rayonnement ionisant, et d'autre part, au moins un élément chimique radio-atténuateur, ce dernier absorbant une partie de l'énergie de ces photons.The principle of radio-attenuation implemented in the context of the invention is based on an interaction which takes place between, on the one hand, the photons resulting from an ionizing radiation, and on the other hand, at least one element radio-attenuator, the latter absorbing part of the energy of these photons.

Ce rayonnement ionisant peut être un rayonnement électromagnétique de type gamma, lorsque celui-ci est émis par un ou plusieurs atomes radioactifs lors de leur désintégration.This ionizing radiation may be an electromagnetic radiation of the gamma type, when the latter is emitted by one or more radioactive atoms during their disintegration.

Ce rayonnement ionisant peut encore être un rayonnement électromagnétique de type X, lorsque celui-ci est produit par un générateur de rayons X, au sein duquel une différence de potentiel allant usuellement de plusieurs dizaines à plusieurs centaines de kilovolts (kV) est appliquée.This ionizing radiation may also be X-type electromagnetic radiation when it is produced by an X-ray generator, in which a potential difference usually ranging from several tens to several hundred kilovolts (kV) is applied.

La probabilité et l'intensité de cette interaction sont étroitement liées à divers paramètres, tels que la nature de l'élément chimique radio-atténuateur, les forces de liaison entre le noyau atomique de cet élément et les différentes couches de son cortège électronique, ou encore l'énergie du rayonnement ionisant.The probability and the intensity of this interaction are closely related to various parameters, such as the nature of the radio-attenuator chemical element, the binding forces between the atomic nucleus of this element and the different layers of its electronic procession, or still the energy of the ionizing radiation.

De manière concrète, la capacité d'un élément chimique à atténuer un rayonnement peut être mesurée par un coefficient d'atténuation massique, qui est proportionnel à cette probabilité d'interaction, celle-ci étant encore appelée « section efficace ».In concrete terms, the ability of a chemical element to attenuate radiation can be measured by a mass attenuation coefficient, which is proportional to this interaction probability, which is again referred to as an " effective cross-section ".

Ainsi, l'atténuation est d'autant plus importante que la section efficace est élevée. Pour un même élément de la classification périodique, la section efficace présente des discontinuités liées aux énergies de liaison des différentes couches électroniques de cet élément.Thus, the attenuation is all the more important that the cross section is high. For the same element of the periodic table, the cross section has discontinuities related to the binding energies of the different electronic layers of this element.

Le phénomène d'absorption d'un photon (gamma ou X) par l'élément chimique radio-atténuateur est constaté lorsque l'énergie du photon est sensiblement supérieure à l'énergie de liaison de l'un des électrons de cet élément chimique. Ce phénomène augmente de manière significative lorsque l'énergie de ce photon est suffisamment importante pour expulser un électron d'une couche électronique plus profonde de l'élément chimique radio-atténuateur.The phenomenon of absorption of a photon (gamma or X) by the radio-attenuator chemical element is observed when the energy of the photon is substantially greater than the binding energy of one of the electrons of this chemical element. This phenomenon increases significantly when the energy of this photon is large enough to expel an electron from a deeper electronic layer of the radio-attenuator chemical element.

Les inventeurs ont ainsi pu mettre en évidence, tel qu'il est explicité de manière ultérieure, l'existence, pour l'erbium et ses composés, d'un maximum d'absorption pour une énergie photonique de l'ordre de 60 kiloélectron-volts (keV). Ce maximum d'absorption est, en outre, supérieur à celui mesuré pour le plomb à la même énergie.The inventors have thus been able to demonstrate, as it is explained later, the existence, for erbium and its compounds, of an absorption maximum for a photon energy of the order of 60 kiloelectrons. volts (keV). This absorption maximum is, in addition, higher than that measured for lead at the same energy.

L'interaction entre les photons issus du rayonnement ionisant et l'élément chimique radio-atténuateur, telle que nous l'avons décrite plus haut, peut se produire suivant plusieurs effets, tels que l'effet photoélectrique, l'effet Compton ou encore l'effet de matérialisation. Les effets prépondérants sont liés de manière étroite au numéro atomique de l'élément chimique qui réalise l'absorption, mais également à l'énergie du rayonnement absorbé.The interaction between the photons resulting from the ionizing radiation and the radio-attenuator chemical element, as described above, can occur according to several effects, such as the photoelectric effect, the Compton effect or the effect of materialization. The predominant effects are closely related to the atomic number of the chemical element which carries out the absorption, but also to the energy of the absorbed radiation.

Dans le cas de l'erbium, élément de numéro atomique 68, soumis à un rayonnement ionisant de 60 keV, l'interaction se produit principalement suivant l'effet photoélectrique, ce qui signifie que chacun des photons du rayonnement ionisant est absorbé en expulsant un électron d'une des couches électroniques de l'atome d'erbium. Celui-ci réorganise de manière subséquente la lacune électronique créée, et restitue l'énergie acquise en émettant un ou plusieurs photons.In the case of erbium, atomic number element 68, subjected to 60 keV ionizing radiation, the interaction occurs mainly according to the photoelectric effect, which means that each of the photons of the ionizing radiation is absorbed by expelling a electron of one of the electron layers of the erbium atom. This one reorganizes the created electronic gap, and restores the acquired energy by emitting one or more photons.

Ainsi, pour cet élément, ces photons constituent la base d'un rayonnement secondaire de type X, d'énergie majoritairement centrée sur 52 keV.Thus, for this element, these photons constitute the base of a secondary radiation of type X, of energy mainly centered on 52 keV.

Les inventeurs ont ainsi pu mettre en évidence que l'erbium et ses composés, notamment ses oxydes, se révèlent particulièrement efficaces dans le domaine de la radio-atténuation, lorsqu'ils sont soumis à un rayonnement ionisant, par exemple un rayonnement électromagnétique de type gamma ou X, d'énergie majoritairement centrée sur 60 keV.The inventors have thus been able to demonstrate that erbium and its compounds, in particular its oxides, prove to be particularly effective in the field of radio-attenuation, when they are subjected to ionizing radiation, for example an electromagnetic radiation of the type gamma or X, of energy mainly centered on 60 keV.

On entend par énergie « majoritairement centrée » sur 60 keV, une énergie pour laquelle une proportion supérieure ou égale à 80% de la distribution de photons d'un spectre énergétique, qui correspond à ce rayonnement, possède une énergie valant 60 keV."Mostly centered" energy on 60 keV means energy for which a proportion greater than or equal to 80% of the photon distribution of an energy spectrum, which corresponds to this radiation, has an energy of 60 keV.

Ce type de rayonnement peut, par exemple, provenir de générateurs de rayons X au sein desquels une différence de potentiel, allant par exemple de 80 à 150 kV, est appliquée.This type of radiation can, for example, come from X-ray generators in which a potential difference, for example ranging from 80 to 150 kV, is applied.

En particulier, pour des différences de potentiel de 80 et 140 kV, les inventeurs ont notamment pu mettre en évidence l'existence d'une distribution élevée de photons ayant une énergie approximativement égale à 60 keV.In particular, for potential differences of 80 and 140 kV, the inventors have in particular been able to demonstrate the existence of a high distribution of photons having an energy approximately equal to 60 keV.

