WO2020079352A1 - Composite material for neutron shielding and for maintaining subcriticality, the manufacturing process and uses thereof - Google Patents

Composite material for neutron shielding and for maintaining subcriticality, the manufacturing process and uses thereof Download PDF

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Publication number
WO2020079352A1
WO2020079352A1 PCT/FR2019/052409 FR2019052409W WO2020079352A1 WO 2020079352 A1 WO2020079352 A1 WO 2020079352A1 FR 2019052409 W FR2019052409 W FR 2019052409W WO 2020079352 A1 WO2020079352 A1 WO 2020079352A1
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weight
meth
parts
ppm
acrylic
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PCT/FR2019/052409
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French (fr)
Inventor
Aatif ALAMI
Fidèle NIZEYIMANA
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Tn International
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F1/00—Shielding characterised by the composition of the materials
    • G21F1/02—Selection of uniform shielding materials
    • G21F1/10—Organic substances; Dispersions in organic carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic 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
    • G21F1/10—Organic substances; Dispersions in organic carriers
    • G21F1/103—Dispersions in organic carriers
    • G21F1/106—Dispersions in organic carriers metallic dispersions
    • 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
    • G21F7/00—Shielded cells or rooms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates

Definitions

  • the present invention relates to a composite material for neutron shielding and for maintaining the subcriticality which exhibits particularly effective thermomechanical properties.
  • the invention also relates to a manufacturing process as well as to the use of such a composite material for neutron shielding and for maintaining subcriticality, in particular in the nuclear industry and, more particularly, as part of the invention.
  • '' packaging intended for the storage, storage and / or transport of radioactive material, in particular nuclear fuels.
  • the composite materials for neutron shielding and for maintaining subcriticality which are used in the nuclear industry must exhibit a certain number of properties.
  • materials must in particular be able to slow down and capture neutrons very effectively, so as to ensure effective shielding against neutrons, on the one hand, and to maintain subcriticality within the packaging and / or a network of packaging, on the other hand, to prevent the neutrons which form there from causing a nuclear chain reaction, in particular when the radioactive material is fissile.
  • they should be highly hydrogenated and include a compound, for example based on boron, capable of ensuring the capture of neutrons.
  • composite materials must also exhibit good resistance to aging at relatively high temperatures under normal conditions of transport and / or storage. Indeed, the presence of radioactive material in the packaging can generate significant temperatures within the composite material, typically of the order of 130 ° C. to 180 ° C.
  • These composite materials must also have a low density so as to weigh down the packaging for which they are intended as little as possible.
  • the composite materials for neutron shielding and for maintaining subcriticality used in the nuclear industry are conventionally obtained from a polymerizable formulation comprising a thermosetting resin and one or more inorganic fillers.
  • thermosetting resin is a vinylester resin and the inorganic filler is a charge capable of slowing down and absorbing neutrons.
  • the composite material described in document [1] has good performance in terms of neutron shielding and maintenance of the subcriticality.
  • the use of such a composite material for the manufacture of parts of complex geometry or of large size is not entirely satisfactory, insofar as it can be observed, under certain conditions of use, the formation of cracks within the structure of these parts.
  • crack is meant a two-dimensional or three-dimensional discontinuity visible to the naked eye, which indicates a very localized lack of material.
  • number and size of the cracks can cause poorer performance in terms of neutron shielding.
  • the object of the present invention is therefore to alleviate the formation of cracks liable to form in parts of complex geometry and / or of large size which are made of a composite material obtained from a thermosetting resin such as that described in the document [1], while retaining the good performance in terms of neutron shielding and maintaining the subcriticality at high temperature, typically greater than or equal to 130 ° C., and for the envisaged duration of use of the packaging.
  • Another object of the present invention is to provide a process for manufacturing such a composite material, this process being able to be easily implemented in the equipment and tools of industrial installations currently used for the manufacture of composite materials based on thermosetting resin. .
  • This manufacturing process must, moreover, make it possible to obtain this composite material in a limited number of stages, with an industrial implementation which is technically and economically optimized, in particular when the parts to be produced have a complex geometry and / or large.
  • this formulation comprises:
  • (A) from 20% by weight to 65% by weight, advantageously from 25% by weight to 60% by weight, of a (meth) acrylic composition comprising:
  • the composite material for neutron shielding and for maintaining the subcriticality according to the invention makes it possible to produce parts, and in particular parts of complex geometry, which do not have any defects, in particular no cracks, within their structure, the term "crack" being as defined above (no two-dimensional or three-dimensional discontinuity visible to the naked eye). The risks of possible neutron leaks within the composite material are thus avoided.
  • the composite material according to the invention is characterized by a thermomechanical resistance which is improved compared to that of the composite materials obtained from a thermosetting formulation.
  • the composite material according to the invention is a thermoformable material, suitable for welding, easy to machine and which, moreover, is recyclable and less expensive than composite material obtained from a formulation comprising a thermosetting resin of the vinylester type as described in document [1].
  • the composite material according to the invention has, moreover, the advantage of being of an implementation similar to that of composite materials based on thermosetting formulations.
  • the composite material according to the invention can, in particular, be manufactured on the same type of equipment as thermoset composite materials such as the composite material described in document [1], without having to heat the equipment (such as machines mixing and pouring the (meth) acrylic formulation) and / or the composite material.
  • the formulation from which the composite material according to the invention is obtained is a formulation comprising a (meth) acrylic composition (A) and one or more specific fillers (B), in this case at least one boron compound and at minus a hydrogenated compound.
  • This (meth) acrylic composition comprises, in specific weight proportions, a liquid (meth) acrylic syrup, a polymerization initiator and, optionally, one or more compounds chosen from a monomer (meth) acrylic M2, a (meth) acrylic monomer M3, a metal compound, a reducing agent, a tertiary amine, a transfer agent, an antioxidant, a free radical scavenger, a thermal stabilizer and a light stabilizer .
  • liquid (meth) acrylic syrup comprises:
  • (meth) acrylic monomer covers both an acrylic monomer and a methacrylic monomer.
  • (meth) acrylic polymer covers both an acrylic homopolymer, a methacrylic homopolymer, an acrylic copolymer and a methacrylic copolymer.
  • the (meth) acrylic polymer PI of the liquid (meth) acrylic syrup can be chosen from alkyl polymethacrylates and polyalkyl acrylates.
  • the (meth) acrylic polymer PI is a polymethyl methacrylate (PMMA), this polymethyl methacrylate (PMMA) can just as easily denote a homopolymer of methyl methacrylate (MMA), a copolymer of MMA as one of their mixtures.
  • PMMA polymethyl methacrylate
  • MMA homopolymer of methyl methacrylate
  • MMA copolymer of MMA
  • the PI (meth) acrylic polymer can be formed by a mixture of at least one MMA homopolymer and at least one MMA copolymer, by a mixture of at least two MMA homopolymers having a different average molecular weight, by a mixture of at least two MMA copolymers having an identical monomer composition and a different average molecular weight or alternatively by a mixture of at least two MMA copolymers having a different monomer composition.
  • the methyl methacrylate (MMA) homopolymer or copolymer comprises at least 70% by weight, advantageously at least 80% by weight, preferably at least 90% by weight and, more preferably, at least 95% by weight of methyl methacrylate (MMA).
  • the methyl methacrylate (MMA) copolymer comprises from 70% to 99.7% by weight of methyl methacrylate (MMA) and from 0.3% to 30% by weight of at least one comonomer containing at least one ethylenic unsaturation which is capable of copolymerizing with methyl methacrylate.
  • the comonomer is an alkyl acrylate in which the alkyl group contains from 1 to 4 carbon atoms.
  • the methyl methacrylate copolymer comprises from 80% to 99.9%, advantageously from 90% to 99.9%, by weight of methyl methacrylate (MMA) and from 0.1% to 20 %, advantageously from 0.1% to 10%, by weight of at least one comonomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate.
  • MMA methyl methacrylate
  • the comonomer is chosen from methyl acrylate, ethyl acrylate and their mixtures.
  • the weight average molecular weight of the (meth) acrylic polymer PI is generally high, typically greater than 50,000 g / mol and preferably greater than 100,000 g / mol. This weight average molecular weight can be measured by size exclusion chromatography (SEC).
  • the (meth) acrylic polymer PI is soluble in the (meth) acrylic monomer Ml or in the mixture of (meth) acrylic monomers. This makes it possible to increase the viscosity of the (meth) acrylic monomer Ml or of the mixture of (meth) acrylic monomers.
  • the liquid (meth) acrylic syrup of the (meth) acrylic composition also comprises a (meth) acrylic monomer Ml comprising only one (meth) acrylic function.
  • the (meth) acrylic monomer M1 can be chosen from acrylic alkyl monomers, methacrylic alkyl monomers, acrylic hydroxyalkyl monomers, methacrylic hydroxyalkyl monomers and mixtures thereof, the alkyl group possibly being linear, branched or cyclic, and contain from 1 to 22 carbon atoms, preferably from 1 to 12 carbon atoms.
  • the (meth) acrylic monomer Ml is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, acrylic acrylate.
  • methyl methacrylate represents at least 50% by weight, advantageously at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight and, more preferably still, at minus 90% by weight of the (meth) acrylic monomer Ml.
  • the (meth) acrylic composition may comprise a (meth) acrylic monomer M2, this (meth) acrylic monomer M2 comprising at least two (meth) acrylic functions.
  • This M2 (meth) acrylic monomer can advantageously be chosen from ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate and mixtures thereof.
  • the (meth) acrylic composition can thus comprise up to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, M2 (meth) acrylic monomer per 100 parts by weight of liquid (meth) acrylic syrup.
  • the (meth) acrylic composition may comprise a (meth) acrylic monomer M3.
  • This (meth) acrylic monomer M3 only has one (meth) acrylic function and is different from the (meth) acrylic monomer Ml.
  • This (meth) acrylic monomer M3 can in particular be a monomer which, once polymerized in the form of a homopolymer, has a glass transition temperature Tg of at least 120 ° C., the temperature Tg of a homopolymer can be determined in accordance with to the publication "Polymer Handbook".
  • the monomer M3 is methacrylic acid.
  • the (meth) acrylic composition can thus comprise up to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of (meth) acrylic monomer M3 per 100 parts by weight of liquid methacrylic syrup.
  • the (meth) acrylic composition comprises at least one (meth) acrylic monomer from the (meth) acrylic monomers M2 and M3, preferably M2.
  • the (meth) acrylic composition comprises the (meth) acrylic monomers M2 and M3.
  • the (meth) acrylic composition also comprises from 0.1 part by weight to 5 parts by weight, per 100 parts by weight of liquid methacrylic syrup, of a polymerization initiator whose role is to ensure the start-up of polymerization of the (meth) acrylic monomers Ml and, where appropriate, M2 and / or M3.
  • the polymerization initiator preferably a radical polymerization initiator, may be in a solid form, if necessary in admixture with a solvent to dissolve it, or else in a liquid form.
  • the polymerization initiator is a peroxide, preferably a peroxide which is liquid at a temperature between 0 ° C and 50 ° C.
  • the peroxide is an organic peroxide comprising from 2 to 30 carbon atoms, for example methyl ethyl ketone (PMEC), methyl isopropyl ketone peroxide (PMIC) or a hydro peroxide.
  • PMEC methyl ethyl ketone
  • PMIC methyl isopropyl ketone peroxide
  • hydro peroxide a hydro peroxide
  • the polymerization initiator is a hydroperoxide or a peroxide comprising at least one hydroperoxide function chosen from te / t-butyl hydroperoxide, monohydroperoxide, para-methane hydroperoxide, te / t-hydroperoxide amyl, methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide and cumene hydroperoxide.
  • the polymerization initiator is monohydroperoxide, methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide or para-methane hydroperoxide.
  • the (meth) acrylic composition can also comprise up to 10 parts by weight of a metallic compound per 100 parts by weight of liquid methacrylic syrup.
  • the metallic compound comprises one or more transition metals chosen from the transition metals of the fourth period of the periodic table of the elements.
  • the metallic compound is a metallic complex, a metallic salt or a mixture of metallic salts.
  • the metallic compound does not comprise cobalt.
  • the metal or metals of the metallic compound are chosen from iron, copper and manganese.
  • the (meth) acrylic composition comprises from 0.01 part by weight to 10 parts by weight and, advantageously, from 0.05 part by weight to 3 parts by weight of metallic compound per 100 parts by weight of liquid methacrylic syrup.
  • the (meth) acrylic composition can also comprise up to 10 parts by weight of a reducing agent per 100 parts by weight of liquid methacrylic syrup.
  • the reducing agent is chosen from ascorbic acid, saccharin, ⁇ -hydroxysulfones, thioureas and their mixtures.
  • the reducing agent is saccharin.
  • the (meth) acrylic composition comprises from 0.01 part by weight to 10 parts by weight, advantageously from 0.1 part by weight to 2 parts by weight and, preferably, from 0.1 part by weight to 1 part by weight of reducing agent per 100 parts by weight of liquid methacrylic syrup.
  • the (meth) acrylic composition can also comprise up to 20,000 ppm of a tertiary amine per 100 parts by weight of liquid methacrylic syrup.
  • the tertiary amine is chosen from L /, / V-dimethyl-p-toluidine (DMPT), L /, / V-dihydroxyethyl-p-toluidine (DHEPT), L /, / V- diethyl-p-toluidine (DEPT) and p-toluidine ethoxylate (PTE).
  • DMPT dimethyl-p-toluidine
  • DHEPT V-dihydroxyethyl-p-toluidine
  • DEPT diethyl-p-toluidine
  • PTE p-toluidine ethoxylate
  • the (meth) acrylic composition comprises from 1,000 ppm to 10,000 ppm of tertiary amine per 100 parts by weight of liquid (meth) acrylic syrup.
  • the (meth) acrylic composition can also comprise up to 10,000 ppm of a transfer agent per 100 parts by weight of liquid (metha) crylic syrup.
  • the transfer agent is chosen from thiols, sulfur molecules comprising aromatic rings and terpene derivatives such as terpinolene.
  • the transfer agent is terpinolene.
  • the (meth) acrylic composition comprises from 0.01 ppm to 5,000 ppm, advantageously from 0.1 ppm to 3,000 ppm, of transfer agent per 100 parts by weight of liquid methacrylic syrup.
  • the (meth) acrylic composition can also comprise up to 10,000 ppm of an antioxidant per 100 parts by weight of liquid methacrylic syrup.
  • the antioxidant is selected from phenolic compounds such as Irganox ®.
  • the (meth) acrylic composition comprises from 0.01 ppm to 5,000 ppm, advantageously from 0.1 ppm to 3,000 ppm, of antioxidant per 100 parts by weight of liquid methacrylic syrup.
  • the (meth) acrylic composition can also comprise up to 1000 ppm of a free radical scavenger per 100 parts by weight of liquid methacrylic syrup.
  • the free radical scavenger is chosen from alkoxylamines and nitroxides.
  • the (meth) acrylic composition comprises from 0.01 ppm to 500 ppm, advantageously from 0.1 ppm to 400 ppm, of free radical scavenger per 100 parts by weight of liquid methacrylic syrup.
  • the (meth) acrylic composition can also comprise up to 10,000 ppm of a thermal stabilizer per 100 parts by weight of liquid methacrylic syrup, this thermal stabilizer making it possible to improve the temperature and aging stability of the composite material according to the invention.