Ce type de rayonnement peut encore être le rayonnement principal émis par un combustible nucléaire, par exemple MOX (constitué d'un mélange d'oxydes de plutonium et d'uranium), pour lequel ce rayonnement principal correspond à l'émission d'un photon gamma par l'américium-241, obtenu lui-même par désintégration β- du plutonium-241 radioactif.This type of radiation may still be the main radiation emitted by a nuclear fuel, for example MOX (consisting of a mixture of plutonium and uranium oxides), for which this main radiation corresponds to the emission of a photon gamma americium-241, itself obtained by β decay - radioactive plutonium-241.

L'existence d'un rayonnement électromagnétique secondaire de type X, tel que décrit précédemment, a également été prise en considération par les inventeurs.The existence of secondary electromagnetic radiation type X, as described above, has also been taken into consideration by the inventors.

De ce fait et conformément à l'invention, l'erbium ou le composé d'erbium est utilisé, dans la composition radio-atténuatrice, en combinaison avec du praséodyme ou un composé de celui-ci.Therefore, and in accordance with the invention, the erbium or erbium compound is used in the radio-attenuating composition in combination with praseodymium or a compound thereof.

En effet, en utilisant une composition radio-atténuatrice associant de l'erbium ou un composé de celui-ci avec du praséodyme ou un composé de celui-ci, les inventeurs ont ainsi pu mettre en évidence, tel qu'il sera démontré ci-après, l'existence de deux maxima d'absorption :

  • grâce à l'erbium ou au composé de celui-ci, par exemple le sesquioxyde d'erbium(III), un maximum d'absorption pour une énergie photonique de l'ordre de 60 keV ; et
  • grâce au praséodyme ou au composé de celui-ci, par exemple l'oxyde de praséodyme(III-IV), un autre maximum d'absorption pour une énergie photonique de l'ordre de 45 keV, correspondant à l'énergie du rayonnement secondaire de type X émis par l'erbium, que nous avons décrit précédemment.
Indeed, by using a radio-attenuator composition associating erbium or a compound thereof with praseodymium or a compound thereof, the inventors have thus been able to highlight, as will be demonstrated hereinafter. after, the existence of two maxima of absorption:
  • thanks to erbium or to the compound thereof, for example erbium sesquioxide (III), an absorption maximum for a photon energy of the order of 60 keV; and
  • thanks to praseodymium or to the compound thereof, for example praseodymium oxide (III-IV), another absorption maximum for a photon energy of the order of 45 keV, corresponding to the energy of the secondary radiation of type X emitted by erbium, which we have described previously.

Le composé d'erbium est, de préférence, un oxyde d'erbium et, plus encore, le sesquioxyde d'erbium(III), de formule Er2O3, tandis que le composé de praséodyme est, de préférence, un oxyde de praséodyme et, plus encore, un oxyde choisi parmi l'oxyde de praséodyme(III), l'oxyde de praséodyme(IV) et l'oxyde de praséodyme(III-IV), de formules respectives Pr2O3, PrO2 et Pr6O11. L'oxyde de praséodyme(III-IV) est tout particulièrement préféré.The erbium compound is preferably an erbium oxide and, even more so, erbium sesquioxide (III), of the formula Er 2 O 3 , while the praseodymium compound is preferably an oxide of praseodymium and, more importantly, a chosen oxide from praseodymium (III) oxide, praseodymium (IV) oxide and praseodymium oxide (III-IV), of the formulas Pr 2 O 3 , PrO 2 and Pr 6 O 11 respectively . Praseodymium (III-IV) oxide is particularly preferred.

Lorsque la composition radio-atténuatrice conforme à l'invention comprend de tels oxydes d'erbium et de praséodyme, celle-ci comprend, de préférence, de 55 à 65% en masse d'oxyde d'erbium et de 35 à 45% en masse d'oxyde de praséodyme; mieux encore, la composition radio-atténuatrice comprend (60 ± 2)% en masse d'oxyde d'erbium et (40 ± 2)% en masse d'oxyde de praséodyme.When the radio-attenuator composition according to the invention comprises such erbium and praseodymium oxides, this preferably comprises from 55 to 65% by weight of erbium oxide and from 35 to 45% by weight. praseodymium oxide mass; more preferably, the radio-attenuator composition comprises (60 ± 2)% by weight of erbium oxide and (40 ± 2)% by weight of praseodymium oxide.

Par ailleurs, les inventeurs ont également pu montrer que le spectre de protection conférée par une composition radio-atténuatrice, qui comprend de l'erbium ou un composé de celui-ci et du praséodyme ou un composé de celui-ci, peut être davantage élargi en les utilisant conjointement avec du bismuth ou un composé de celui-ci.Furthermore, the inventors have also been able to show that the spectrum of protection conferred by a radio-attenuator composition, which comprises erbium or a compound thereof and praseodymium or a compound thereof, can be further expanded. using them together with bismuth or a compound thereof.

Aussi, selon une disposition particulièrement préférée de l'invention, l'erbium ou le composé d'erbium et le praséodyme ou le composé de praséodyme sont utilisés au sein de la composition radio-atténuatrice, de manière conjointe avec au moins du bismuth, introduit sous forme élémentaire ou sous la forme d'un composé, par exemple le sesquioxyde de bismuth(III), de formule Bi2O3, dans des proportions qui dépendent notamment de l'énergie du rayonnement ionisant reçu par la composition radio-atténuatrice ainsi constituée.Also, according to a particularly preferred embodiment of the invention, the erbium or the erbium compound and the praseodymium or the praseodymium compound are used within the radio-attenuator composition, together with at least bismuth, introduced in elemental form or in the form of a compound, for example bismuth sesquioxide (III), of formula Bi 2 O 3 , in proportions which depend in particular on the energy of the ionizing radiation received by the radio-attenuator composition and incorporated.

Ainsi, en utilisant une composition radio-atténuatrice associant de l'erbium ou un composé de celui-ci, du praséodyme ou un composé de celui-ci et du bismuth ou un composé de celui-ci, les inventeurs ont pu mettre en évidence, tel qu'il sera démontré ci-après, l'existence de trois maxima d'absorption :

  • grâce à l'erbium ou au composé d'erbium, par exemple le sesquioxyde d'erbium(III), un maximum d'absorption pour une énergie photonique de l'ordre de 60 keV ;
  • grâce au praséodyme ou au composé de praséodyme, par exemple l'oxyde de praséodyme(III-IV), un maximum d'absorption pour une énergie photonique de l'ordre de 45 keV ;
  • enfin, grâce au bismuth ou au composé de bismuth, un maximum d'absorption pour une énergie photonique de l'ordre de 90 keV, auquel s'ajoutent des propriétés de radio-atténuation très satisfaisantes pour des rayonnements ionisants possédant des énergies photoniques de l'ordre de 40 keV et inférieures.
Thus, by using a radio-attenuating composition associating erbium or a compound thereof, praseodymium or a compound thereof and bismuth or a compound thereof, the inventors have been able to highlight, as will be shown below, the existence of three maxima of absorption:
  • using erbium or the erbium compound, for example erbium sesquioxide (III), an absorption maximum for a photon energy of the order of 60 keV;
  • thanks to praseodymium or to the praseodymium compound, for example praseodymium oxide (III-IV), an absorption maximum for a photon energy of the order of 45 keV;
  • finally, thanks to the bismuth or the bismuth compound, an absorption maximum for a photonic energy of the order of 90 keV, to which are added very satisfactory radiating attenuation properties for ionizing radiation having photonic energies of order of 40 keV and lower.