  • the thermal stabilizer is a disulfide such as poly-te / t-amylphenoldisulfide.
  • the (meth) acrylic composition comprises from 0.01 ppm to 5,000 ppm, advantageously from 0.1 ppm to 3,000 ppm, of thermal stabilizer per 100 parts by weight of liquid methacrylic syrup.
  • the (meth) acrylic composition can also comprise up to 10,000 ppm of a light stabilizer per 100 parts by weight of liquid methacrylic syrup.
  • the light stabilizer is chosen from stabilizers of the hindered amine type (or HALS for Hindered Amine Light Stabilizer), for example bis (2,2,6,6-tetramethyl-4-piperidyl) sebaceate and phosphites.
  • the (meth) acrylic composition comprises from 0.01 ppm to 7000 ppm, advantageously from 0.1 ppm to 5000 ppm, of light stabilizer per 100 parts by weight of liquid methacrylic syrup.
  • the formulation from which the composite material according to the invention is obtained comprises one or more specific fillers (B).
  • This or these charges comprise at least one boron compound and at least one hydrogenated compound.
  • the hydrogenated compound (s), the role of which is to slow down the neutrons, can be formed as well by inorganic fillers as by organic fillers.
  • These hydrogenated compounds can, in particular, be chosen from hydroxides and polyolefins.
  • the hydrogenated compound (s) are hydroxides
  • these can be chosen from alumina hydrate (or aluminum trihydroxide) AI (OH) 3 and magnesium hydroxide Mg (OH) 2 .
  • Alumina hydrate is more particularly preferred in the sense that this hydrogenated compound also confers on the composite material self-extinguishing properties.
  • the hydrogenated compound (s) are polyolefins
  • these can in particular be a polyethylene.
  • the composite material according to the invention which is obtained from a formulation comprising a polyethylene, has the advantage of being lighter than a composite material comprising alumina hydrate and can advantageously be used in packages in which the temperature is lower than that mentioned above, and in particular between 130 ° C and 150 ° C.
  • the boron compound (s), the role of which is to absorb the neutrons once slowed down by the hydrogenated compound (s), can in particular be chosen from boric acid H3BO3, colemanite Ca 2 O 4 B 6 Hio, borates of zinc such as 4ZhO, 6B 2 q 3 , 7H 2 q, 4ZhO, B 2 q 3 , H 2 q, 2Zn0.3B 2 03 and 3ZhO, 2B 2 q 3 , boron carbide B 4 C, boron nitride BN and boron oxide B2O3.
  • boric acid H3BO3, colemanite Ca 2 O 4 B 6 Hio borates of zinc such as 4ZhO, 6B 2 q 3 , 7H 2 q, 4ZhO, B 2 q 3 , H 2 q, 2Zn0.3B 2 03 and 3ZhO, 2B 2 q 3 , boron carbide B 4 C, boron nitride
  • the boron compound or compounds comprise hydrogen and can in particular be chosen from hydrated zinc borates such as 4ZhO, 6B 2 q 3 , 7H 2 q or also 4ZhO, B 2 q 3 , H 2 q.
  • borates hydrates also make it possible to confer self-extinguishing properties on the composite material according to the invention.
  • the formulation comprises:
  • the weight proportions of boron and hydrogenated compounds can be advantageously adapted as a function of the properties desired from the shielding and / or subcritical properties.
  • the particular charge (s) (B) comprising at least one boron compound and at least one hydrogenated compound are in a divided form (for example, in the form of granules, grains, beads, powders, flakes ...) which is designated below by the generic term of particles.
  • this or these charges (B) are in the form of particles the largest dimension of which is at most equal to 1 cm, the size of the particles being able to be determined by laser diffraction.
  • This larger dimension of the filler particles (B) can in particular be between 1 pm and 1 mm, advantageously between 5 pm and 500 pm and, preferably, between 10 pm and 200 pm.
  • the formulation comprises from 20% by weight to 65% by weight of (meth) acrylic composition (A) and from 35% by weight to 80% by weight of the particular filler (s) (B) described above.
  • the formulation comprises from 25% by weight to 60% by weight of (meth) acrylic composition (A) and from 40% by weight to 75% by weight of filler (s) (B).
  • a composite material is obtained which has good resistance to aging, at a high temperature, in particular at 160 ° C. which corresponds to the temperature capable of being reached by the composite material more particularly placed in a packaging for storing, storing and / or transporting radioactive material.
  • the loss of hydrogen mass of the composite material according to the invention is less than 10%.
  • the formulation from which the composite material according to the invention is obtained has the property of being able to be cast, allowing its easy transfer into a mold.
  • This formulation has a viscosity preferably less than or equal to 25 Pa.s.
  • the formulation can also comprise one or more other additional compounds, for example metallic fillers (such as lead) for gamma shielding and / or additives making it possible to increase the temperature resistance, the flexibility and / or the impact resistance. composite material.
  • metallic fillers such as lead
  • the present invention relates, secondly, to a process for manufacturing a composite material for neutron shielding and for maintaining subcriticality from the particular formulation as described above.
  • this method comprises:
  • the method according to the invention comprises:
  • (A) from 20% by weight to 65% by weight, advantageously from 25% by weight to 60% by weight, of a (meth) acrylic composition comprising:
  • liquid (meth) acrylic syrup being prepared first and the polymerization initiator being introduced last into the formulation
  • the manufacturing process according to the invention is therefore a process the implementation of which is particularly simple, rapid and economical.
  • the method according to the invention makes it possible to obtain a composite material of shape (design) specifically adapted to the packaging. for which it is intended. This process can, moreover, be easily implemented in installations currently dedicated to the processes for manufacturing composite materials obtained from thermosetting formulations, such as that described in document [1] ⁇
  • the characteristics described above in connection with the (meth) acrylic composition and, in particular, the characteristics relating to the (meth) acrylic polymer PI and to the (meth) acrylic monomer Ml forming the (meth) acrylic syrup, to the (meth) acrylic monomers M2 and M3, the metallic compound, the reducing agent, the tertiary amine, the polymerization initiator, the transfer agent, the antioxidant, the free radical scavenger, the thermal stabilizers and to light, to the filler (s) (B) and to the additional compounds, are of course applicable to the present method of manufacturing the composite material.
  • Step (1) of the manufacturing process according to the invention is carried out by mixing all of the compounds entering into the (meth) acrylic composition (A) and the particular filler (s) (B), taking care to prepare, in the first place, the liquid (meth) acrylic syrup and then to introduce, into this (meth) acrylic syrup, the polymerization initiator and, where appropriate, the (meth) acrylic monomers M2 and / or M3, the metal compound, the reducing agent, the tertiary amine, the transfer agent, the antioxidant, the free radical scavenger, the thermal and light stabilizers, the charge (s) (B) and to the compounds additional, the polymerization initiator being introduced last.
  • Such mixing can be manual or else carried out by means of a mixer.
  • the formulation can be poured into a mold for the subsequent implementation of step (2) of molding.
  • the formulation can be poured directly into the packaging intended for the storage, storage and / or transport of radioactive material.
  • packaging can, for example, include peripheral housings into which the formulation is poured.
  • Step (2) of molding the formulation as obtained at the end of step (1) is carried out at room temperature, that is to say at a temperature typically between 18 ° C. and 25 ° C., and makes it possible to carry out the polymerization of the matrix and, in so doing, to obtain the composite material for neutron shielding and for maintaining the subcriticality according to the invention.
  • the mechanism of this polymerization reaction is radical.
  • the invention relates, thirdly, to the use of the composite material for neutron shielding and for maintaining the subcriticality as defined above, the advantageous characteristics of this composite material being able to be taken alone or in combination.
  • the invention also relates to the use of the formulation as described above for obtaining the composite material for neutron shielding and for maintaining subcriticality according to the invention, the advantageous characteristics of this formulation possibly being taken alone or in combination.
  • the composite material according to the invention as well as the formulation from which this composite material is obtained can in particular be used for the manufacture of a piece of packaging intended for the storage, storage and / or transport of material radioactive.
  • the invention relates, fourthly, to a packaging for storing, storing and / or transporting radioactive material.
  • this packaging for storing, storing and / or transporting radioactive material comprises a composite material for neutron shielding and for maintaining the subcriticality as defined above, the advantageous characteristics of this composite material. can be taken alone or in combination.
  • Figure 1 represents curves translating the evolution of the loss of mass (noted A m and expressed in%) as a function of the aging time (noted t and expressed in h) of two composite materials placed in an environment at 160 ° C , one being a composite material according to the invention and obtained from formulation 1 (curve denoted 1) and the other being a comparative composite material obtained from formulation C (curve denoted C).
  • FIG. 2 represents curves translating the evolution of the loss of mass (noted A m and expressed in%) as a function of the aging time (noted t and expressed in h) of three composite materials placed in an environment at 180 ° C. , two being composite materials in accordance with the invention and obtained from formulations 4 and 5 (curves respectively denoted 4 and 5) and the third being a comparative composite material obtained from formulation C (curve denoted C).
  • FIG. 3 represents curves showing the evolution of the mass loss (denoted A m and expressed in%) as a function of the aging time (denoted t and expressed in h) of two composite materials in accordance with the invention, obtained at starting from formulations 1 and 5 and placed in an environment at 180 ° C (curves respectively noted 1 and 5).
  • the compounds used for the preparation of the (meth) acrylic compositions, denoted A and A ′, used for obtaining the composite materials according to the invention are the following: as a (meth) acrylic polymer PI: a PMMA formed by a copolymer of methyl methacrylate and ethyl acrylate sold by the Altuglas Company under the name Altuglas ® BS 520,
  • (meth) acrylic monomer M1 a methyl methacrylate stabilized by hydroquinone of monomethyl ether (MEHQ.),
  • M2 (meth) acrylic monomer a 1,4-butanediol dimethacrylate sold by the company Sartomer under the name SR214,
  • tertiary amine an L /, / V-dihydroxyethyl-p-toluidine (DHEPT),
  • transfer agent a terpinolene sold by the company DRT under the name Terpinolene 95,
  • antioxidant bis [3- (3,5-di-te / t-butyl-4-hydroxyphenyl) proprionate] thiodiethylene marketed by BASF under the name Irganox ® 1035,
  • thermal stabilizer a poly-te / t-amylphenoldisulfide marketed by the company Arkema under the name Vultac-3 ® , and
  • composition C used to obtain the comparative composite material are the following: - as vinylester resin: a vinylester epoxy resin sold by the Ashland Company under the name Derakane TM Momentum 470-300,
  • As hardening accelerator a mixture of cobalt (ll) 2-ethylhexanoate and barium carboxylate sold by the company Akzo Nobel under the name Accelerator 55028.
  • the charges used for the preparation of the various formulations making it possible to obtain the materials according to the invention and the comparative material are the following:
  • a liquid (meth) acrylic syrup is prepared by dissolving 25 parts by weight of the (meth) acrylic polymer PI in 75 parts by weight of the (meth) acrylic monomer Ml.
  • composition A 5 parts by weight of (meth) acrylic monomer M2 are added to the 100 parts by weight of liquid (meth) acrylic syrup, to obtain the (meth) acrylic composition, denoted composition A.
  • a stabilized (meth) acrylic composition is formed by the above (meth) acrylic composition A to which are added:
  • one or more fillers are introduced into the (meth) acrylic composition A or A ′ as obtained, in the weight proportions as indicated in Table 1 below, then, lastly, 0.75 part by weight of the polymerization initiator (Butanox ® M-50) and one proceeds to mixing of all compounds to obtain formulations, denoted 1 to 5, perfectly homogeneous.
  • the different formulations 1 to 5 thus prepared are degassed under vacuum (pressure less than 0.01 MPa) and then poured, at room temperature (21 ° C), into a mold.
  • thermosetting composition denoted composition c, is prepared in accordance with Example 2 of document [1].
  • thermosetting formulation The mixing of all the compounds is carried out so as to obtain a perfectly homogeneous thermosetting formulation.
  • thermosetting formulation denoted C
  • degassed under vacuum pressure less than 0.01 MPa
  • room temperature 21 ° C
  • each of formulations 1 to 5 is carried out at room temperature (21 ° C).
  • thermosetting formulation C is carried out at room temperature (21 ° C) 2. Assessment of the properties of composite materials
  • the resistance to thermal aging of a composite material can be assessed by tests which consist in measuring its characteristics, in particular the loss of mass, when it is maintained at different temperatures for a defined period of time, and to determine from of the results obtained the maximum temperature for which the loss of mass of the composite material is acceptable for the period of intended use of the packaging.
  • Boron compounds being stable in temperature we will focus more particularly on the loss of mass of hydrogen whose sensitivity to high temperatures is more marked, knowing that the boron and hydrogen contents are the essential elements to be taken into account for assess the performance of such a composite material with respect to the functions of neutron shielding and of maintaining the subcriticality, and this throughout the duration of use of the packaging.
  • the composite material according to the invention (obtained from formulation 1) has a loss of mass well below 10% and comparable, although very slightly greater, than that of the comparative composite material .
  • the composite materials according to the invention (obtained from formulations 4 and 5) have a loss of mass of less than 10%. Even if the loss in mass of these composite materials according to the invention is slightly greater than that of the comparative composite material obtained from formulation C, the loss of hydrogen is however very much lower. Indeed, after 2000 h of aging time, the loss of hydrogen is estimated to be less than 4% for the composite materials obtained from formulations 4 and 5 whereas it is greater than 9% for that obtained at from formulation C.
  • FIG. 3 The results of the aging tests carried out at 180 ° C. on the materials obtained from formulations 1 and 5 are shown in FIG. 3.
  • the composite material according to the invention obtained from formulation 5 has a loss in mass, at 180 ° C., less than that of the composite material according to the invention obtained from formulation 1 This difference is directly linked to the (meth) acrylic composition of the formulation which, in the case of formulation 5, is stabilized, which is not the case of the (meth) acrylic composition of formulation 1.
  • a formulation comprising a stabilized (meth) acrylic composition.

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Abstract

The invention relates to a composite material for neutron shielding and for maintaining subcriticality on the basis of a formulation comprising: (A) from 20% by weight to 65% by weight of a meth(acrylic) composition comprising: - 100 parts by weight of a liquid meth(acrylic) syrup comprising: (a1) from 10% by weight to 50% by weight of a meth(acrylic) polymer P1, and (a2) from 50% by weight to 90% by weight of a meth(acrylic) monomer M1 comprising only one meth(acrylic) function, and - from 0.1 parts by weight to 5 parts by weight of a polymerisation initiator; and (B) from 35% by weight to 80% by weight of one or more charges comprising at least one boron component and at least one hydrogenated component. The invention also relates to a manufacturing process and to a use of this composite material.

Description

MATÉRIAU COMPOSITE DE BLINDAGE NEUTRONIQUE ET DE MAINTIEN DE LA SOUS- CRITICITÉ, SON PROCÈDE DE FABRICATION ET SES UTILISATIONS  COMPOSITE NEUTRONIC SHIELDING AND SUB-CRITICITY MAINTAINING MATERIAL, MANUFACTURING METHOD THEREOF AND USES THEREOF
DESCRIPTIONDESCRIPTION
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention se rapporte à un matériau composite de blindage neutronique et de maintien de la sous-criticité qui présente des propriétés thermomécaniques particulièrement performantes. The present invention relates to a composite material for neutron shielding and for maintaining the subcriticality which exhibits particularly effective thermomechanical properties.