Au surplus, on peut noter que l'utilisation d'une composition associant de l'erbium ou un composé de celui-ci, du praséodyme ou un composé de celui-ci et du bismuth ou un composé de celui-ci permet l'atténuation d'un rayonnement ionisant ayant une large gamme énergétique, par exemple comprise entre 0 et 100 keV, les propriétés de radio-atténuation de chacun de ces trois éléments n'étant pas discrètes mais continues.In addition, it may be noted that the use of a composition combining erbium or a compound thereof, praseodymium or a compound thereof and bismuth or a compound thereof allows the attenuation ionizing radiation having a wide energy range, for example between 0 and 100 keV, the radio-attenuation properties of each of these three elements are not discrete but continuous.

De préférence, le bismuth est utilisé sous forme élémentaire.Preferably, the bismuth is used in elemental form.

De préférence également, lorsque du bismuth est présent dans la composition radio-atténuatrice, celle-ci comprend de 30 à 45% en masse d'oxyde d'erbium, de 20 à 30% en masse d'oxyde de praséodyme et de 30 à 45% en masse de bismuth ; mieux encore, elle comprend de 33 à 42% et, de façon particulièrement préférée, (36 ± 2)% en masse d'oxyde d'erbium, de 22 à 28% et, de façon particulièrement préférée, (24 ± 2)% en masse d'oxyde de praséodyme, et de 30 à 45% et, de façon particulièrement préférée, (40 ± 2)% en masse de bismuth.Also preferably, when bismuth is present in the radio-attenuator composition, it comprises from 30 to 45% by weight of erbium oxide, from 20 to 30% by weight of praseodymium oxide and from 30 to 30% by weight. 45% by weight of bismuth; more preferably, it comprises from 33 to 42% and, particularly preferably, (36 ± 2)% by weight of erbium oxide, from 22 to 28% and, particularly preferably, (24 ± 2)% in weight of praseodymium oxide, and 30 to 45% and particularly preferably (40 ± 2)% by weight of bismuth.

En variante, il est également possible d'associer l'erbium ou le composé de celui-ci et le praséodyme ou le composé de celui-ci avec de l'antimoine, du baryum, de l'étain, du tantale, du tungstène, de l'uranium, l'un de leurs composés et des mélanges de ceux-ci.Alternatively, it is also possible to associate erbium or the compound thereof and praseodymium or the compound thereof with antimony, barium, tin, tantalum, tungsten, uranium, one of their compounds and mixtures thereof.

Conformément à l'invention, l'erbium ou son composé, le praséodyme ou son composé et, le cas échéant, le bismuth ou son composé sont, de préférence, utilisés sous la forme de poudres dispersées dans une matrice.According to the invention, erbium or its compound, praseodymium or its compound and, where appropriate, bismuth or its compound are preferably used in the form of powders dispersed in a matrix.

L'invention a donc également pour objet un matériau radio-atténuateur qui comprend une matrice dans laquelle est dispersée une composition radio-atténuatrice, la composition étant sous la forme d'une poudre, et qui caractérisé en ce que ladite composition comprend :

  • de 30 à 70% en masse d'erbium ou d'un composé de celui-ci ;
  • de 20 à 50% en masse de praséodyme ou d'un composé de celui-ci ; et
  • de 0 à 50% en masse de bismuth ou d'un composé de celui-ci.
The subject of the invention is therefore also a radio-attenuator material which comprises a matrix in which a radio-attenuator composition is dispersed, the composition being in the form of a powder, and characterized in that said composition comprises:
  • from 30 to 70% by weight of erbium or a compound thereof;
  • from 20 to 50% by weight of praseodymium or a compound thereof; and
  • from 0 to 50% by weight of bismuth or a compound thereof.

Comme mentionné précédemment, le composé d'erbium est typiquement un oxyde et, en particulier, le sesquioxyde d'erbium(III), de formule Er2O3.As mentioned previously, the erbium compound is typically an oxide and, in particular, erbium (III) sesquioxide of formula Er 2 O 3 .

De même, le composé de praséodyme est typiquement un oxyde, lequel est, de préférence, choisi parmi l'oxyde de praséodyme(III), l'oxyde de praséodyme(IV) et l'oxyde de praséodyme(III-IV), de formules respectives Pr2O3, PrO2 et Pr6O11, l'oxyde de praséodyme(III-IV) étant tout particulièrement préféré.Similarly, the praseodymium compound is typically an oxide, which is preferably chosen from praseodymium (III) oxide, praseodymium (IV) oxide and praseodymium (III-IV) oxide, from respective formulas Pr 2 O 3 , PrO 2 and Pr 6 O 11 , praseodymium oxide (III-IV) being very particularly preferred.

Lorsque la composition radio-atténuatrice conforme à l'invention comprend de tels oxydes d'erbium et de praséodyme, celle-ci comprend, de préférence, de 55 à 65% en masse d'oxyde d'erbium et de 35 à 45% en masse d'oxyde de praséodyme; mieux encore, cette composition comprend (60 ± 2)% en masse d'oxyde d'erbium et (40 ± 2)% en masse d'oxyde de praséodyme.When the radio-attenuator composition according to the invention comprises such erbium and praseodymium oxides, this preferably comprises from 55 to 65% by weight of erbium oxide and from 35 to 45% by weight. praseodymium oxide mass; more preferably, this composition comprises (60 ± 2)% by weight of erbium oxide and (40 ± 2)% by weight of praseodymium oxide.

Lorsque la composition radio-atténuatrice conforme à l'invention comprend un oxyde d'erbium, un oxyde de praséodyme et du bismuth, celle-ci comprend, de préférence, de 30 à 45% en masse d'oxyde d'erbium, de 20 à 30% en masse d'oxyde de praséodyme et de 30 à 45% en masse de bismuth ; mieux encore, elle comprend de 33 à 42% et, de façon particulièrement préférée, (36 ± 2)% en masse d'oxyde d'erbium, de 22 à 28% et, de façon particulièrement préférée, (24 ± 2)% en masse d'oxyde de praséodyme, et de 30 à 45% et, de façon particulièrement préférée, (40 ± 2)% en masse de bismuth.When the radio attenuator composition according to the invention comprises an erbium oxide, a praseodymium oxide and bismuth, the latter preferably comprises from 30 to 45% by weight of erbium oxide, 30% by weight of praseodymium oxide and 30 to 45% by weight of bismuth; more preferably, it comprises from 33 to 42% and, particularly preferably, (36 ± 2)% by weight of erbium oxide, from 22 to 28% and, particularly preferably, (24 ± 2)% in weight of praseodymium oxide, and 30 to 45% and particularly preferably (40 ± 2)% by weight of bismuth.

Conformément à l'invention, les proportions respectives de la matrice et de la composition radio-atténuatrice dans le matériau peuvent varier dans une large mesure en fonction de l'usage auquel ce matériau est destiné et, notamment, du niveau de radio-atténuation recherché dans le cadre de cet usage.According to the invention, the respective proportions of the matrix and the radio-attenuator composition in the material can vary to a large extent according to the use for which this material is intended and, in particular, the desired level of radio-attenuation. as part of this usage.

Ceci étant, on préfère généralement que la matrice représente de 10 à 25% en masse de la masse du matériau et que la composition radio-atténuatrice représente, elle, de 75 à 90% en masse de la masse du matériau.This being so, it is generally preferred that the matrix represents from 10 to 25% by weight of the mass of the material and that the radio-attenuator composition represents from 75 to 90% by weight of the mass of the material.

Pour la fabrication d'articles de radioprotection et, notamment, d'articles de protection individuelle tels qu'un tablier de protection, on préfère que la matrice représente (15 ± 2)% en masse de la masse du matériau et que la composition radio-atténuatrice représente (85 ± 2)% en masse de la masse du matériau.For the manufacture of radiation protection articles and, in particular, personal protective articles such as a protective apron, it is preferred that the matrix represents (15 ± 2)% by mass of the mass of the material and that the radio composition attenuator represents (85 ± 2)% by weight of the mass of the material.

Par ailleurs, et ce, de manière à obtenir une répartition de cette composition la plus homogène possible dans la matrice, la composition radio-atténuatrice est, de préférence, constituée de particules dont au moins 90% en nombre ont une taille moyenne de particules inférieure ou égale à 20 µm et, mieux encore, inférieure ou égale à 1 µm.Furthermore, in order to obtain a distribution of this composition as homogeneous as possible in the matrix, the radio-attenuator composition is preferably composed of particles of which at least 90% in number have a lower average particle size. or equal to 20 microns and, more preferably, less than or equal to 1 micron.

Quant à la matrice, elle est également choisie en fonction de l'usage auquel est destiné le matériau radio-atténuateur.As for the matrix, it is also chosen according to the use for which the radio-attenuator material is intended.

Ainsi, par exemple, pour la fabrication d'un article de protection individuelle du type gant, tablier, chasuble, veste, jupe, manchette, protège-thyroïde, protège-gonades, vêtement de protection du creux axillaire, bandeau de protection oculaire, champ opératoire, rideau, nappe, les propriétés mécaniques recherchées, les caractéristiques de souplesse et de confort de cet article, orientent de préférence vers une matrice à base d'un matériau thermoplastique, en particulier, le polychlorure de vinyle, ou encore à base d'un matériau élastomère, choisi en particulier parmi le caoutchouc naturel, les polyisoprènes de synthèse, les polybutadiènes, les polychloroprènes, les polyéthylènes chlorosulfonés, les polyuréthanes élastomères, les élastomères fluorés (ou fluoroélastomères), les copolymères d'isoprène-iso-butylène (ou caoutchoucs butyles), les copolymères d'éthylène-propylène-diène (ou EPDM), les copolymères séquencés de styrène-isoprène-styrène (ou SIS), les copolymères séquencés de styrène-éthylène-butylène-styrène (ou SEBS), et les mélanges de ceux-ci.Thus, for example, for the manufacture of an individual protective article such as glove, apron, chasuble, jacket, skirt, cuff, thyroid protector, gonad protector, axillary hollow protective clothing, eye protection strip, field operating, curtain, tablecloth, the mechanical properties sought, the characteristics of flexibility and comfort of this article, preferably orient towards a matrix based on a thermoplastic material, in particular, polyvinyl chloride, or based on an elastomeric material, chosen in particular from natural rubber, synthetic polyisoprenes, polybutadienes, polychloroprenes, chlorosulfonated polyethylenes, elastomeric polyurethanes, fluoroelastomers (fluoroelastomers), isoprene- iso- butylene copolymers (or butyl rubbers), ethylene-propylene-diene copolymers (or EPDM), block copolymers of styrene-isoprene-s tyrene (or SIS), block copolymers of styrene-ethylene-butylene-styrene (or SEBS), and mixtures thereof.

En variante, pour la fabrication d'un article de protection collective du type matelas, panneau, écran de protection, la recherche de caractéristiques de durabilité et de résistance à l'usure du matériau orientent de préférence vers des matrices de type siliceuse, en particulier le verre, des matrices à base d'une résine thermodurcissable, choisie en particulier parmi les résines de type époxydes, vinylesters et polyesters insaturés, ou encore un matériau à base d'un thermoplastique, choisi en particulier parmi le polyéthylène, le polypropylène, un polycarbonate, par exemple, le polycarbonate de bisphénol A, l'acrylonitrile-butadiène-styrène (ou ABS) et les produits obtenus par co-extrusion de l'ABS avec des composés de type (méth)acrylate, tel que le polyméthacrylate de méthyle (ou PMMA).As a variant, for the manufacture of a collective protection article of the mattress, panel or protective screen type, the search for characteristics of durability and resistance to wear of the material preferably orient towards siliceous matrices, in particular glass, matrices based on a thermosetting resin, chosen in particular from unsaturated epoxy, vinyl ester and polyester resins, or a material based on a thermoplastic, chosen in particular from polyethylene, polypropylene, polycarbonate, for example, bisphenol A polycarbonate, acrylonitrile-butadiene-styrene (or ABS) and products obtained by coextrusion of ABS with (meth) acrylate type compounds , such as polymethylmethacrylate (or PMMA).

L'invention a également pour objet un article de protection contre les rayonnements ionisants, comprenant un matériau radio-atténuateur tel que précédemment défini.The invention also relates to a protection article against ionizing radiation, comprising a radio-attenuator material as defined above.

De préférence, l'article de protection est un article de protection individuelle tel qu'un gant, un tablier, une chasuble, une veste, une jupe, une manchette, un protège-thyroïde, un protège-gonades, un vêtement de protection du creux axillaire, un bandeau de protection oculaire, un champ opératoire, un rideau, une nappe, ou un article de protection collective tel qu'un matelas, un panneau ou un écran de protection.Preferably, the protective article is an individual protective article such as a glove, an apron, a chasuble, a jacket, a skirt, a cuff, a thyroid protector, a gonad shield, a protective clothing of the an axillary hollow, an eye protection strip, an operative field, a curtain, a sheet, or a collective protective article such as a mattress, panel, or shield.

L'invention présente de nombreux avantages.The invention has many advantages.