L'invention se rapporte également à un procédé de fabrication ainsi qu'à l'utilisation d'un tel matériau composite de blindage neutronique et de maintien de la sous-criticité, notamment dans l'industrie nucléaire et, plus particulièrement, comme pièce d'un emballage destiné à l'entreposage, au stockage et/ou au transport de matière radioactive, notamment de combustibles nucléaires.  The invention also relates to a manufacturing process as well as to the use of such a composite material for neutron shielding and for maintaining subcriticality, in particular in the nuclear industry and, more particularly, as part of the invention. '' packaging intended for the storage, storage and / or transport of radioactive material, in particular nuclear fuels.
ÉTAT DE LA TECHNIQUE ANTÉRIEURE PRIOR STATE OF THE ART
Les matériaux composites de blindage neutronique et de maintien de la sous-criticité qui sont utilisés dans l'industrie nucléaire doivent présenter un certain nombre de propriétés. The composite materials for neutron shielding and for maintaining subcriticality which are used in the nuclear industry must exhibit a certain number of properties.
Ces matériaux doivent notamment être capables de ralentir et de capturer très efficacement les neutrons, de manière à assurer un blindage efficace contre les neutrons, d'une part, et à maintenir la sous-criticité au sein de l'emballage et/ou d'un réseau d'emballages, d'autre part, pour éviter que les neutrons qui s'y forment ne provoquent une réaction nucléaire en chaîne, notamment lorsque la matière radioactive est fissile. Pour que des matériaux soient aptes à ralentir les neutrons pour ensuite pouvoir les capturer, il convient qu'ils soient fortement hydrogénés et qu'ils comprennent un composé, par exemple à base de bore, propre à assurer la capture des neutrons.  These materials must in particular be able to slow down and capture neutrons very effectively, so as to ensure effective shielding against neutrons, on the one hand, and to maintain subcriticality within the packaging and / or a network of packaging, on the other hand, to prevent the neutrons which form there from causing a nuclear chain reaction, in particular when the radioactive material is fissile. In order for materials to be able to slow down neutrons and then be able to capture them, they should be highly hydrogenated and include a compound, for example based on boron, capable of ensuring the capture of neutrons.
Ces matériaux composites doivent également présenter une bonne tenue au vieillissement à des températures relativement élevées en conditions normales de transport et/ou d'entreposage. En effet, la présence de matière radioactive dans les emballages peut générer des températures importantes au sein du matériau composite, typiquement de l'ordre de 130 °C à 180 °C. These composite materials must also exhibit good resistance to aging at relatively high temperatures under normal conditions of transport and / or storage. Indeed, the presence of radioactive material in the packaging can generate significant temperatures within the composite material, typically of the order of 130 ° C. to 180 ° C.
Ces matériaux composites doivent encore être auto-extinguibles, c'est- à-dire qu'ils cessent de brûler sitôt que les flammes sont éteintes. Cette caractéristique prend tout son intérêt dans le cadre de l'épreuve de feu relative aux conditions accidentelles de transport issue de la réglementation en vigueur auxquelles l'emballage doit être soumis. Des essais sont alors réalisés avec un emballage placé dans un feu à 800 °C pendant 30 mn.  These composite materials must still be self-extinguishing, that is, they stop burning as soon as the flames are extinguished. This characteristic takes all its interest within the framework of the fire test relating to the accidental conditions of transport resulting from the regulations in force to which the packaging must be subjected. Tests are then carried out with a packaging placed in a fire at 800 ° C for 30 min.
Ces matériaux composites doivent également présenter une densité peu élevée de manière à alourdir le moins possible l'emballage auquel ils sont destinés.  These composite materials must also have a low density so as to weigh down the packaging for which they are intended as little as possible.
Les matériaux composites de blindage neutronique et de maintien de la sous-criticité utilisés dans l'industrie nucléaire sont classiquement obtenus à partir d'une formulation polymérisable comprenant une résine thermodurcissable et une ou plusieurs charges inorganiques.  The composite materials for neutron shielding and for maintaining subcriticality used in the nuclear industry are conventionally obtained from a polymerizable formulation comprising a thermosetting resin and one or more inorganic fillers.
En particulier, le document US 7,160,486, référencé [1] dans la suite de la présente description, décrit un matériau composite de blindage neutronique et de maintien de la sous-criticité dans lequel la résine thermodurcissable est une résine vinylester et la charge inorganique est une charge capable de ralentir et d'absorber les neutrons.  In particular, document US 7,160,486, referenced [1] in the remainder of this description, describes a composite material for neutron shielding and for maintaining subcriticality in which the thermosetting resin is a vinylester resin and the inorganic filler is a charge capable of slowing down and absorbing neutrons.
Le matériau composite décrit dans le document [1] présente de bonnes performances en termes de blindage neutronique et de maintien de la sous-criticité. Toutefois, la mise en œuvre d'un tel matériau composite pour la fabrication de pièces de géométrie complexe ou de grande taille n'est pas totalement satisfaisante, dans la mesure où l'on peut observer, dans certaines conditions de mise en œuvre, la formation de fissures au sein de la structure de ces pièces. Par "fissure", il faut comprendre une discontinuité bidimensionnelle ou tridimensionnelle visible à l'œil nu, qui traduit un manque de matière très localisé. De telles fissures peuvent engendrer, selon la forme, le nombre et la taille des fissures, une moindre performance en termes de blindage neutronique. Pour limiter au mieux la formation éventuelle de telles fissures, il devient nécessaire de mettre en place des procédures de fabrication contraignantes économiquement incompatibles avec une production industrielle ou encore des modifications de la forme (design) de l'emballage. The composite material described in document [1] has good performance in terms of neutron shielding and maintenance of the subcriticality. However, the use of such a composite material for the manufacture of parts of complex geometry or of large size is not entirely satisfactory, insofar as it can be observed, under certain conditions of use, the formation of cracks within the structure of these parts. By "crack" is meant a two-dimensional or three-dimensional discontinuity visible to the naked eye, which indicates a very localized lack of material. Depending on the shape, number and size of the cracks, such cracks can cause poorer performance in terms of neutron shielding. To best limit the possible formation of such cracks, it becomes necessary to set up restrictive manufacturing procedures that are economically incompatible with industrial production or even modifications to the shape (design) of the packaging.
Le but de la présente invention est donc de pallier la formation de fissures susceptible de se former dans des pièces de géométrie complexe et/ou de grande taille qui sont réalisées en un matériau composite obtenu à partir d'une résine thermodurcissable tel que celui décrit dans le document [1], tout en en conservant les bonnes performances en termes de blindage neutronique et de maintien de la sous- criticité à haute température, typiquement supérieure ou égale à 130 °C, et pour la durée d'utilisation envisagée de l'emballage.  The object of the present invention is therefore to alleviate the formation of cracks liable to form in parts of complex geometry and / or of large size which are made of a composite material obtained from a thermosetting resin such as that described in the document [1], while retaining the good performance in terms of neutron shielding and maintaining the subcriticality at high temperature, typically greater than or equal to 130 ° C., and for the envisaged duration of use of the packaging.
Un autre but de la présente invention est de proposer un procédé de fabrication d'un tel matériau composite, ce procédé pouvant être facilement mis en œuvre dans les équipements et outillages des installations industrielles actuellement utilisées pour la fabrication de matériaux composites à base de résine thermodurcissable.  Another object of the present invention is to provide a process for manufacturing such a composite material, this process being able to be easily implemented in the equipment and tools of industrial installations currently used for the manufacture of composite materials based on thermosetting resin. .
Ce procédé de fabrication doit, en outre, permettre d'obtenir ce matériau composite en un nombre limité d'étapes, avec une mise en œuvre industrielle qui soit techniquement et économiquement optimisée, en particulier lorsque les pièces à fabriquer présentent une géométrie complexe et/ou de grande taille.  This manufacturing process must, moreover, make it possible to obtain this composite material in a limited number of stages, with an industrial implementation which is technically and economically optimized, in particular when the parts to be produced have a complex geometry and / or large.
EXPOSÉ DE L'INVENTION STATEMENT OF THE INVENTION
Ces buts ainsi que d'autres encore sont atteints, en premier lieu, par un matériau composite de blindage neutronique et de maintien de la sous-criticité qui est obtenu à partir d'une formulation particulière. These and other goals are achieved, first, by a composite material for neutron shielding and maintaining subcriticality which is obtained from a particular formulation.
Selon l'invention, cette formulation comprend :  According to the invention, this formulation comprises:
(A) de 20% en poids à 65% en poids, avantageusement de 25% en poids à 60% en poids, d'une composition (méth)acrylique comprenant :  (A) from 20% by weight to 65% by weight, advantageously from 25% by weight to 60% by weight, of a (meth) acrylic composition comprising:
(a) 100 parties en poids d'un sirop (méth)acrylique liquide comprenant :  (a) 100 parts by weight of a liquid (meth) acrylic syrup comprising:
(ai) de 10 % en poids à 50 % en poids d'un polymère (méth)acrylique PI, et (a2) de 50 % en poids à 90 % en poids d'un monomère (méth)acrylique Ml ne comprenant qu'une fonction (méth)acrylique, (ai) from 10% by weight to 50% by weight of a (meth) acrylic polymer PI, and (a 2 ) from 50% by weight to 90% by weight of a (meth) acrylic monomer Ml comprising only one (meth) acrylic function,
(b) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids d'un monomère (méth)acrylique M2 comprenant au moins deux fonctions (méth)acryliques,  (b) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 parts by weight to 10 parts by weight of a (meth) acrylic monomer M2 comprising at least two (meth) acrylic functions,
(c) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un monomère (méth)acrylique M3 ne comprenant qu'une fonction (méth)acrylique, le monomère M3 étant différent du monomère (méth)acrylique Ml,  (c) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of a (meth) acrylic monomer M3 comprising only one (meth) acrylic function, the monomer M3 being different from the (meth) acrylic monomer Ml,
(d) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un composé métallique,  (d) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of a metallic compound,
(e) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un agent réducteur,  (e) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 parts by weight to 10 parts by weight, of a reducing agent,
(f) de 0 ppm à 20 000 ppm, avantageusement de 1 000 ppm à 10 000 ppm, d'une amine tertiaire,  (f) from 0 ppm to 20,000 ppm, advantageously from 1,000 ppm to 10,000 ppm, of a tertiary amine,
(g) de 0,1 partie en poids à 5 parties en poids d'un initiateur de polymérisation,  (g) from 0.1 part by weight to 5 parts by weight of a polymerization initiator,
(h) de 0 ppm à 10 000 ppm d'un agent de transfert,  (h) from 0 ppm to 10,000 ppm of a transfer agent,
(i) de 0 ppm à 10 000 ppm d'un antioxydant,  (i) from 0 ppm to 10,000 ppm of an antioxidant,
(j) de 0 ppm à 1 000 ppm d'un agent piégeur de radicaux libres,  (j) from 0 ppm to 1000 ppm of a free radical scavenger,
(k) de 0 ppm à 10 000 ppm d'un stabilisant thermique, et  (k) from 0 ppm to 10,000 ppm of a thermal stabilizer, and
(L) de 0 ppm à 10 000 ppm d'un stabilisant à la lumière ; et  (L) from 0 ppm to 10,000 ppm of a light stabilizer; and
(B) de 35% en poids à 80% en poids, avantageusement de 40% en poids à 75% en poids, d'une ou plusieurs charges, la ou les charges comprenant :  (B) from 35% by weight to 80% by weight, advantageously from 40% by weight to 75% by weight, of one or more fillers, the charge or fillers comprising:
. au moins un composé du bore, et  . at least one boron compound, and
. au moins un composé hydrogéné.  . at least one hydrogenated compound.
Comme on le verra dans les exemples ci-après, le matériau composite de blindage neutronique et de maintien de la sous-criticité selon l'invention permet de réaliser des pièces, et notamment des pièces de géométrie complexe, qui ne présentent pas de défauts, en particulier pas de fissures, au sein de leur structure, le terme "fissure" étant tel que défini précédemment (pas de discontinuité bidimensionnelle ou tridimensionnelle visible à l'œil nu). Les risques d'éventuelles fuites neutroniques au sein du matériau composite sont ainsi évités. As will be seen in the examples below, the composite material for neutron shielding and for maintaining the subcriticality according to the invention makes it possible to produce parts, and in particular parts of complex geometry, which do not have any defects, in particular no cracks, within their structure, the term "crack" being as defined above (no two-dimensional or three-dimensional discontinuity visible to the naked eye). The risks of possible neutron leaks within the composite material are thus avoided.
Par ailleurs, s'il présente des performances en termes de blindage neutronique et de maintien de la sous-criticité qui sont tout à fait comparables à celle du matériau composite décrit dans le document [1], avec une concentration en bore comprise entre 5.1020 et 6.1021 atomes par cm3 et une concentration en hydrogène comprise entre 4.1022 et 8.1022 atomes par cm3, le matériau composite selon l'invention se caractérise par une résistance thermomécanique qui est améliorée par rapport à celle des matériaux composites obtenus à partir d'une formulation thermodurcissable. Furthermore, if it has performances in terms of neutron shielding and maintenance of the subcriticality which are entirely comparable to that of the composite material described in document [1], with a boron concentration of between 5.10 20 and 6.10 21 atoms per cm 3 and a hydrogen concentration between 4.10 22 and 8.10 22 atoms per cm 3 , the composite material according to the invention is characterized by a thermomechanical resistance which is improved compared to that of the composite materials obtained from a thermosetting formulation.
En outre, étant obtenu à partir d'une formulation (méth)acrylique, le matériau composite selon l'invention est un matériau thermoformable, apte à la soudure, facile à usiner et qui, de surcroît, est recyclable et moins onéreux qu'un matériau composite obtenu à partir d'une formulation comprenant une résine thermodurcissable du type vinylester comme décrit dans le document [1].  In addition, being obtained from a (meth) acrylic formulation, the composite material according to the invention is a thermoformable material, suitable for welding, easy to machine and which, moreover, is recyclable and less expensive than composite material obtained from a formulation comprising a thermosetting resin of the vinylester type as described in document [1].
Cette formulation (méth)acrylique spécifique étant de faible viscosité, le matériau composite selon l'invention présente, en outre, l'avantage d'être d'une mise en œuvre similaire à celle des matériaux composites à base de formulations thermodurcissables. Le matériau composite selon l'invention peut, en particulier, être fabriqué sur le même type d'équipements que les matériaux composites thermodurcis tels que le matériau composite décrit dans le document [1], sans recourir au chauffage des équipements (tels que les machines de mélange et de coulée de la formulation (méth)acrylique) et/ou du matériau composite.  This specific (meth) acrylic formulation being of low viscosity, the composite material according to the invention has, moreover, the advantage of being of an implementation similar to that of composite materials based on thermosetting formulations. The composite material according to the invention can, in particular, be manufactured on the same type of equipment as thermoset composite materials such as the composite material described in document [1], without having to heat the equipment (such as machines mixing and pouring the (meth) acrylic formulation) and / or the composite material.
La formulation à partir de laquelle est obtenu le matériau composite selon l'invention est une formulation comprenant une composition (méth)acrylique (A) et une ou plusieurs charges particulières (B), en l'espèce au moins un composé du bore et au moins un composé hydrogéné.  The formulation from which the composite material according to the invention is obtained is a formulation comprising a (meth) acrylic composition (A) and one or more specific fillers (B), in this case at least one boron compound and at minus a hydrogenated compound.