En effet, elle permet de réaliser des matériaux et des articles de protection qui présentent des propriétés remarquables d'atténuation des rayonnements ionisants, en particulier des rayonnements électromagnétiques de type gamma et X, d'énergie pouvant se situer dans une large gamme, typiquement comprise entre 0 et 100 keV, et ce, à partir de métaux et d'oxydes métalliques qui ne possèdent pas de toxicité connue à ce jour pour la santé humaine et l'environnement.Indeed, it makes it possible to produce materials and protective articles which have remarkable properties of attenuation of ionizing radiation, in particular electromagnetic radiation of the gamma and X type, with energy that can be in a wide range, typically comprised between 0 and 100 keV, from metals and metal oxides that have no known toxicity to human health and the environment.

En outre, l'élimination des déchets issus de leur fabrication ne nécessite donc pas de filière spécifique de collecte et de traitement.In addition, the disposal of waste resulting from their manufacture does not require a specific collection and treatment system.

Enfin, de manière similaire, l'élimination de ces matériaux et articles de protection après usage ne nécessite pas de filière spécifique autre que celles qui sont imposées par une éventuelle contamination par des matières toxiques ou radioactives.Finally, similarly, the disposal of these materials and articles of protection after use does not require a specific path other than those imposed by a possible contamination by toxic or radioactive materials.

D'autres caractéristiques et avantages de l'invention apparaîtront mieux à la lecture du complément de description qui suit, qui se rapporte à des exemples de fabrication de matériaux conformes à l'invention ainsi que de démonstration des propriétés de radio-atténuation de ces matériaux.Other features and advantages of the invention will appear better on reading the additional description which follows, which relates to examples of manufacture of materials according to the invention as well as demonstration of the radio-attenuation properties of these materials. .

Bien entendu, ces exemples ne sont donnés qu'à titre d'illustrations de l'objet de l'invention et ne constituent en aucun cas une limitation de cet objet.Of course, these examples are given only as illustrations of the subject of the invention and do not constitute in any way a limitation of this object.

BRÈVE DESCRIPTION DES FIGURESBRIEF DESCRIPTION OF THE FIGURES

  • La Figure 1 est une représentation graphique comparée du coefficient d'atténuation massique, noté N, en fonction de l'énergie photonique, notée E, dans le cas des éléments plomb (courbe repérée par un pictogramme représentant une croix) et erbium (courbe repérée par un pictogramme représentant un disque).The Figure 1 is a comparative graphical representation of the mass attenuation coefficient, denoted N, as a function of the photonic energy, denoted E, in the case of the elements lead (curve marked by a pictogram representing a cross) and erbium (curve indicated by a pictogram representing a disk).
  • La Figure 2 représente la répartition des composantes de l'interaction entre des photons issus d'un rayonnement ionisant, à la fois en fonction du numéro atomique de l'élément radio-atténuateur, noté Z, et de l'énergie photonique, notée E, les portions de surface notées « EP », « EC » et « EM » représentant respectivement les domaines d'observation de l'effet photoélectrique, de l'effet Compton et de l'effet de matérialisation.The Figure 2 represents the distribution of the components of the interaction between photons resulting from an ionizing radiation, both as a function of the atomic number of the radio-attenuator element, denoted Z, and the photonic energy, denoted E, the portions "EP", "EC" and "EM" respectively representing the fields of observation of the photoelectric effect, the Compton effect and the effect of materialization.
  • La Figure 3 (respectivement, la Figure 4) représente la section efficace, notée N, de photons issus d'un générateur de rayons X au sein duquel une différence de potentiel de 80 kV (respectivement, 140 kV) est appliquée, en fonction de l'énergie photonique, notée E.The Figure 3 (respectively, the Figure 4 ) represents the effective cross section, denoted N, of photons originating from an X-ray generator in which a potential difference of 80 kV (respectively, 140 kV) is applied, as a function of the photonic energy, denoted E.
  • La Figure 5 est une représentation graphique comparée, du coefficient d'atténuation massique, noté N, en fonction de l'énergie photonique, notée E, dans le cas des éléments erbium (courbe repérée par un pictogramme représentant un disque) et praséodyme (courbe repérée par un pictogramme représentant un triangle).The Figure 5 is a comparative graphical representation of the mass attenuation coefficient, denoted N, as a function of the photonic energy, denoted E, in the case of erbium elements (curve indicated by a pictogram representing a disk) and praseodymium (curve indicated by a pictogram representing a triangle).
  • La Figure 6 est une représentation graphique comparée, reprenant le formalisme et la signalétique utilisés dans la Figure 5, en y adjoignant le cas de l'élément bismuth (courbe repérée par un pictogramme représentant un carré).The Figure 6 is a graphical representation comparing the formalism and the descriptive used in the Figure 5 , adding the case of the bismuth element (curve marked by a pictogram representing a square).
  • La Figure 7 représente, en trait épais, la section efficace, notée n, de photons issus d'un rayonnement ionisant de type gamma émis par de l'américium-241, en fonction de l'énergie photonique, notée E. Les portions de surface situées en dessous de la courbe en trait fin représentent la section efficace des photons issus d'un matériau à base d'erbium conforme à l'invention, ayant reçu le rayonnement ionisant, en fonction de l'énergie photonique.The Figure 7 represents, in thick line, the effective cross-section, denoted n, of photons resulting from gamma-type ionizing radiation emitted by americium-241, as a function of the photon energy, denoted E. The surface portions located in below the curve in fine line represent the effective cross section of photons derived from an erbium-based material according to the invention, having received the ionizing radiation, as a function of the photon energy.
EXPOSÉ DÉTAILLÉ DE MODES DE RÉALISATION PARTICULIERSDETAILED PRESENTATION OF PARTICULAR EMBODIMENTS Exemple 1 : Fabrication de matériaux conformes à l'invention Example 1 Manufacture of Materials in Accordance with the Invention

Cinq échantillons, respectivement E1, E2, E3, E4 et E5, de matériaux conformes à l'invention ont été réalisés.Five samples, respectively E1, E2, E3, E4 and E5, of materials in accordance with the invention were made.

Les échantillons E1, E2 et E3 correspondent à des matériaux qui comprennent une composition radio-atténuatrice composée d'Er2O3 et de Pr6O11 tandis que les échantillons E4 et E5 correspondent à des matériaux qui comprennent une composition radio-atténuatrice composée d'Er2O3, de Pr6O11, et de bismuth sous forme élémentaire.Samples E1, E2 and E3 correspond to materials that comprise a radio-attenuator composition composed of Er 2 O 3 and Pr 6 O 11 while samples E4 and E5 correspond to materials that comprise a radio-attenuator composition composed of Er 2 O 3 , Pr 6 O 11 , and bismuth in elemental form.

Ces échantillons, qui se présentent sous la forme de carrés d'approximativement 30 centimètres de côté, sont réalisés par technique d'enduction.These samples, which are in the form of squares approximately 30 centimeters apart, are made by coating technique.

En outre, ces échantillons mettent en oeuvre une composition radio-atténuatrice sous la forme de poudres dont au moins 90% des particules constituant ces poudres possèdent une taille moyenne des particules inférieure ou égale à 20 µm.In addition, these samples use a radio-attenuator composition in the form of powders of which at least 90% of the particles constituting these powders have an average particle size of less than or equal to 20 μm.