Cette composition (méth)acrylique comprend, dans des proportions pondérales spécifiques, un sirop (méth)acrylique liquide, un initiateur de polymérisation et, de manière optionnelle, un ou plusieurs composés choisis parmi un monomère (méth)acrylique M2, un monomère (méth)acrylique M3, un composé métallique, un agent réducteur, une amine tertiaire, un agent de transfert, un antioxydant, un agent piégeur de radicaux libres, un stabilisant thermique et un stabilisant à la lumière. This (meth) acrylic composition comprises, in specific weight proportions, a liquid (meth) acrylic syrup, a polymerization initiator and, optionally, one or more compounds chosen from a monomer (meth) acrylic M2, a (meth) acrylic monomer M3, a metal compound, a reducing agent, a tertiary amine, a transfer agent, an antioxidant, a free radical scavenger, a thermal stabilizer and a light stabilizer .
Plus particulièrement, le sirop (méth)acrylique liquide comprend :  More particularly, the liquid (meth) acrylic syrup comprises:
(ai) de 10 % en poids à 50 % en poids d'un polymère (méth)acrylique PI, et (a2) de 50 % en poids à 90 % en poids d'un monomères (méth)acrylique Ml ne comprenant qu'une fonction (méth)acrylique. (ai) from 10% by weight to 50% by weight of a (meth) acrylic polymer PI, and (a 2 ) from 50% by weight to 90% by weight of a (meth) acrylic monomer Ml comprising only 'a (meth) acrylic function.
L'expression "monomère (méth)acrylique" couvre aussi bien un monomère acrylique qu'un monomère méthacrylique. De la même manière, l'expression "polymère (méth)acrylique" couvre aussi bien un homopolymère acrylique, un homopolymère méthacrylique, un copolymère acrylique et qu'un copolymère méthacrylique.  The term "(meth) acrylic monomer" covers both an acrylic monomer and a methacrylic monomer. Likewise, the expression "(meth) acrylic polymer" covers both an acrylic homopolymer, a methacrylic homopolymer, an acrylic copolymer and a methacrylic copolymer.
Il est, par ailleurs, précisé que l'expression "de... à..." qui vient d'être citée et qui est utilisée dans la présente demande doit être comprise comme définissant non seulement les valeurs de l'intervalle, mais également les valeurs des bornes de cet intervalle.  It is, moreover, specified that the expression "from ... to ..." which has just been cited and which is used in the present application must be understood as defining not only the values of the interval, but also the values of the limits of this interval.
Le polymère (méth)acrylique PI du sirop (méth)acrylique liquide peut être choisi parmi les polyméthacrylates d'alkyle et les polyacrylates d'alkyle.  The (meth) acrylic polymer PI of the liquid (meth) acrylic syrup can be chosen from alkyl polymethacrylates and polyalkyl acrylates.
Selon un mode de réalisation avantageux, le polymère (méth)acrylique PI est un polyméthacrylate de méthyle (PMMA), ce polyméthacrylate de méthyle (PMMA) pouvant aussi bien désigner un homopolymère de méthacrylate de méthyle (MMA), un copolymère de MMA qu'un de leurs mélanges.  According to an advantageous embodiment, the (meth) acrylic polymer PI is a polymethyl methacrylate (PMMA), this polymethyl methacrylate (PMMA) can just as easily denote a homopolymer of methyl methacrylate (MMA), a copolymer of MMA as one of their mixtures.
Le polymère (méth)acrylique PI peut être formé par un mélange d'au moins un homopolymère de MMA et d'au moins un copolymère de MMA, par un mélange d'au moins deux homopolymères de MMA ayant un poids moléculaire moyen différent, par un mélange d'au moins deux copolymères de MMA ayant une composition en monomères identique et un poids moléculaire moyen différent ou encore par un mélange d'au moins deux copolymères de MMA ayant une composition en monomères différente. Selon un mode de réalisation, l'homopolymère ou le copolymère de méthacrylate de méthyle (MMA) comprend au moins 70 % en poids, avantageusement au moins 80 % en poids, de préférence au moins 90 % en poids et, plus préférentiellement, au moins 95 % en poids de méthacrylate de méthyle (MMA). The PI (meth) acrylic polymer can be formed by a mixture of at least one MMA homopolymer and at least one MMA copolymer, by a mixture of at least two MMA homopolymers having a different average molecular weight, by a mixture of at least two MMA copolymers having an identical monomer composition and a different average molecular weight or alternatively by a mixture of at least two MMA copolymers having a different monomer composition. According to one embodiment, the methyl methacrylate (MMA) homopolymer or copolymer comprises at least 70% by weight, advantageously at least 80% by weight, preferably at least 90% by weight and, more preferably, at least 95% by weight of methyl methacrylate (MMA).
Selon un mode de réalisation, le copolymère de méthacrylate de méthyle (MMA) comprend de 70 % à 99,7 % en poids de méthacrylate de méthyle (MMA) et de 0,3 % à 30 % en poids d'au moins un comonomère contenant au moins une insaturation éthylénique qui est apte à copolymériser avec le méthacrylate de méthyle.  According to one embodiment, the methyl methacrylate (MMA) copolymer comprises from 70% to 99.7% by weight of methyl methacrylate (MMA) and from 0.3% to 30% by weight of at least one comonomer containing at least one ethylenic unsaturation which is capable of copolymerizing with methyl methacrylate.
Parmi ces comonomères, on peut notamment citer l'acide acrylique, l'acide méthacrylique et les (méth)acrylates d'alkyle dans lesquels le groupe alkyle contient de 1 à 12 atomes de carbone. À titre d'exemples, on peut mentionner l'acrylate de méthyle, le (méth)acrylate d'éthyle, le (méth)acrylate de butyle et le (méth)acrylate de 2-éthylhexyle. De préférence, le comonomère est un acrylate d'alkyle dans lequel le groupe alkyle contient de 1 à 4 atomes de carbone.  Among these comonomers, mention may in particular be made of acrylic acid, methacrylic acid and alkyl (meth) acrylates in which the alkyl group contains from 1 to 12 carbon atoms. By way of examples, mention may be made of methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. Preferably, the comonomer is an alkyl acrylate in which the alkyl group contains from 1 to 4 carbon atoms.
Selon un mode de réalisation préféré, le copolymère de méthacrylate de méthyle comprend de 80 % à 99,9 %, avantageusement de 90 % à 99,9 %, en poids de méthacrylate de méthyle (MMA) et de 0,1 % à 20 %, avantageusement de 0,1 % à 10 %, en poids d'au moins un comonomère contenant au moins une insaturation éthylénique qui peut copolymériser avec le méthacrylate de méthyle. De préférence, le comonomère est choisi parmi l'acrylate de méthyle, l'acrylate d'éthyle et leurs mélanges.  According to a preferred embodiment, the methyl methacrylate copolymer comprises from 80% to 99.9%, advantageously from 90% to 99.9%, by weight of methyl methacrylate (MMA) and from 0.1% to 20 %, advantageously from 0.1% to 10%, by weight of at least one comonomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate. Preferably, the comonomer is chosen from methyl acrylate, ethyl acrylate and their mixtures.
Le poids moléculaire moyen en poids du polymère (méth)acrylique PI est généralement élevé, typiquement supérieur à 50 000 g/mol et, de préférence, supérieur à 100 000 g/mol. Ce poids moléculaire moyen en poids peut être mesuré par chromatographie d'exclusion stérique (SEC).  The weight average molecular weight of the (meth) acrylic polymer PI is generally high, typically greater than 50,000 g / mol and preferably greater than 100,000 g / mol. This weight average molecular weight can be measured by size exclusion chromatography (SEC).
Le polymère (méth)acrylique PI est soluble dans le monomère (méth)acrylique Ml ou dans le mélange de monomères (méth)acryliques. Ceci permet d'augmenter la viscosité du monomère (méth)acrylique Ml ou du mélange de monomères (méth)acryliques. Le sirop (méth)acrylique liquide de la composition (méth)acrylique comprend également un monomère (méth)acrylique Ml ne comprenant qu'une fonction (méth)acrylique. The (meth) acrylic polymer PI is soluble in the (meth) acrylic monomer Ml or in the mixture of (meth) acrylic monomers. This makes it possible to increase the viscosity of the (meth) acrylic monomer Ml or of the mixture of (meth) acrylic monomers. The liquid (meth) acrylic syrup of the (meth) acrylic composition also comprises a (meth) acrylic monomer Ml comprising only one (meth) acrylic function.
Le monomère (méth)acrylique Ml peut être choisi parmi les monomères acryliques d'alkyle, les monomères méthacryliques d'alkyle, les monomères acryliques d'hydroxyalkyle, les monomères méthacryliques d'hydroxyalkyle et leurs mélanges, le groupe alkyle pouvant être linéaire, ramifié ou cyclique, et contenir de 1 à 22 atomes de carbone, de préférence de 1 à 12 atomes de carbone.  The (meth) acrylic monomer M1 can be chosen from acrylic alkyl monomers, methacrylic alkyl monomers, acrylic hydroxyalkyl monomers, methacrylic hydroxyalkyl monomers and mixtures thereof, the alkyl group possibly being linear, branched or cyclic, and contain from 1 to 22 carbon atoms, preferably from 1 to 12 carbon atoms.
Avantageusement, le monomère (méth)acrylique Ml est choisi parmi le méthacrylate de méthyle, le méthacrylate d'éthyle, l'acrylate de méthyle, l'acrylate d'éthyle, l'acide méthacrylique, l'acide acrylique, l'acrylate de n-butyle, l'acrylate d'/'sobutyle, le méthacrylate de n-butyle, le méthacrylate d'/'sobutyle, l'acrylate de cyclohexyle, le méthacrylate de cyclohexyle, l'acrylate d'/'sobornyle, le méthacrylate d'/'sobornyle, l'acrylate d'hydroxyéthyle, le méthacrylate d'hydroxyéthyle, le méthacrylate d'hydroxyéthyle et leurs mélanges. Advantageously, the (meth) acrylic monomer Ml is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, acrylic acrylate. n-butyl acrylate / 'sobutyle methacrylate, n-butyl methacrylate /' sobutyle, cyclohexyl acrylate, cyclohexyl methacrylate, acrylate / 'sobornyle methacrylate d '/' sobornyle, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate and mixtures thereof.
Selon un mode de réalisation, le méthacrylate de méthyle représente au moins 50 % en poids, avantageusement au moins 60 % en poids, de préférence au moins 70 % en poids, plus préférentiellement au moins 80 % en poids et, plus préférentiellement encore, au moins 90 % en poids du monomère (méth)acrylique Ml.  According to one embodiment, methyl methacrylate represents at least 50% by weight, advantageously at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight and, more preferably still, at minus 90% by weight of the (meth) acrylic monomer Ml.
Selon une variante avantageuse, la composition (méth)acrylique peut comprendre un monomère (méth)acrylique M2, ce monomère (méth)acrylique M2 comprenant au moins deux fonctions (méth)acryliques.  According to an advantageous variant, the (meth) acrylic composition may comprise a (meth) acrylic monomer M2, this (meth) acrylic monomer M2 comprising at least two (meth) acrylic functions.
Ce monomère (méth)acrylique M2 peut avantageusement être choisi parmi le diméthacrylate d'éthylène glycol, le diacrylate de néopentyle glycol, le diméthacrylate de néopentyle glycol, le diméthacrylate de 1,4-butanediol, le diacrylate de 1,4-butanediol, le diacrylate de 1,3-butylène glycol, le diméthacrylate de 1,3-butylène glycol, le diméthacrylate de triéthylène glycol, le diacrylate de triéthylène glycol et leurs mélanges.  This M2 (meth) acrylic monomer can advantageously be chosen from ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate and mixtures thereof.
La composition (méth)acrylique peut ainsi comprendre jusqu'à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, de monomère (méth)acrylique M2 pour 100 parties en poids de sirop (méth)acrylique liquide. The (meth) acrylic composition can thus comprise up to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, M2 (meth) acrylic monomer per 100 parts by weight of liquid (meth) acrylic syrup.
Selon une variante avantageuse, la composition (méth)acrylique peut comprendre un monomère (méth)acrylique M3. Ce monomère (méth)acrylique M3 ne comprend qu'une fonction (méth)acrylique et est différent du monomère (méth)acrylique Ml.  According to an advantageous variant, the (meth) acrylic composition may comprise a (meth) acrylic monomer M3. This (meth) acrylic monomer M3 only has one (meth) acrylic function and is different from the (meth) acrylic monomer Ml.
Ce monomère (méth)acrylique M3 peut notamment être un monomère qui, une fois polymérisé sous forme d'un homopolymère, présente une température de transition vitreuse Tg d'au moins 120 °C, la température Tg d'un homopolymère pouvant être déterminée conformément à la publication "Polymer Handbook".  This (meth) acrylic monomer M3 can in particular be a monomer which, once polymerized in the form of a homopolymer, has a glass transition temperature Tg of at least 120 ° C., the temperature Tg of a homopolymer can be determined in accordance with to the publication "Polymer Handbook".
Avantageusement, le monomère M3 est l'acide méthacrylique.  Advantageously, the monomer M3 is methacrylic acid.
La composition (méth)acrylique peut ainsi comprendre jusqu'à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, de monomère (méth)acrylique M3 pour 100 parties en poids de sirop méthacrylique liquide.  The (meth) acrylic composition can thus comprise up to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of (meth) acrylic monomer M3 per 100 parts by weight of liquid methacrylic syrup.
Dans une variante avantageuse, la composition (méth)acrylique comprend au moins un monomère (méth)acrylique parmi les monomères (méth)acryliques M2 et M3, de préférence M2.  In an advantageous variant, the (meth) acrylic composition comprises at least one (meth) acrylic monomer from the (meth) acrylic monomers M2 and M3, preferably M2.
Dans une variante encore plus préférentielle, la composition (méth)acrylique comprend les monomères (méth)acryliques M2 et M3.  In an even more preferred variant, the (meth) acrylic composition comprises the (meth) acrylic monomers M2 and M3.
La composition (méth)acrylique comprend , en outre, de 0,1 partie en poids à 5 parties en poids, pour 100 parties en poids de sirop méthacrylique liquide, d'un initiateur de polymérisation dont le rôle est d'assurer le démarrage de la polymérisation des monomères (méth)acryliques Ml et, le cas échéant, M2 et/ou M3.  The (meth) acrylic composition also comprises from 0.1 part by weight to 5 parts by weight, per 100 parts by weight of liquid methacrylic syrup, of a polymerization initiator whose role is to ensure the start-up of polymerization of the (meth) acrylic monomers Ml and, where appropriate, M2 and / or M3.
L'initiateur de polymérisation, de préférence un initiateur de polymérisation radicalaire, peut se présenter sous une forme solide, le cas échéant en mélange avec un solvant pour le solubiliser, ou bien sous une forme liquide.  The polymerization initiator, preferably a radical polymerization initiator, may be in a solid form, if necessary in admixture with a solvent to dissolve it, or else in a liquid form.
Selon une variante, l'initiateur de polymérisation est un peroxyde, de préférence un peroxyde qui est liquide à une température comprise entre 0° C et 50 °C.  According to a variant, the polymerization initiator is a peroxide, preferably a peroxide which is liquid at a temperature between 0 ° C and 50 ° C.
Selon une variante avantageuse, le peroxyde est un peroxyde organique comprenant de 2 à 30 atomes de carbone, par exemple le peroxyde de méthyléthylcétone (PMEC), le peroxyde de méthylisopropylcétone (PMIC) ou un hydro peroxyde. According to an advantageous variant, the peroxide is an organic peroxide comprising from 2 to 30 carbon atoms, for example methyl ethyl ketone (PMEC), methyl isopropyl ketone peroxide (PMIC) or a hydro peroxide.
Avantageusement, l'initiateur de polymérisation est un hydroperoxyde ou un peroxyde comprenant au moins une fonction hydroperoxyde choisi parmi l'hydroperoxyde de te/t-butyle, le monohydroperoxyde, l'hydroperoxyde de para- méthane, l'hydroperoxyde de te/t-amyle, le peroxyde de méthyléthylcétone, le peroxyde de méthylisopropylcétone et l'hydroperoxyde de cumène.  Advantageously, the polymerization initiator is a hydroperoxide or a peroxide comprising at least one hydroperoxide function chosen from te / t-butyl hydroperoxide, monohydroperoxide, para-methane hydroperoxide, te / t-hydroperoxide amyl, methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide and cumene hydroperoxide.
Préférentiellement, l'initiateur de polymérisation est le monohydroperoxyde, le peroxyde de méthyléthylcétone, le peroxyde de méthylisopropylcétone ou l'hydroperoxyde de para-méthane.  Preferably, the polymerization initiator is monohydroperoxide, methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide or para-methane hydroperoxide.
La composition (méth)acrylique peut également comprendre jusqu'à 10 parties en poids d'un composé métallique pour 100 parties en poids de sirop méthacrylique liquide.  The (meth) acrylic composition can also comprise up to 10 parts by weight of a metallic compound per 100 parts by weight of liquid methacrylic syrup.
Selon une variante, le composé métallique comprend un ou plusieurs métaux de transition choisis parmi les métaux de transition de la quatrième période du tableau périodique des éléments.  According to a variant, the metallic compound comprises one or more transition metals chosen from the transition metals of the fourth period of the periodic table of the elements.
Selon une variante, le composé métallique est un complexe métallique, un sel métallique ou un mélange de sels métalliques.  According to a variant, the metallic compound is a metallic complex, a metallic salt or a mixture of metallic salts.
Selon une variante avantageuse, le composé métallique ne comprend pas de cobalt.  According to an advantageous variant, the metallic compound does not comprise cobalt.
Selon une variante préférentielle, le ou les métaux du composé métallique sont choisis parmi le fer, le cuivre et le manganèse.  According to a preferred variant, the metal or metals of the metallic compound are chosen from iron, copper and manganese.
Selon un mode de réalisation, la composition (méth)acrylique comprend de 0,01 partie en poids à 10 parties en poids et, avantageusement, de 0,05 partie en poids à 3 parties en poids de composé métallique pour 100 parties en poids de sirop méthacrylique liquide.  According to one embodiment, the (meth) acrylic composition comprises from 0.01 part by weight to 10 parts by weight and, advantageously, from 0.05 part by weight to 3 parts by weight of metallic compound per 100 parts by weight of liquid methacrylic syrup.
La composition (méth)acrylique peut également comprendre jusqu'à 10 parties en poids d'un agent réducteur pour 100 parties en poids de sirop méthacrylique liquide. Selon une variante, l'agent réducteur est choisi parmi l'acide ascorbique, la saccharine, les a-hydroxysulfones, les thio-urées et leurs mélanges. The (meth) acrylic composition can also comprise up to 10 parts by weight of a reducing agent per 100 parts by weight of liquid methacrylic syrup. According to a variant, the reducing agent is chosen from ascorbic acid, saccharin, α-hydroxysulfones, thioureas and their mixtures.
De préférence, l'agent réducteur est la saccharine.  Preferably, the reducing agent is saccharin.
Selon un mode de réalisation, la composition (méth)acrylique comprend de 0,01 partie en poids à 10 parties en poids, avantageusement de 0,1 partie en poids à 2 parties en poids et, préférentiellement, de 0,1 partie en poids à 1 partie en poids d'agent réducteur pour 100 parties en poids de sirop méthacrylique liquide.  According to one embodiment, the (meth) acrylic composition comprises from 0.01 part by weight to 10 parts by weight, advantageously from 0.1 part by weight to 2 parts by weight and, preferably, from 0.1 part by weight to 1 part by weight of reducing agent per 100 parts by weight of liquid methacrylic syrup.
La composition (méth)acrylique peut également comprendre jusqu'à 20 000 ppm d'une amine tertiaire pour 100 parties en poids de sirop méthacrylique liquide.  The (meth) acrylic composition can also comprise up to 20,000 ppm of a tertiary amine per 100 parts by weight of liquid methacrylic syrup.
Selon une variante, l'amine tertiaire est choisie parmi la L/,/V-diméthyl-p- toluidine (DMPT), la L/,/V-dihydroxyéthyl-p-toluidine (DHEPT), la L/,/V-diéthyl-p-toluidine (DEPT) et l'éthoxylate de p-toluidine (PTE).  According to a variant, the tertiary amine is chosen from L /, / V-dimethyl-p-toluidine (DMPT), L /, / V-dihydroxyethyl-p-toluidine (DHEPT), L /, / V- diethyl-p-toluidine (DEPT) and p-toluidine ethoxylate (PTE).
Selon un mode de réalisation, la composition (méth)acrylique comprend de 1 000 ppm à 10 000 ppm d'amine tertiaire pour 100 parties en poids de sirop (méth)acrylique liquide.  According to one embodiment, the (meth) acrylic composition comprises from 1,000 ppm to 10,000 ppm of tertiary amine per 100 parts by weight of liquid (meth) acrylic syrup.
La composition (méth)acrylique peut également comprendre jusqu'à 10 000 ppm d'un agent de transfert pour 100 parties en poids de sirop (métha)crylique liquide.  The (meth) acrylic composition can also comprise up to 10,000 ppm of a transfer agent per 100 parts by weight of liquid (metha) crylic syrup.
Selon une variante, l'agent de transfert est choisi parmi les thiols, des molécules soufrées comprenant des cycles aromatiques et des dérivés terpéniques tels que le terpinolène.  According to a variant, the transfer agent is chosen from thiols, sulfur molecules comprising aromatic rings and terpene derivatives such as terpinolene.
Selon une variante avantageuse, l'agent de transfert est le terpinolène. According to an advantageous variant, the transfer agent is terpinolene.
Selon un mode de réalisation, la composition (méth)acrylique comprend de 0,01 ppm à 5 000 ppm, avantageusement de 0,1 ppm à 3 000 ppm, d'agent de transfert pour 100 parties en poids de sirop méthacrylique liquide. According to one embodiment, the (meth) acrylic composition comprises from 0.01 ppm to 5,000 ppm, advantageously from 0.1 ppm to 3,000 ppm, of transfer agent per 100 parts by weight of liquid methacrylic syrup.
La composition (méth)acrylique peut également comprendre jusqu'à 10 000 ppm d'un antioxydant pour 100 parties en poids de sirop méthacrylique liquide.  The (meth) acrylic composition can also comprise up to 10,000 ppm of an antioxidant per 100 parts by weight of liquid methacrylic syrup.
Selon une variante, l'antioxydant est choisi parmi les composés phénoliques tels que les Irganox®. Selon un mode de réalisation, la composition (méth)acrylique comprend de 0,01 ppm à 5 000 ppm, avantageusement de 0,1 ppm à 3 000 ppm, d'antioxydant pour 100 parties en poids de sirop méthacrylique liquide. Alternatively, the antioxidant is selected from phenolic compounds such as Irganox ®. According to one embodiment, the (meth) acrylic composition comprises from 0.01 ppm to 5,000 ppm, advantageously from 0.1 ppm to 3,000 ppm, of antioxidant per 100 parts by weight of liquid methacrylic syrup.
La composition (méth)acrylique peut également comprendre jusqu'à 1 000 ppm d'un agent piégeur de radicaux libres pour 100 parties en poids de sirop méthacrylique liquide.  The (meth) acrylic composition can also comprise up to 1000 ppm of a free radical scavenger per 100 parts by weight of liquid methacrylic syrup.
Selon une variante, l'agent piégeur de radicaux libres est choisi parmi les alkoxylamines et les nitroxydes.  According to a variant, the free radical scavenger is chosen from alkoxylamines and nitroxides.
Selon un mode de réalisation, la composition (méth)acrylique comprend de 0,01 ppm à 500 ppm, avantageusement de 0,1 ppm à 400 ppm, d'agent piégeur de radicaux libres pour 100 parties en poids de sirop méthacrylique liquide.  According to one embodiment, the (meth) acrylic composition comprises from 0.01 ppm to 500 ppm, advantageously from 0.1 ppm to 400 ppm, of free radical scavenger per 100 parts by weight of liquid methacrylic syrup.
La composition (méth)acrylique peut également comprendre jusqu'à 10 000 ppm d'un stabilisant thermique pour 100 parties en poids de sirop méthacrylique liquide, ce stabilisant thermique permettant d'améliorer la stabilité en température et au vieillissement du matériau composite selon l'invention.  The (meth) acrylic composition can also comprise up to 10,000 ppm of a thermal stabilizer per 100 parts by weight of liquid methacrylic syrup, this thermal stabilizer making it possible to improve the temperature and aging stability of the composite material according to the invention.
Selon une variante, le stabilisant thermique est un disulfure tel que le poly-te/t-amylphénoldisulfure.  According to one variant, the thermal stabilizer is a disulfide such as poly-te / t-amylphenoldisulfide.
Selon un mode de réalisation, la composition (méth)acrylique comprend de 0,01 ppm à 5 000 ppm, avantageusement de 0,1 ppm à 3 000 ppm, de stabilisant thermique pour 100 parties en poids de sirop méthacrylique liquide.  According to one embodiment, the (meth) acrylic composition comprises from 0.01 ppm to 5,000 ppm, advantageously from 0.1 ppm to 3,000 ppm, of thermal stabilizer per 100 parts by weight of liquid methacrylic syrup.
La composition (méth)acrylique peut également comprendre jusqu'à 10 000 ppm d'un stabilisant à la lumière pour 100 parties en poids de sirop méthacrylique liquide.  The (meth) acrylic composition can also comprise up to 10,000 ppm of a light stabilizer per 100 parts by weight of liquid methacrylic syrup.
Selon une variante, le stabilisant à la lumière est choisi parmi les stabilisants du type amine encombrée (ou HALS pour Hindered Amine Light Stabiliser), par exemple le sébacéate de bis(2,2,6,6-tétraméthyl-4-pipéridyle) et les phosphites.  According to a variant, the light stabilizer is chosen from stabilizers of the hindered amine type (or HALS for Hindered Amine Light Stabilizer), for example bis (2,2,6,6-tetramethyl-4-piperidyl) sebaceate and phosphites.
Selon un mode de réalisation, la composition (méth)acrylique comprend de 0,01 ppm à 7 000 ppm, avantageusement de 0,1 ppm à 5 000 ppm, de stabilisant à la lumière pour 100 parties en poids de sirop méthacrylique liquide. Outre la composition (méth)acrylique qui vient d'être décrite, la formulation à partir de laquelle est obtenu le matériau composite selon l'invention comprend une ou plusieurs charges particulières (B). According to one embodiment, the (meth) acrylic composition comprises from 0.01 ppm to 7000 ppm, advantageously from 0.1 ppm to 5000 ppm, of light stabilizer per 100 parts by weight of liquid methacrylic syrup. In addition to the (meth) acrylic composition which has just been described, the formulation from which the composite material according to the invention is obtained comprises one or more specific fillers (B).
Cette ou ces charges comprennent au moins un composé du bore et au moins un composé hydrogéné.  This or these charges comprise at least one boron compound and at least one hydrogenated compound.
Le ou les composés hydrogénés, dont le rôle est de ralentir les neutrons, peuvent être aussi bien formés par des charges inorganiques que par des charges organiques. Ces composés hydrogénés peuvent, en particulier, être choisis parmi les hydroxydes et les polyoléfines.  The hydrogenated compound (s), the role of which is to slow down the neutrons, can be formed as well by inorganic fillers as by organic fillers. These hydrogenated compounds can, in particular, be chosen from hydroxides and polyolefins.
Lorsque le ou les composés hydrogénés sont des hydroxydes, ceux-ci peuvent être choisis parmi l'hydrate d'alumine (ou trihydroxyde d'aluminium) AI(OH)3 et l'hydroxyde de magnésium Mg(OH)2. When the hydrogenated compound (s) are hydroxides, these can be chosen from alumina hydrate (or aluminum trihydroxide) AI (OH) 3 and magnesium hydroxide Mg (OH) 2 .
L'hydrate d'alumine est plus particulièrement préféré dans le sens où ce composé hydrogéné confère, en outre, au matériau composite des propriétés d'autoextinguibilité.  Alumina hydrate is more particularly preferred in the sense that this hydrogenated compound also confers on the composite material self-extinguishing properties.
Lorsque le ou les composés hydrogénés sont des polyoléfines, celles-ci peuvent notamment être un polyéthylène. Le matériau composite selon l'invention, qui est obtenu à partir d'une formulation comprenant un polyéthylène, présente l'avantage d'être plus léger qu'un matériau composite comprenant de l'hydrate d'alumine et peut avantageusement être utilisé dans des emballages au sein desquels la température est plus faible que celle mentionnée ci-dessus, et notamment comprise entre 130 °C et 150 °C.  When the hydrogenated compound (s) are polyolefins, these can in particular be a polyethylene. The composite material according to the invention, which is obtained from a formulation comprising a polyethylene, has the advantage of being lighter than a composite material comprising alumina hydrate and can advantageously be used in packages in which the temperature is lower than that mentioned above, and in particular between 130 ° C and 150 ° C.
Le ou les composés du bore, dont le rôle est d'absorber les neutrons une fois ralentis par le ou les composés hydrogénés, peuvent notamment être choisis parmi l'acide borique H3BO3, la colémanite Ca20i4B6Hio, les borates de zinc tels que 4ZhO,6B2q3,7H2q, 4ZhO,B2q3,H2q, 2Zn0,3B203 et 3ZhO,2B2q3, le carbure de bore B4C, le nitrure de bore BN et l'oxyde de bore B2O3. The boron compound (s), the role of which is to absorb the neutrons once slowed down by the hydrogenated compound (s), can in particular be chosen from boric acid H3BO3, colemanite Ca 2 O 4 B 6 Hio, borates of zinc such as 4ZhO, 6B 2 q 3 , 7H 2 q, 4ZhO, B 2 q 3 , H 2 q, 2Zn0.3B 2 03 and 3ZhO, 2B 2 q 3 , boron carbide B 4 C, boron nitride BN and boron oxide B2O3.
Dans une variante de l'invention, le ou les composés du bore comprennent de l'hydrogène et peuvent notamment être choisis parmi les borates de zinc hydratés tels que 4ZhO,6B2q3,7H2q ou encore 4ZhO,B2q3,H2q. De tels borates hydratés permettent, en outre, de conférer des propriétés d'autoextinguibilité au matériau composite selon l'invention. In a variant of the invention, the boron compound or compounds comprise hydrogen and can in particular be chosen from hydrated zinc borates such as 4ZhO, 6B 2 q 3 , 7H 2 q or also 4ZhO, B 2 q 3 , H 2 q. Such borates hydrates also make it possible to confer self-extinguishing properties on the composite material according to the invention.