Les caractéristiques propres à chacun de ces échantillons sont regroupées dans le Tableau 1. TABLEAU 1 Échantillon E1 E2 E3 E4 E5 Épaisseur (mm) 4,6 2,3 5,2 1,6 3,2 Masse surfacique (kg/m2) 13,4 5,8 13,8 4,8 9,6 Base de la matrice Silicone PVC PVC Silicone Silicone Proportion massique composition/matrice (%/%) 75/25 68/32 68/32 75/25 75/25 Proportion massique Er2O3/Pr6O11/Bi dans la composition (%/%/%) 60/40/0 70/30/0 70/30/0 36/24/40 36/24/40 The characteristics of each of these samples are summarized in Table 1. TABLE 1 Sample E1 E2 E3 E4 E5 Thickness (mm) 4.6 2.3 5.2 1.6 3.2 Mass per unit area (kg / m 2 ) 13.4 5.8 13.8 4.8 9.6 Base of the matrix Silicone PVC PVC Silicone Silicone Proportion mass composition / matrix (% /%) 75/25 68/32 68/32 75/25 75/25 Mass ratio Er 2 O 3 / Pr 6 O 11 / Bi in the composition (% /% /%) 60/40/0 70/30/0 70/30/0 36/24/40 36/24/40

Exemple 2 : Propriétés de radio-atténuation de matériaux conformes à l'invention Example 2: Radio-attenuation properties of materials according to the invention

Les échantillons obtenus à l'Exemple 1 ci-avant ont été soumis à des tests visant à évaluer leur capacité à atténuer les rayonnements ionisants de type X, qui proviennent de générateurs de rayons X au sein desquels une différence de potentiel particulière est appliquée, ou de type gamma, qui sont par exemple émis par des poudres entrant dans la fabrication de combustibles nucléaires.The samples obtained in Example 1 above were subjected to tests to evaluate their ability to attenuate ionizing radiation type X, which originates from X-ray generators in which a particular potential difference is applied, or of the gamma type, which are for example emitted by powders used in the manufacture of nuclear fuels.

1. Propriétés de radio-atténuation en présence d'un rayonnement ionisant de type X 1. Radio-attenuation properties in the presence of X-type ionizing radiation

Les propriétés d'atténuation d'un rayonnement ionisant de type X par des matériaux conformes à l'invention sont évaluées en appliquant les prescriptions de la norme NF EN 61331-1, intitulée « Dispositifs de protection radiologique contre les rayonnements X pour diagnostic médical. - Partie 1 : détermination des propriétés d'atténuation des matériaux » . The attenuation properties of type X ionizing radiation by materials according to the invention are evaluated by applying the prescriptions of the standard NF EN 61331-1, entitled "Radiological protection devices against X-rays for medical diagnosis. - Part 1: Determination of the attenuation properties of materials .

Les résultats tels qu'obtenus avec diverses différences de potentiel sont exprimés en termes d'épaisseur équivalente en plomb théorique, notée ethéo(X), et d'épaisseur équivalente en plomb mesurée, notée eexp(X).The results as obtained with various potential differences are expressed in terms of theoretical lead equivalent thickness, denoted e theo (X) , and measured equivalent lead thickness, denoted e exp (X) .

On définit également un facteur de gain, noté FX, pour une différence de potentiel et des proportions massiques de Er2O3/Pr6O11/Bi particulières au sein de la composition radio-atténuatrice, comme étant le rapport de eexp(X) à ethéo(X).A gain factor, denoted F X , for a potential difference and specific proportions of Er 2 O 3 / Pr 6 O 11 / Bi in the radio attenuator composition, is also defined as being the ratio of e exp (X) to e theo (X) .

Lorsque le rapport FX vaut 1, l'efficacité d'un matériau est équivalente, en terme de radio-atténuation, à celle d'un matériau de même masse surfacique mais constitué uniquement de plomb.When the ratio F X is 1, the efficiency of a material is equivalent, in terms of radio-attenuation, to that of a material of the same surface mass but consisting solely of lead.

Les résultats obtenus pour les échantillons E1, E2, E4 et E5 figurent dans le Tableau 2 ci-après. TABLEAU 2 Différence de potentiel (kV) Échantillon Proportion massique Er2O3/Pr6O11/Bi (%/%/%) ethéo(X) (mm) eexp(X) (mm) FX (Ø) 80 E1 60/40/0 0,88 1,35 1,53 E2 70/30/0 0,35 0,43 1,22 E4 36/24/40 0,31 0,43 1,37 E5 36/24/40 0,63 1,03 1,63 110 E4 36/24/40 0,31 0,48 1,52 E5 36/24/40 0,63 1,02 1,61 150 E2 70/30/0 0,35 0,40 1,14 E4 36/24/40 0,31 0,39 1,24 E5 36/24/40 0,63 0,76 1,19 The results obtained for samples E1, E2, E4 and E5 are shown in Table 2 below. TABLE 2 Potential difference (kV) Sample Mass ratio Er 2 O 3 / Pr 6 O 11 / Bi (% /% /%) e theo (X) (mm) e exp (X) (mm) F X (Ø) 80 E1 60/40/0 0.88 1.35 1.53 E2 70/30/0 0.35 0.43 1.22 E4 36/24/40 0.31 0.43 1.37 E5 36/24/40 0.63 1.03 1.63 110 E4 36/24/40 0.31 0.48 1.52 E5 36/24/40 0.63 1.02 1.61 150 E2 70/30/0 0.35 0.40 1.14 E4 36/24/40 0.31 0.39 1.24 E5 36/24/40 0.63 0.76 1.19

Des facteurs de gain compris entre 1,14 et 1,63 sont obtenus avec les matériaux conformes à l'invention, ce qui signifie que ces matériaux présentent des propriétés radio-atténuatrices accrues par rapport à des matériaux contenant un agent radio-atténuateur constitué uniquement de plomb.Gain factors between 1.14 and 1.63 are obtained with the materials according to the invention, which means that these materials have increased radio attenuating properties compared to materials containing a radio-attenuator agent consisting only of lead.

2. Propriétés de radio-atténuation en présence d'un rayonnement ionisant de type gamma 2. Radio-attenuation properties in the presence of gamma-type ionizing radiation

Les propriétés d'atténuation d'un rayonnement ionisant de type gamma par des matériaux conformes à l'invention sont évaluées par l'intermédiaire d'un dispositif mettant en oeuvre ces matériaux, placés à une certaine distance entre, d'une part, une source radioactive constituée par de l'américium-241, qui émet un rayonnement ionisant de type gamma d'énergie 59 keV, et d'autre part, un spectromètre sur lequel est assemblé un détecteur gamma au germanium.The attenuation properties of a gamma-type ionizing radiation by materials in accordance with the invention are evaluated by means of a device using these materials, placed at a distance between, on the one hand, a a radioactive source consisting of americium-241, which emits ionizing radiation of gamma type energy 59 keV, and secondly, a spectrometer on which is assembled a germanium gamma detector.