Dans une variante de l'invention, la formulation comprend :  In a variant of the invention, the formulation comprises:
. de 2% en poids à 45% en poids de composé(s) de bore, et  . from 2% by weight to 45% by weight of boron compound (s), and
. de 30% en poids à 73% en poids de composé(s) hydrogéné(s).  . from 30% by weight to 73% by weight of hydrogenated compound (s).
Les proportions pondérales en composés de bore et hydrogénés peuvent être avantageusement adaptées en fonction des propriétés recherchées parmi les propriétés de blindage et/ou de sous-criticité.  The weight proportions of boron and hydrogenated compounds can be advantageously adapted as a function of the properties desired from the shielding and / or subcritical properties.
Selon un mode de réalisation particulier, la ou les charges particulières (B) comprenant au moins un composé du bore et au moins un composé hydrogéné se présentent sous une forme divisée (par exemple, sous la forme de granulés, de grains, de billes, de poudres, de paillettes...) que l'on désigne ci-après par le terme générique de particules.  According to a particular embodiment, the particular charge (s) (B) comprising at least one boron compound and at least one hydrogenated compound are in a divided form (for example, in the form of granules, grains, beads, powders, flakes ...) which is designated below by the generic term of particles.
Dans une variante particulière, cette ou ces charges (B) se présentent sous la forme de particules dont la plus grande dimension est au plus égale à 1 cm, la taille des particules pouvant être déterminée par diffraction laser.  In a particular variant, this or these charges (B) are in the form of particles the largest dimension of which is at most equal to 1 cm, the size of the particles being able to be determined by laser diffraction.
Cette plus grande dimension des particules de charge(s) (B) peut notamment être comprise entre 1 pm et 1 mm, avantageusement comprise entre 5 pm et 500 pm et, de préférence, comprise entre 10 pm et 200 pm.  This larger dimension of the filler particles (B) can in particular be between 1 pm and 1 mm, advantageously between 5 pm and 500 pm and, preferably, between 10 pm and 200 pm.
La formulation comprend de 20 % en poids à 65 % en poids de composition (méth)acrylique (A) et de 35 % en poids à 80 % en poids de la ou des charges particulières (B) décrites ci-dessus.  The formulation comprises from 20% by weight to 65% by weight of (meth) acrylic composition (A) and from 35% by weight to 80% by weight of the particular filler (s) (B) described above.
Dans une variante avantageuse, la formulation comprend de 25 % en poids à 60 % en poids de composition (méth)acrylique (A) et de 40 % en poids à 75 % en poids de charge(s) (B).  In an advantageous variant, the formulation comprises from 25% by weight to 60% by weight of (meth) acrylic composition (A) and from 40% by weight to 75% by weight of filler (s) (B).
La viscosité de la composition (méth)acrylique (A) étant réduite, il est possible d'incorporer une forte proportion pondérale de charge(s) (B). Ce faisant, on obtient un matériau composite qui présente une bonne tenue au vieillissement, à une température élevée, en particulier à 160 °C qui correspond à la température susceptible d'être atteinte par le matériau composite plus particulièrement disposé dans un emballage d'entreposage, de stockage et/ou de transport de matière radioactive. À titre d'illustration, après vieillissement pendant 100 jours à une température de 160 °C, la perte de masse en hydrogène du matériau composite selon l'invention est inférieure à 10 %. The viscosity of the (meth) acrylic composition (A) being reduced, it is possible to incorporate a high proportion by weight of filler (s) (B). In doing so, a composite material is obtained which has good resistance to aging, at a high temperature, in particular at 160 ° C. which corresponds to the temperature capable of being reached by the composite material more particularly placed in a packaging for storing, storing and / or transporting radioactive material. By way of illustration, after aging for 100 days at a temperature of 160 ° C., the loss of hydrogen mass of the composite material according to the invention is less than 10%.
Au demeurant, la formulation à partir de laquelle est obtenu le matériau composite selon l'invention présente la propriété de pouvoir être coulée, permettant son transfert aisé dans un moule. Cette formulation présente une viscosité préférentiellement inférieure ou égale à 25 Pa.s.  Moreover, the formulation from which the composite material according to the invention is obtained has the property of being able to be cast, allowing its easy transfer into a mold. This formulation has a viscosity preferably less than or equal to 25 Pa.s.
La formulation peut également comprendre un ou plusieurs autres composés additionnels, par exemple des charges métalliques (telles que le plomb) pour le blindage gamma et/ou des additifs permettant d'augmenter la tenue en température, la souplesse et/ou la tenue aux chocs du matériau composite.  The formulation can also comprise one or more other additional compounds, for example metallic fillers (such as lead) for gamma shielding and / or additives making it possible to increase the temperature resistance, the flexibility and / or the impact resistance. composite material.
La présente invention se rapporte, en deuxième lieu, à un procédé de fabrication d'un matériau composite de blindage neutronique et de maintien de la sous- criticité à partir de la formulation particulière telle que décrite ci-dessus. The present invention relates, secondly, to a process for manufacturing a composite material for neutron shielding and for maintaining subcriticality from the particular formulation as described above.
Selon l'invention, ce procédé comprend :  According to the invention, this method comprises:
(1) le mélange des composés de la formulation telle que décrite ci-dessus, le sirop (méth)acrylique liquide étant préparé en premier et l'initiateur de polymérisation étant introduit en dernier dans la formulation, et  (1) mixing the compounds of the formulation as described above, the liquid (meth) acrylic syrup being prepared first and the polymerization initiator being introduced last into the formulation, and
(2) le moulage à température ambiante de la formulation obtenue à l'étape (l).En d'autres termes, le procédé selon l'invention comprend :  (2) the molding at room temperature of the formulation obtained in step (l). In other words, the method according to the invention comprises:
(1) le mélange des composés suivants :  (1) the mixture of the following compounds:
(A) de 20 % en poids à 65 % en poids, avantageusement de 25% en poids à 60% en poids, d'une composition (méth)acrylique comprenant :  (A) from 20% by weight to 65% by weight, advantageously from 25% by weight to 60% by weight, of a (meth) acrylic composition comprising:
(a) 100 parties en poids d'un sirop (méth)acrylique liquide comprenant :  (a) 100 parts by weight of a liquid (meth) acrylic syrup comprising:
(ai) de 10 % en poids à 50 % en poids d'un polymère (méth)acrylique PI, et (a2) de 50 % en poids à 90 % en poids d'un monomère (méth)acrylique Ml ne comprenant qu'une fonction (méth)acrylique, (b) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids d'un monomère (méth)acrylique M2 comprenant au moins deux fonctions (méth)acryliques, (ai) from 10% by weight to 50% by weight of a (meth) acrylic polymer PI, and (a 2 ) from 50% by weight to 90% by weight of a (meth) acrylic monomer Ml comprising only 'a (meth) acrylic function, (b) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 parts by weight to 10 parts by weight of a (meth) acrylic monomer M2 comprising at least two (meth) acrylic functions,
(c) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un monomère (méth)acrylique M3 ne comprenant qu'une fonction (méth)acrylique, le monomère M3 étant différent du monomère (méth)acrylique Ml,  (c) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of a (meth) acrylic monomer M3 comprising only one (meth) acrylic function, the monomer M3 being different from the (meth) acrylic monomer Ml,
(d) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un composé métallique,  (d) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of a metallic compound,
(e) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un agent réducteur,  (e) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 parts by weight to 10 parts by weight, of a reducing agent,
(f) de 0 ppm à 20 000 ppm, avantageusement de 1 000 ppm à 10 000 ppm, d'une amine tertiaire,  (f) from 0 ppm to 20,000 ppm, advantageously from 1,000 ppm to 10,000 ppm, of a tertiary amine,
(g) de 0,1 partie en poids à 5 parties en poids d'un initiateur de polymérisation,  (g) from 0.1 part by weight to 5 parts by weight of a polymerization initiator,
(h) de 0 ppm à 10 000 ppm d'un agent de transfert,  (h) from 0 ppm to 10,000 ppm of a transfer agent,
(i) de 0 ppm à 10 000 ppm d'un antioxydant,  (i) from 0 ppm to 10,000 ppm of an antioxidant,
(j) de 0 ppm à 1 000 ppm d'un agent piégeur de radicaux libres,  (j) from 0 ppm to 1000 ppm of a free radical scavenger,
(k) de 0 ppm à 10 000 ppm d'un stabilisant thermique, et  (k) from 0 ppm to 10,000 ppm of a thermal stabilizer, and
(L) de 0 ppm à 10 000 ppm d'un stabilisant à la lumière ; et  (L) from 0 ppm to 10,000 ppm of a light stabilizer; and
(B) de 35 % en poids à 80 % en poids, avantageusement de 40 % en poids à 75 % en poids, d'une ou plusieurs charges, la ou les charges comprenant :  (B) from 35% by weight to 80% by weight, advantageously from 40% by weight to 75% by weight, of one or more fillers, the charge or fillers comprising:
. au moins un composé de bore, et  . at least one boron compound, and
. au moins un composé hydrogéné.  . at least one hydrogenated compound.
le sirop (méth)acrylique liquide étant préparé en premier et l'initiateur de polymérisation étant introduit en dernier dans la formulation, et the liquid (meth) acrylic syrup being prepared first and the polymerization initiator being introduced last into the formulation, and
(2) le moulage à température ambiante de la formulation obtenue à l'étape (l).Le procédé de fabrication selon l'invention est donc un procédé dont la mise en œuvre est particulièrement simple, rapide et économique. Le procédé selon l'invention permet d'obtenir un matériau composite de forme (design) spécifiquement adaptée à l'emballage auquel il est destiné. Ce procédé peut, en outre, être facilement mis en œuvre dans les installations actuellement dédiées aux procédés de fabrication de matériaux composites obtenus à partir de formulations thermodurcissables, tels que celui décrit dans le document [1]· (2) the molding at room temperature of the formulation obtained in step (l). The manufacturing process according to the invention is therefore a process the implementation of which is particularly simple, rapid and economical. The method according to the invention makes it possible to obtain a composite material of shape (design) specifically adapted to the packaging. for which it is intended. This process can, moreover, be easily implemented in installations currently dedicated to the processes for manufacturing composite materials obtained from thermosetting formulations, such as that described in document [1] ·
Les caractéristiques décrites précédemment en liaison avec la composition (méth)acrylique et, notamment, les caractéristiques relatives au polymère (méth)acrylique PI et au monomère (méth)acrylique Ml formant le sirop (méth)acrylique, aux monomères (méth)acryliques M2 et M3, au composé métallique, à l'agent réducteur, à l'amine tertiaire, à l'initiateur de polymérisation, à l'agent de transfert, à l'antioxydant, à l'agent piégeur de radicaux libres, aux stabilisants thermiques et à la lumière, à la ou aux charges (B) et aux composés additionnels, sont bien entendu applicables au présent procédé de fabrication du matériau composite.  The characteristics described above in connection with the (meth) acrylic composition and, in particular, the characteristics relating to the (meth) acrylic polymer PI and to the (meth) acrylic monomer Ml forming the (meth) acrylic syrup, to the (meth) acrylic monomers M2 and M3, the metallic compound, the reducing agent, the tertiary amine, the polymerization initiator, the transfer agent, the antioxidant, the free radical scavenger, the thermal stabilizers and to light, to the filler (s) (B) and to the additional compounds, are of course applicable to the present method of manufacturing the composite material.
L'étape (1) du procédé de fabrication selon l'invention est réalisée par mélange de l'ensemble des composés entrant dans la composition (méth)acrylique (A) et de la ou des charges particulières (B), en prenant le soin de préparer, en premier lieu, le sirop (méth)acrylique liquide puis d'introduire, dans ce sirop (méth)acrylique, l'initiateur de polymérisation et, le cas échéant, les monomères (méth)acryliques M2 et/ou M3, le composé métallique, l'agent réducteur, l'amine tertiaire, l'agent de transfert, l'antioxydant, l'agent piégeur de radicaux libres, les stabilisants thermiques et à la lumière, la ou les charges (B) et aux composés additionnels, l'initiateur de polymérisation étant introduit en dernier lieu.  Step (1) of the manufacturing process according to the invention is carried out by mixing all of the compounds entering into the (meth) acrylic composition (A) and the particular filler (s) (B), taking care to prepare, in the first place, the liquid (meth) acrylic syrup and then to introduce, into this (meth) acrylic syrup, the polymerization initiator and, where appropriate, the (meth) acrylic monomers M2 and / or M3, the metal compound, the reducing agent, the tertiary amine, the transfer agent, the antioxidant, the free radical scavenger, the thermal and light stabilizers, the charge (s) (B) and to the compounds additional, the polymerization initiator being introduced last.
Un tel mélange peut être manuel ou bien réalisé au moyen d'un mélangeur.  Such mixing can be manual or else carried out by means of a mixer.
Dans une première variante de l'invention, la formulation peut être coulée dans un moule pour la mise en œuvre ultérieure de l'étape (2) de moulage.  In a first variant of the invention, the formulation can be poured into a mold for the subsequent implementation of step (2) of molding.
Dans une seconde variante de l'invention, la formulation peut être coulée directement dans l'emballage destiné à l'entreposage, le stockage et/ou le transport de matière radioactive. Un tel emballage peut, par exemple, comporter des logements périphériques dans lesquels est coulée la formulation. L'étape (2) de moulage de la formulation telle qu'obtenue à l'issue de l'étape (1) s'effectue à la température ambiante, c'est-à-dire à une température typiquement comprise entre 18 °C et 25 °C, et permet de réaliser la polymérisation de la matrice et, ce faisant, d'obtenir le matériau composite de blindage neutronique et de maintien de la sous-criticité selon l'invention. In a second variant of the invention, the formulation can be poured directly into the packaging intended for the storage, storage and / or transport of radioactive material. Such packaging can, for example, include peripheral housings into which the formulation is poured. Step (2) of molding the formulation as obtained at the end of step (1) is carried out at room temperature, that is to say at a temperature typically between 18 ° C. and 25 ° C., and makes it possible to carry out the polymerization of the matrix and, in so doing, to obtain the composite material for neutron shielding and for maintaining the subcriticality according to the invention.
Le mécanisme de cette réaction de polymérisation est radicalaire.  The mechanism of this polymerization reaction is radical.
L'invention se rapporte, en troisième lieu, à l'utilisation du matériau composite de blindage neutronique et de maintien de la sous-criticité tel que défini ci- dessus, les caractéristiques avantageuses de ce matériau composite pouvant être prises seules ou en combinaison.  The invention relates, thirdly, to the use of the composite material for neutron shielding and for maintaining the subcriticality as defined above, the advantageous characteristics of this composite material being able to be taken alone or in combination.
L'invention se rapporte également à l'utilisation de la formulation telle que décrite ci-dessus pour l'obtention du matériau composite de blindage neutronique et de maintien de la sous-criticité selon l'invention, les caractéristiques avantageuses de cette formulation pouvant être prises seules ou en combinaison.  The invention also relates to the use of the formulation as described above for obtaining the composite material for neutron shielding and for maintaining subcriticality according to the invention, the advantageous characteristics of this formulation possibly being taken alone or in combination.