La méthode employée consiste à déterminer l'atténuation du rayonnement de type gamma issu de l'américium-241, en mesurant la surface des pics d'absorption photoélectrique enregistrés par le détecteur. Cette surface est comparée, par la même méthode, à des surfaces obtenues avec des écrans de plomb d'épaisseur connue.The method used is to determine the attenuation of gamma-type radiation from americium-241, by measuring the area of the photoelectric absorption peaks recorded by the detector. This surface is compared, by the same method, to surfaces obtained with lead screens of known thickness.

Comme dans le paragraphe 1 précédent, on définit une épaisseur équivalente en plomb théorique, notée ethéo(γ), calculée à partir de la masse surfacique des matériaux testés, et de la masse volumique du plomb sous forme métallique. En d'autres termes, cette épaisseur correspond à l'épaisseur d'un matériau de même masse que les matériaux testés, mais composé uniquement de plomb.As in the previous paragraph 1, we define an equivalent theoretical lead thickness, denoted e theo (γ) , calculated from the mass per unit area of the tested materials, and the density of the lead in metallic form. In other words, this thickness corresponds to the thickness of a material of the same mass as the materials tested, but composed only of lead.

On définit encore une épaisseur équivalente en plomb mesurée, notée eexp(γ).We still define an equivalent measured lead thickness, denoted e exp (γ) .

On définit enfin un facteur de gain Fγ, correspondant au rapport eexp(γ)/ethéo(γ).Finally, we define a gain factor F γ , corresponding to the ratio e exp (γ) / e theo (γ) .

Les résultats obtenus pour les échantillons E2 et E3 figurent dans le Tableau 3 ci-après. TABLEAU 3 Échantillon Proportion massique Er2O3/Pr6O11/Bi (%/%/%) ethéo(X) (mm) eexp(X) (mm) Fγ (Ø) E2 70/30/0 0,35 0,80 2,28 E3 70/30/0 0,82 1,67 2,03 The results obtained for samples E2 and E3 are shown in Table 3 below. TABLE 3 Sample Mass ratio Er 2 O 3 / Pr 6 O 11 / Bi (% /% /%) e theo (X) (mm) e exp (X) (mm) F γ (Ø) E2 70/30/0 0.35 0.80 2.28 E3 70/30/0 0.82 1.67 2.03

Des facteurs de gain supérieurs à 2 sont obtenus avec les matériaux conformes à l'invention, qui possèdent ainsi des propriétés radio-atténuatrices accrues par rapport à des matériaux contenant un agent radio-atténuateur constitué uniquement de plomb.Gain factors greater than 2 are obtained with the materials according to the invention, which thus have increased radio-attenuating properties compared to materials containing a radio-attenuator agent consisting solely of lead.

Une représentation graphique de la section efficace, notée n, en fonction de l'énergie photonique, notée E, est montrée sur la Figure 7.A graphical representation of the effective cross-section, denoted n, as a function of the photonic energy, denoted E, is shown on FIG. Figure 7 .

La courbe en trait épais, qui représente la section efficace de photons issus d'un rayonnement ionisant de type gamma émis par de l'américium-241, en fonction de l'énergie photonique, présente un maximum correspondant à une distribution élevée de photons ayant une énergie majoritairement centrée sur 59,6 keV.The thick line curve, which represents the effective cross-section of photons resulting from gamma-type ionizing radiation emitted by americium-241, as a function of the photon energy, has a maximum corresponding to a high distribution of photons having an energy mainly centered on 59.6 keV.

En comparant les portions de surface situées sous la courbe en trait fin, on constate une forte atténuation du rayonnement d'énergie majoritairement centrée sur 59,6 keV.Comparing the surface portions below the curve in fine lines, there is a strong attenuation of energy radiation mainly centered on 59.6 keV.

En outre, on peut également observer l'émission d'un rayonnement secondaire de type X, qui se matérialise sous la forme de deux raies notées « RS » et « RS » sur la Figure 7, et dont les énergies respectives sont majoritairement centrées sur 49 et 55 keV.In addition, one can also observe the emission of secondary radiation of type X, which materializes in the form of two lines denoted "RS" and "RS" on the Figure 7 , and whose respective energies are mainly centered on 49 and 55 keV.

Comme exposé précédemment, un tel matériau conforme à l'invention peut être utilisé à des fins d'atténuation d'un rayonnement issu du combustible MOX.As explained above, such a material according to the invention can be used for attenuation of radiation from the MOX fuel.

À cet égard, et à titre de complément, on peut ajouter que, selon la variabilité de la composition isotopique de ce combustible, celui-ci étant placé à faible distance d'un point de mesure, typiquement 50 centimètres, ce rayonnement ionisant de type gamma représente une proportion allant de 75 à 85% de l'ensemble du rayonnement gamma et X issu de ce dernier.In this respect, and as a complement, it can be added that, according to the variability of the isotopic composition of this fuel, the latter being placed at a small distance from a measurement point, typically 50 centimeters, this ionizing radiation of the type gamma represents a proportion ranging from 75 to 85% of all gamma radiation and X from the latter.

Cette proportion importante rend d'autant plus légitime la mise en oeuvre d'une composition radio-atténuatrice telle que décrite plus haut dans la fabrication d'articles de protection contre les rayonnements ionisants.This important proportion makes it all the more legitimate the implementation of a radio-attenuator composition as described above in the manufacture of protective articles against ionizing radiation.

RÉFÉRENCES CITÉESREFERENCES CITED

  1. [1] Demande internationale PCT WO 2006/069007 [1] International application PCT WO 2006/069007
  2. [2] Demande de brevet US 2008/0128658 [2] Patent application US 2008/0128658
  3. [3] Demande de brevet FR 2 948 672 [3] Patent application FR 2 948 672
  4. [4] Demande internationale PCT WO 2005/017556 [4] International application PCT WO 2005/017556
  5. [5] Demande de brevet DE 10 2006 958 [5] Patent application DE 10 2006 958

Claims (14)