Le matériau composite selon l'invention ainsi que la formulation à partir de laquelle ce matériau composite est obtenu peuvent notamment être utilisés pour la fabrication d'une pièce d'un emballage destiné à l'entreposage, le stockage et/ou le transport de matière radioactive.  The composite material according to the invention as well as the formulation from which this composite material is obtained can in particular be used for the manufacture of a piece of packaging intended for the storage, storage and / or transport of material radioactive.
L'invention se rapporte, en quatrième lieu, à un emballage d'entreposage, de stockage et/ou de transport de matière radioactive.  The invention relates, fourthly, to a packaging for storing, storing and / or transporting radioactive material.
Selon l'invention, cet emballage d'entreposage, de stockage et/ou de transport de matière radioactive comprend un matériau composite de blindage neutronique et de maintien de la sous-criticité tel que défini ci-dessus, les caractéristiques avantageuses de ce matériau composite pouvant être prises seules ou en combinaison.  According to the invention, this packaging for storing, storing and / or transporting radioactive material comprises a composite material for neutron shielding and for maintaining the subcriticality as defined above, the advantageous characteristics of this composite material. can be taken alone or in combination.
D'autres avantages et caractéristiques de la présente invention ressortiront plus clairement de la description qui suit, qui se rapporte à des exemples de préparation de matériaux composites, certains conformes à l'invention et d'autres conformes à l'enseignement du document [1], ainsi qu'à l'évaluation de leurs propriétés thermomécaniques. Bien entendu, ces modes de réalisation particuliers de l'invention ne sont donnés qu'à titre d'illustration de l'objet de l'invention et ne constituent, en aucun cas, une limitation de cet objet. Other advantages and characteristics of the present invention will emerge more clearly from the description which follows, which relates to examples of the preparation of composite materials, some in accordance with the invention and others in accordance with the teaching of document [1 ], as well as the evaluation of their thermomechanical properties. Of course, these particular embodiments of the invention are given only by way of illustration of the object of the invention and do not in any way constitute a limitation of this object.
BRÈVE DESCRIPTION DES DESSINS BRIEF DESCRIPTION OF THE DRAWINGS
La figure 1 représente des courbes traduisant l'évolution de la perte de masse (notée Am et exprimée en %) en fonction du temps de vieillissement (noté t et exprimé en h) de deux matériaux composites placés dans un environnement à 160 °C, l'un étant un matériau composite conforme à l'invention et obtenu à partir de la formulation 1 (courbe notée 1) et l'autre étant un matériau composite comparatif obtenu à partir de la formulation C (courbe notée C). Figure 1 represents curves translating the evolution of the loss of mass (noted A m and expressed in%) as a function of the aging time (noted t and expressed in h) of two composite materials placed in an environment at 160 ° C , one being a composite material according to the invention and obtained from formulation 1 (curve denoted 1) and the other being a comparative composite material obtained from formulation C (curve denoted C).
La figure 2 représente des courbes traduisant l'évolution de la perte de masse (notée Am et exprimée en %) en fonction du temps de vieillissement (noté t et exprimé en h) de trois matériaux composites placés dans un environnement à 180 °C, deux étant des matériaux composites conformes à l'invention et obtenus à partir des formulations 4 et 5 (courbes respectivement notées 4 et 5) et le troisième étant un matériau composite comparatif obtenu à partir de la formulation C (courbe notée C). FIG. 2 represents curves translating the evolution of the loss of mass (noted A m and expressed in%) as a function of the aging time (noted t and expressed in h) of three composite materials placed in an environment at 180 ° C. , two being composite materials in accordance with the invention and obtained from formulations 4 and 5 (curves respectively denoted 4 and 5) and the third being a comparative composite material obtained from formulation C (curve denoted C).
La figure 3 représente des courbes traduisant l'évolution de la perte de masse (notée Am et exprimée en %) en fonction du temps de vieillissement (noté t et exprimé en h) de deux matériaux composites conformes à l'invention, obtenus à partir des formulations 1 et 5 et placés dans un environnement à 180 °C (courbes respectivement notées 1 et 5). FIG. 3 represents curves showing the evolution of the mass loss (denoted A m and expressed in%) as a function of the aging time (denoted t and expressed in h) of two composite materials in accordance with the invention, obtained at starting from formulations 1 and 5 and placed in an environment at 180 ° C (curves respectively noted 1 and 5).
EXPOSÉ DÉTAILLÉ DE MODES DE RÉALISATION PARTICULIERS DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
1. Obtention des matériaux selon l'invention et du matériau comparatif 1. Obtaining the materials according to the invention and the comparative material
1.1. Composés mis en œuvre 1.1. Compounds used
Les composés utilisés pour la préparation des compositions (méth)acryliques, notées A et A', mises en œuvre pour l'obtention des matériaux composites selon l'invention sont les suivants : - comme polymère (méth)acrylique PI : un PMMA formé par un copolymère de méthacrylate de méthyle et d'acrylate d'éthyle commercialisé par la Société Altuglas sous la dénomination Altuglas® BS 520, The compounds used for the preparation of the (meth) acrylic compositions, denoted A and A ′, used for obtaining the composite materials according to the invention are the following: as a (meth) acrylic polymer PI: a PMMA formed by a copolymer of methyl methacrylate and ethyl acrylate sold by the Altuglas Company under the name Altuglas ® BS 520,
- comme monomère (méth)acrylique Ml : un méthacrylate de méthyle stabilisé par de l'hydroquinone de monométhyléther (MEHQ.),  - as (meth) acrylic monomer M1: a methyl methacrylate stabilized by hydroquinone of monomethyl ether (MEHQ.),
- comme monomère (méth)acrylique M2 : un diméthacrylate de 1,4-butanediol commercialisé par la Société Sartomer sous la dénomination SR214,  as M2 (meth) acrylic monomer: a 1,4-butanediol dimethacrylate sold by the company Sartomer under the name SR214,
- comme monomère (méth)acrylique M3 : un acide méthacrylique,  - as (meth) acrylic monomer M3: a methacrylic acid,
- comme composé métallique : un complexe de fer commercialisé par la Société Akzo Nobel sous la dénomination Nouryact® CF40, - as a metallic compound: an iron complex sold by the Akzo Nobel Company under the name Nouryact ® CF40,
- comme agent réducteur : une saccharine,  - as reducing agent: a saccharin,
- comme amine tertiaire : une L/,/V-dihydroxyéthyl-p-toluidine (DHEPT),  - as tertiary amine: an L /, / V-dihydroxyethyl-p-toluidine (DHEPT),
- comme initiateur de polymérisation : un peroxyde de méthyléthylcétone commercialisé par la Société Akzo Nobel sous la dénomination Butanox®M-50,- as a polymerization initiator: a methyl ethyl ketone peroxide sold by Akzo Nobel under the name Butanox ® M-50,
- comme agent de transfert : un terpinolène commercialisé par la Société DRT sous la dénomination Terpinolène 95, as transfer agent: a terpinolene sold by the company DRT under the name Terpinolene 95,
- comme antioxydant : un bis[3-(3,5-di-te/t-butyl-4-hydroxyphényl)proprionate] de thiodiéthylène commercialisé par la Société BASF sous la dénomination lrganox®1035, - as an antioxidant: bis [3- (3,5-di-te / t-butyl-4-hydroxyphenyl) proprionate] thiodiethylene marketed by BASF under the name Irganox ® 1035,
- comme agent piégeur de radicaux libres : un 4-hydroxy-2,2,6,6-tétra méthylpipéridine-/V-oxyle commercialisé par la Société 3V Sigma sous la dénomination Tempoxy LO,  as a free radical scavenger: a 4-hydroxy-2,2,6,6-tetra methylpiperidine- / V-oxyl sold by the company 3V Sigma under the name Tempoxy LO,
- comme stabilisant thermique : un poly-te/t-amylphénoldisulfure commercialisé par la Société Arkema sous la dénomination Vultac-3®, et - as thermal stabilizer: a poly-te / t-amylphenoldisulfide marketed by the company Arkema under the name Vultac-3 ® , and
- comme stabilisant à la lumière : un sébacate de £>/'s(2,2,6,6-tétraméthyl-4- pipéridyle commercialisé par la Société BASF sous la dénomination Tinuvin®770. - as light stabilizer: a £ sebacate> / 's (2,2,6,6-tetramethyl-4- piperidyl marketed by BASF under the name Tinuvin 770 ®.
Les composés utilisés pour la préparation de la composition thermodurcissable, notée composition C, mise en œuvre pour l'obtention du matériau composite comparatif sont les suivants : - comme résine vinylester : une résine époxy vinylester commercialisée par la Société Ashland sous la dénomination Derakane™ Momentum 470-300, The compounds used for the preparation of the thermosetting composition, denoted composition C, used to obtain the comparative composite material are the following: - as vinylester resin: a vinylester epoxy resin sold by the Ashland Company under the name Derakane ™ Momentum 470-300,
- comme catalyseur : un peroxyde de méthyléthylcétone commercialisé par la Société Akzo Nobel sous la dénomination Butanox®M-50, et - as a catalyst: a methyl ethyl ketone peroxide sold by Akzo Nobel under the name Butanox ® M-50, and
- comme accélérateur de durcissement : un mélange de 2-éthylhexanoate de cobalt(ll) et de carboxylate de baryum commercialisé par la Société Akzo Nobel sous la dénomination Accelerator 55028.  - As hardening accelerator: a mixture of cobalt (ll) 2-ethylhexanoate and barium carboxylate sold by the company Akzo Nobel under the name Accelerator 55028.
Les charges mises en œuvre pour la préparation des différentes formulations permettant d'obtenir les matériaux selon l'invention et le matériau comparatif sont les suivantes :  The charges used for the preparation of the various formulations making it possible to obtain the materials according to the invention and the comparative material are the following:
- comme charge hydrogénée :  - as hydrogenated charge:
. un hydrate d'alumine AI(OH)3, noté ATH, commercialisé par la société Nabaltec sous la dénomination Apyral®20X, . an alumina hydrate AI (OH) 3, denoted ATH sold by Nabaltec under the name ® Apyral 20X,
. un polyéthylène commercialisé par la société Celanese sous la dénomination GUR®4050-3 . a polyethylene marketed by Celanese under the name GUR ® 4050-3
- comme charge borée :  - as boron charge:
. un borate de zinc 4ZhO,6B2q3,7H20 fabriqué par la société Borax et commercialisé par la société Univar sous la dénomination Firebrake®ZB. a zinc borate 4ZhO, 6B 2 q 3 , 7H 2 0 manufactured by the company Borax and marketed by the company Univar under the name Firebrake ® ZB
1.2. Préparation des formulations 1.2. Preparation of formulations
1.2.1. Préparation des formulations selon l'invention 1.2.1. Preparation of the formulations according to the invention
Dans une première étape, on prépare un sirop (méth)acrylique liquide par dissolution de 25 parties en poids du polymère (méth)acrylique PI dans 75 parties en poids du monomère (méth)acrylique Ml.  In a first step, a liquid (meth) acrylic syrup is prepared by dissolving 25 parts by weight of the (meth) acrylic polymer PI in 75 parts by weight of the (meth) acrylic monomer Ml.
Dans une deuxième étape, on ajoute aux 100 parties en poids de sirop (méth)acrylique liquide, 5 parties en poids de monomère (méth)acrylique M2, pour l'obtention de la composition (méth)acrylique, notée composition A.  In a second step, 5 parts by weight of (meth) acrylic monomer M2 are added to the 100 parts by weight of liquid (meth) acrylic syrup, to obtain the (meth) acrylic composition, denoted composition A.
Une composition (méth)acrylique stabilisée, notée A', est formée par la composition (méth)acrylique A ci-dessus à laquelle sont ajoutés :  A stabilized (meth) acrylic composition, denoted A ′, is formed by the above (meth) acrylic composition A to which are added:
5 parties en poids de monomère méthacrylique M3,  5 parts by weight of methacrylic monomer M3,
1 partie en poids de composé métallique (Nouryact® CF40), 0,3 parties en poids d'agent réducteur (saccharine), 1 part by weight of metallic compound (Nouryact ® CF40), 0.3 parts by weight of reducing agent (saccharin),
4000 ppm d'amine tertiaire (DHEPT),  4000 ppm tertiary amine (DHEPT),
1500 ppm d'agent de transfert (terpinolène),  1500 ppm of transfer agent (terpinolene),
1000 ppm d'antioxydant (lrganox®1035), 1000 ppm of antioxidant (lrganox ® 1035),
200 ppm de piégeur de radicaux libres (Tempoxy LO),  200 ppm of free radical scavenger (Tempoxy LO),
1000 ppm de stabilisant thermique (Vultac-3®), et 1000 ppm of thermal stabilizer (Vultac-3 ® ), and
1000 ppm de stabilisant à la lumière (Tinuvin®770). 1000 ppm light stabilizer (Tinuvin ® 770).
Dans une troisième étape, on introduit à la composition (méth)acrylique A ou A' telle qu'obtenue, une ou plusieurs charges, dans les proportions pondérales telles qu'indiquées dans le Tableau 1 ci-dessous, puis, en dernier lieu, 0,75 partie en poids de l'initiateur de polymérisation (Butanox®M-50) et on procède au malaxage de l'ensemble des composés de manière à obtenir des formulations, notées 1 à 5, parfaitement homogènes. In a third step, one or more fillers are introduced into the (meth) acrylic composition A or A ′ as obtained, in the weight proportions as indicated in Table 1 below, then, lastly, 0.75 part by weight of the polymerization initiator (Butanox ® M-50) and one proceeds to mixing of all compounds to obtain formulations, denoted 1 to 5, perfectly homogeneous.
Les différentes formulations 1 à 5 ainsi préparées sont dégazées sous vide (pression inférieure à 0,01 MPa) puis coulées, à la température ambiante (21 °C), dans un moule. The different formulations 1 to 5 thus prepared are degassed under vacuum (pressure less than 0.01 MPa) and then poured, at room temperature (21 ° C), into a mold.
On observe une bonne coulabilité de la matière dans le moule pour l'ensemble des formulations 1 à 5.  Good flowability of the material in the mold is observed for all of the formulations 1 to 5.
1.2.2. Préparation de la formulation thermodurcissable comparative 1.2.2. Preparation of the comparative thermosetting formulation
On prépare une composition thermodurcissable, notée composition c, conforme à l'exemple 2 du document [1].  A thermosetting composition, denoted composition c, is prepared in accordance with Example 2 of document [1].
On procède au malaxage de l'ensemble des composés de manière à obtenir une formulation thermodurcissable parfaitement homogène.  The mixing of all the compounds is carried out so as to obtain a perfectly homogeneous thermosetting formulation.
La formulation thermodurcissable, notée C, ainsi préparée est dégazée sous vide (pression inférieure à 0,01 MPa) puis coulée, à la température ambiante (21 °C), dans un moule.
Figure imgf000024_0001
The thermosetting formulation, denoted C, thus prepared is degassed under vacuum (pressure less than 0.01 MPa) then poured, at room temperature (21 ° C), into a mold.
Figure imgf000024_0001
Tableau 1  Table 1
1.3. Obtention des matériaux composites 1.3. Obtaining composite materials
1.3.1. Obtention et caractérisation des matériaux composites selon l'invention  1.3.1. Obtaining and characterizing the composite materials according to the invention
La polymérisation de chacune des formulations 1 à 5 est réalisée à la température ambiante (21 °C).  The polymerization of each of formulations 1 to 5 is carried out at room temperature (21 ° C).