  1. Use of a mixture comprising:
    - 30 to 70% by mass of erbium or of a compound thereof;
    - 20 to 50% by mass of praseodymium or of a compound thereof; and
    - 0 to 50% by mass of bismuth or of a compound thereof;
    as a radiation attenuating composition.
  2. Use according to claim 1, characterised in that the erbium compound is an erbium oxide, said erbium oxide being preferably sesquioxide of erbium(III), of formula Er2O3.
  3. Use according to claim 1 or 2, characterised in that the praseodymium compound is a praseodymium oxide, said praseodymium oxide being preferably oxide of praseodymium(III-IV), of formula Pr6O11.
  4. Use according to claim 3, characterised in that the radiation attenuating composition comprises:
    - 55 to 65% by mass, and preferably (60 ± 2)% by mass, of erbium oxide, and
    - 35 to 45% by mass, and preferably (40 ± 2)% by mass, of praseodymium oxide.
  5. Use according to claim 3, characterised in that the radiation attenuating composition comprises:
    - 30 to 45% by mass, and preferably 33 to 42% by mass, of erbium oxide,
    - 20 to 30% by mass, and preferably 22 to 28% by mass, of praseodymium oxide, and
    - 30 to 45% by mass of bismuth.
  6. Radiation attenuating material comprising a matrix in which a radiation attenuating composition is dispersed, said composition being in the form of a powder, characterised in that said composition comprises:
    - 30 to 70% by mass of erbium or of a compound thereof;
    - 20 to 50% by mass of praseodymium or of a compound thereof; and
    - 0 to 50% by mass of bismuth or of a compound thereof.
  7. Radiation attenuating material according to claim 6, characterised in that the erbium compound is an erbium oxide, said erbium oxide being preferably sesquioxide of erbium(III), of formula Er2O3.
  8. Radiation attenuating material according to claim 6 or 7, characterised in that the praseodymium compound is a praseodymium oxide, said praseodymium oxide being preferably oxide of praseodymium(III-IV), of formula Pr6O11.
  9. Radiation attenuating material according to claim 8, characterised in that the radiation attenuating composition comprises:
    - 55 to 65% by mass, and preferably (60 ± 2)% by mass, of erbium oxide, and
    - 35 to 45% by mass, and preferably (40 ± 2)% by mass, of praseodymium oxide.
  10. Radiation attenuating material according to claim 8, characterised in that the radiation attenuating composition comprises:
    - 30 to 45% by mass, and preferably 33 to 42% by mass, of erbium oxide,
    - 20 to 30% by mass, and preferably 22 to 28% by mass, of praseodymium oxide, and
    - 30 to 45% by mass of bismuth.
  11. Radiation attenuating material according to any of claims 6 to 10, characterised in that:
    - the matrix represents 10 to 25% by mass, and preferably (15 ± 2)% by mass, of the mass of the material, whereas
    - the radiation attenuating composition represents 75 to 90% by mass, and preferably (85 ± 2)% by mass, of the mass of the material.
  12. Radiation attenuating material according to any of claims 6 to 11, characterised in that the radiation attenuating composition is constituted of particles of which at least 90% by number have an average particle size less than or equal to 20 µm.
  13. Article providing protection against ionising radiation, in particular X-and gamma-type electromagnetic radiation, comprising a radiation attenuating material according to any of claims 6 to 12.
  14. Article providing protection according to claim 13, characterised in that it is a glove, an overall, a chasuble, a jacket, a skirt, an oversleeve, a thyroid protector, a gonad protector, an armpit protective clothing, an ocular protection headband, an operation area, a curtain, a sheet, a bedding, a panel or a protective screen.
EP12813051.5A 2011-12-30 2012-12-28 Use of a mixture on the basis of erbium and praseodym as a radiation attenuating composition, radiation attenuating material and protection device against ionisating radiation containing such composition Active EP2798643B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1104168A FR2985364A1 (en) 2011-12-30 2011-12-30 USE OF ERBIUM OR ERBIUM COMPOUND AS RADIO-ATTENUATING AGENT, RADIATION-ATTENUATING MATERIAL, AND IONIZING RADIATION PROTECTION ARTICLE COMPRISING SUCH AN AGENT
PCT/EP2012/077037 WO2013098382A1 (en) 2011-12-30 2012-12-28 Use of a mixture comprising erbium and praseodymium as a radiation attenuating composition, radiation attenuating material, and article providing protection against ionising radiation and comprising such a composition

Publications (2)

Publication Number Publication Date
EP2798643A1 EP2798643A1 (en) 2014-11-05
EP2798643B1 true EP2798643B1 (en) 2016-02-24

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Country Status (7)

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US (1) US9006695B2 (en)
EP (1) EP2798643B1 (en)
JP (1) JP2015504159A (en)
CN (1) CN104054135B (en)
FR (1) FR2985364A1 (en)
RU (1) RU2601874C2 (en)
WO (1) WO2013098382A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3024379B1 (en) 2014-07-30 2020-08-14 Areva Nc CYCLONIC SEPARATION DEVICE INCLUDING TWO CYCLONES CONNECTED BY AN OPTIMIZED PIPING UNIT
CN109338741B (en) * 2018-10-16 2021-03-16 济南平安环保设备有限公司 Lead-free X-ray protection plate and preparation method thereof
CN111128317A (en) * 2019-11-20 2020-05-08 中国辐射防护研究院 Ionizing radiation tissue equivalent material formula design method and system
CN111685405A (en) * 2020-04-30 2020-09-22 中国辐射防护研究院 Protective clothing capable of preventing ionizing radiation and electromagnetic radiation

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Publication number Priority date Publication date Assignee Title
RU2156509C2 (en) * 1997-02-11 2000-09-20 Российский Федеральный Ядерный Центр - Всероссийский Научно-Исследовательский Институт Экспериментальной Физики Laminated x-ray-protective material
AU6765398A (en) * 1997-03-24 1998-10-20 Science Applications International Corporation Radiation shielding materials and containers incorporating same
US7476889B2 (en) 1998-12-07 2009-01-13 Meridian Research And Development Radiation detectable and protective articles
DE10340124A1 (en) * 2002-12-17 2004-07-01 Bayer Ag Lead-free mixture as a radiation protection additive
ATE333701T1 (en) 2002-12-17 2006-08-15 Lanxess Deutschland Gmbh LEAD-FREE MIXTURE AS A RADIATION PROTECTION ADDITIVE
US8022116B2 (en) * 2003-07-18 2011-09-20 Advanced Shielding Components, Llc Lightweight rigid structural compositions with integral radiation shielding including lead-free structural compositions
JP2007504467A (en) * 2003-09-03 2007-03-01 マヴィック ゲゼルシャフト ミット ベシュレンクテル ハフツング Radiation protection material based on silicone
DE102004001328A1 (en) * 2003-09-03 2005-04-07 Mavig Gmbh Lightweight radiation protection material for a wide range of energy applications
JP2007085865A (en) * 2005-09-21 2007-04-05 Toshiba Corp Radiation-shielding sheet and x-ray apparatus using the same
DE102006028958B4 (en) * 2006-06-23 2008-12-04 Mavig Gmbh Layered lead-free X-ray protective material
CN101137285B (en) * 2007-10-12 2010-08-25 魏宗源 Composite shielding material for medical X-ray protection
FR2948672B1 (en) 2009-07-31 2011-09-23 Areva Nc ELASTOMERIC MATERIAL RADIO-ATTENUATOR, MULTILAYER GLOVE PROTECTING AGAINST IONIZING RADIATION AND USES THEREOF
CN102782769A (en) * 2009-12-30 2012-11-14 射线防护产品股份有限公司 A multi-layer light-weight garment material with low radiation buildup providing scattered-radiation shielding
RU2491667C1 (en) * 2011-12-29 2013-08-27 Общество с ограниченной ответственностью "АполлО" Composite material for protection against radiation

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Publication number Publication date
RU2014131484A (en) 2016-02-20
CN104054135B (en) 2016-12-14
EP2798643A1 (en) 2014-11-05
US20140361199A1 (en) 2014-12-11
JP2015504159A (en) 2015-02-05
FR2985364A1 (en) 2013-07-05
WO2013098382A1 (en) 2013-07-04
CN104054135A (en) 2014-09-17
US9006695B2 (en) 2015-04-14
RU2601874C2 (en) 2016-11-10

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