La qualité des matériaux composites obtenus à partir de chacune de ces formulations 1 à 5 est confirmée. L'examen de tronçons réalisés dans les échantillons de matériaux composites obtenus à partir des formulations 1 à 5 n'a révélé aucun défaut visible (fissure) à l'œil nu.  The quality of the composite materials obtained from each of these formulations 1 to 5 is confirmed. Examination of sections made in the samples of composite materials obtained from formulations 1 to 5 did not reveal any visible defect (crack) with the naked eye.
Un test d'usinabilité a également été conduit de manière positive sur chacun de ces matériaux composites.  A machinability test was also conducted positively on each of these composite materials.
1.3.2. Obtention du matériau composite comparatif 1.3.2. Obtaining the comparative composite material
La polymérisation de la formulation thermodurcissable C est réalisée à la température ambiante (21 °C) 2. Évaluation des propriétés des matériaux composites The polymerization of thermosetting formulation C is carried out at room temperature (21 ° C) 2. Assessment of the properties of composite materials
La tenue au vieillissement thermique d'un matériau composite peut s'apprécier par des essais qui consistent à mesurer ses caractéristiques, notamment la perte de masse, lorsqu'il est maintenu à différentes températures pendant une période de temps définie, et à déterminer à partir des résultats obtenus la température maximale pour laquelle la perte de masse du matériau composite est acceptable pour la durée d'utilisation envisagée de l'emballage.  The resistance to thermal aging of a composite material can be assessed by tests which consist in measuring its characteristics, in particular the loss of mass, when it is maintained at different temperatures for a defined period of time, and to determine from of the results obtained the maximum temperature for which the loss of mass of the composite material is acceptable for the period of intended use of the packaging.
Les composés de bore étant stables en température, on s'intéressera plus particulièrement à la perte de masse en hydrogène dont la sensibilité aux températures élevées est plus marquée, sachant que les teneurs en bore et en hydrogène sont les éléments essentiels à prendre en compte pour apprécier les performances d'un tel matériau composite vis-à-vis des fonctions de blindage neutronique et de maintien de la sous-criticité, et ce pendant toute la durée d'utilisation de l'emballage.  Boron compounds being stable in temperature, we will focus more particularly on the loss of mass of hydrogen whose sensitivity to high temperatures is more marked, knowing that the boron and hydrogen contents are the essential elements to be taken into account for assess the performance of such a composite material with respect to the functions of neutron shielding and of maintaining the subcriticality, and this throughout the duration of use of the packaging.
* Une première série de tests de vieillissement thermique a été conduite, à 160 °C, sur les matériaux composites obtenus à partir des formulations 1 et C.  * A first series of thermal aging tests was conducted, at 160 ° C, on the composite materials obtained from formulations 1 and C.
Les résultats de ces tests de vieillissement sont reportés sur la figure 1. The results of these aging tests are shown in Figure 1.
Comme il ressort de cette figure 1, le matériau composite selon l'invention (obtenu à partir de la formulation 1), présente une perte de masse bien inférieure à 10 % et comparable, bien que très légèrement supérieure, à celle du matériau composite comparatif. As can be seen from this FIG. 1, the composite material according to the invention (obtained from formulation 1) has a loss of mass well below 10% and comparable, although very slightly greater, than that of the comparative composite material .
Même si la perte de masse du matériau composite selon l'invention est très légèrement supérieure à celle du matériau composite comparatif, la perte d'hydrogène est en revanche nettement inférieure, comme le montrent les données figurant dans le Tableau 2 ci-dessous.  Even if the loss of mass of the composite material according to the invention is very slightly greater than that of the comparative composite material, the loss of hydrogen is, on the other hand, significantly lower, as shown by the data appearing in Table 2 below.
Pour déterminer cette perte d'hydrogène (en %), on procède à une analyse comparative de l'hydrogène contenu dans des échantillons vieillis des différents matériaux composites par rapport à l'hydrogène contenu dans des échantillons neufs de ces mêmes matériaux avant vieillissement. Pour ce faire, chaque échantillon, vieilli ou neuf, est broyé puis ensuite transformé par combustion sous oxygène à une température d'environ 1050 °C. L'hydrogène est alors quantifié par spectrométrie infrarouge. To determine this loss of hydrogen (in%), a comparative analysis is carried out of the hydrogen contained in aged samples of the different composite materials compared to the hydrogen contained in new samples of these same materials before aging. To do this, each sample, aged or new, is ground and then transformed by combustion under oxygen at a temperature of around 1050 ° C. The hydrogen is then quantified by infrared spectrometry.
Figure imgf000026_0001
Figure imgf000026_0001
Tableau 2 Le matériau composite selon l'invention, qui se caractérise par une perte d'hydrogène bien inférieure à celle du matériau composite comparatif, présente donc de meilleures performances en termes d'efficacité neutronique pour un emballage le comprenant.  Table 2 The composite material according to the invention, which is characterized by a loss of hydrogen much lower than that of the comparative composite material, therefore exhibits better performance in terms of neutron efficiency for a package comprising it.
* Une deuxième série de tests de vieillissement thermique a également été conduite, à 180 °C, sur les matériaux composites obtenus à partir des formulations 1, 4, 5 et C.  * A second series of thermal aging tests was also conducted, at 180 ° C, on the composite materials obtained from formulations 1, 4, 5 and C.
Les résultats de ces tests de vieillissement sont reportés sur les figures 2 et 3.  The results of these aging tests are reported in Figures 2 and 3.
Comme il ressort de la figure 2, les matériaux composites selon l'invention (obtenus à partir des formulations 4 et 5) présentent une perte de masse inférieure à 10 %. Même si la perte de masse de ces matériaux composites selon l'invention est légèrement supérieure à celle du matériau composite comparatif obtenu à partir de la formulation C, la perte d'hydrogène est en revanche très nettement inférieure. En effet, au bout de 2000 h de temps de vieillissement, on estime la perte d'hydrogène à moins de 4 % pour les matériaux composites obtenus à partir des formulations 4 et 5 alors qu'elle est supérieure à 9 % pour celui obtenu à partir de la formulation C.  As can be seen from FIG. 2, the composite materials according to the invention (obtained from formulations 4 and 5) have a loss of mass of less than 10%. Even if the loss in mass of these composite materials according to the invention is slightly greater than that of the comparative composite material obtained from formulation C, the loss of hydrogen is however very much lower. Indeed, after 2000 h of aging time, the loss of hydrogen is estimated to be less than 4% for the composite materials obtained from formulations 4 and 5 whereas it is greater than 9% for that obtained at from formulation C.
Les résultats des tests de vieillissement réalisés à 180 °C sur les matériaux obtenus à partir des formulations 1 et 5 sont reportés sur la figure 3. Comme il ressort de la figure 3, le matériau composite selon l'invention obtenu à partir de la formulation 5 présente une perte de masse, à 180 °C, inférieure à celle du matériau composite selon l'invention obtenu à partir de la formulation 1. Cette différence est directement liée à la composition (méth)acrylique de la formulation qui, dans le cas de la formulation 5, est stabilisée, ce qui n'est pas le cas de la composition (méth)acrylique de la formulation 1. The results of the aging tests carried out at 180 ° C. on the materials obtained from formulations 1 and 5 are shown in FIG. 3. As can be seen from FIG. 3, the composite material according to the invention obtained from formulation 5 has a loss in mass, at 180 ° C., less than that of the composite material according to the invention obtained from formulation 1 This difference is directly linked to the (meth) acrylic composition of the formulation which, in the case of formulation 5, is stabilized, which is not the case of the (meth) acrylic composition of formulation 1.
Ainsi, pour des applications requérant une tenue thermique à des valeurs de températures de 180 °C, on préférera mettre en œuvre une formulation comprenant une composition (méth)acrylique stabilisée.  Thus, for applications requiring thermal resistance at temperature values of 180 ° C., it is preferable to use a formulation comprising a stabilized (meth) acrylic composition.
BIBLIOGRAPHIE BIBLIOGRAPHY
[1] US 7,160,486 B2  [1] US 7,160,486 B2

Claims

REVENDICATIONS
1. Matériau composite de blindage neutronique et de maintien de la sous-criticité obtenu à partir d'une formulation comprenant : 1. Composite material for neutron shielding and for maintaining the subcriticality obtained from a formulation comprising:
(A) de 20 % en poids à 65 % en poids, avantageusement de 25 % en poids à 60 % en poids, d'une composition (méth)acrylique comprenant :  (A) from 20% by weight to 65% by weight, advantageously from 25% by weight to 60% by weight, of a (meth) acrylic composition comprising:
(a) 100 parties en poids d'un sirop (méth)acrylique liquide comprenant :  (a) 100 parts by weight of a liquid (meth) acrylic syrup comprising:
(ai) de 10 % en poids à 50 % en poids d'un polymère (méth)acrylique PI, et (a2) de 50 % en poids à 90 % en poids d'un monomère (méth)acrylique Ml ne comprenant qu'une fonction (méth)acrylique, (ai) from 10% by weight to 50% by weight of a (meth) acrylic polymer PI, and (a 2 ) from 50% by weight to 90% by weight of a (meth) acrylic monomer Ml comprising only 'a (meth) acrylic function,
(b) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids d'un monomère (méth)acrylique M2 comprenant au moins deux fonctions (méth)acryliques,  (b) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 parts by weight to 10 parts by weight of a (meth) acrylic monomer M2 comprising at least two (meth) acrylic functions,
(c) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un monomère (méth)acrylique M3 ne comprenant qu'une fonction (méth)acrylique, le monomère M3 étant différent du monomère (méth)acrylique Ml,  (c) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of a (meth) acrylic monomer M3 comprising only one (meth) acrylic function, the monomer M3 being different from the (meth) acrylic monomer Ml,
(d) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un composé métallique,  (d) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of a metallic compound,
(e) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un agent réducteur,  (e) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 parts by weight to 10 parts by weight, of a reducing agent,
(f) de 0 ppm à 20 000 ppm, avantageusement de 1 000 ppm à 10 000 ppm, d'une amine tertiaire,  (f) from 0 ppm to 20,000 ppm, advantageously from 1,000 ppm to 10,000 ppm, of a tertiary amine,
(g) de 0,1 partie en poids à 5 parties en poids d'un initiateur de polymérisation,  (g) from 0.1 part by weight to 5 parts by weight of a polymerization initiator,
(h) de 0 ppm à 10 000 ppm d'un agent de transfert,  (h) from 0 ppm to 10,000 ppm of a transfer agent,
(i) de 0 ppm à 10 000 ppm d'un antioxydant,  (i) from 0 ppm to 10,000 ppm of an antioxidant,
(j) de 0 ppm à 1 000 ppm d'un agent piégeur de radicaux libres,  (j) from 0 ppm to 1000 ppm of a free radical scavenger,
(k) de 0 ppm à 10 000 ppm d'un stabilisant thermique, et (I) de 0 ppm à 10 000 ppm d'un stabilisant à la lumière ; et (k) from 0 ppm to 10,000 ppm of a thermal stabilizer, and (I) from 0 ppm to 10,000 ppm of a light stabilizer; and
(B) de 35 % en poids à 80 % en poids, avantageusement de 40 % en poids à 75 % en poids, d'une ou plusieurs charges, la ou les charges comprenant :  (B) from 35% by weight to 80% by weight, advantageously from 40% by weight to 75% by weight, of one or more fillers, the charge or fillers comprising:
. au moins un composé du bore, et  . at least one boron compound, and
. au moins un composé hydrogéné.  . at least one hydrogenated compound.
2. Matériau composite selon la revendication 1, dans lequel le polymère (méth)acrylique PI est choisi parmi les polyméthacrylates d'alkyle et les polyacrylates d'alkyle et est, avantageusement, un homopolymère de méthacrylate de méthyle, un copolymère de méthacrylate de méthyle ou un de leurs mélanges. 2. Composite material according to claim 1, in which the (meth) acrylic polymer PI is chosen from alkyl polymethacrylates and alkyl polyacrylates and is advantageously a homopolymer of methyl methacrylate, a copolymer of methyl methacrylate or one of their mixtures.
3. Matériau composite selon la revendication 1 ou 2, dans lequel le monomère (méth)acrylique Ml est choisi parmi les monomères acryliques d'alkyle, les monomères méthacryliques d'alkyle, les monomères acryliques d'hydroxyalkyle, les monomères méthacryliques d'hydroxyalkyle et leurs mélanges, le groupe alkyle de ces monomères (méth)acryliques pouvant être linéaire, ramifié ou cyclique, et contenir de 1 à 22 atomes de carbone, de préférence de 1 à 12 atomes de carbone. 3. Composite material according to claim 1 or 2, in which the (meth) acrylic monomer M1 is chosen from acrylic alkyl monomers, methacrylic alkyl monomers, acrylic hydroxyalkyl monomers, methacrylic hydroxyalkyl monomers and their mixtures, the alkyl group of these (meth) acrylic monomers possibly being linear, branched or cyclic, and containing from 1 to 22 carbon atoms, preferably from 1 to 12 carbon atoms.
4. Matériau composite selon la revendication 3, dans lequel le méthacrylate de méthyle représente au moins 50 % en poids, avantageusement au moins 60 % en poids, de préférence au moins 70 % en poids, plus préférentiellement au moins 80 % en poids et, plus préférentiellement encore, au moins 90 % en poids du monomère (méth)acrylique Ml. 4. Composite material according to claim 3, in which the methyl methacrylate represents at least 50% by weight, advantageously at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight and, more preferably still, at least 90% by weight of the (meth) acrylic monomer Ml.
5. Matériau composite selon l'une quelconque des revendications 1 à 4, dans lequel le monomère (méth)acrylique M2 est choisi parmi le diméthacrylate d'éthylène glycol, le diacrylate de néopentyle glycol, le diméthacrylate de néopentyle glycol, le diméthacrylate de 1,4-butanediol, le diacrylate de 1,4-butanediol, le diacrylate de 1,3-butylène glycol, le diméthacrylate de 1,3-butylène glycol, le diméthacrylate de triéthylène glycol, le diacrylate de triéthylène glycol et leurs mélanges. 5. Composite material according to any one of claims 1 to 4, in which the (meth) acrylic monomer M2 is chosen from ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, dimethacrylate 1 , 4-butanediol, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate and mixtures thereof.
6. Matériau composite selon l'une quelconque des revendications 1 à 5, dans lequel le monomère (méth)acrylique M3 est l'acide méthacrylique. 6. Composite material according to any one of claims 1 to 5, in which the (meth) acrylic monomer M3 is methacrylic acid.
7. Matériau composite selon l'une quelconque des revendications 1 à 6, dans lequel le composé métallique comprend un ou plusieurs métaux de transition choisis parmi les métaux de transition de la quatrième période du tableau périodique des éléments, de préférence choisis parmi le fer, le cuivre et le manganèse. 7. Composite material according to any one of claims 1 to 6, in which the metallic compound comprises one or more transition metals chosen from the transition metals of the fourth period of the periodic table of the elements, preferably chosen from iron, copper and manganese.
8. Matériau composite selon l'une quelconque des revendications 1 à 7, dans lequel l'agent réducteur est choisi parmi l'acide ascorbique, la saccharine, les a- hydroxysulfones, les thio-urées et leurs mélanges. 8. Composite material according to any one of claims 1 to 7, in which the reducing agent is chosen from ascorbic acid, saccharin, α-hydroxysulfones, thioureas and their mixtures.
9. Matériau composite selon l'une quelconque des revendications 1 à 8, dans lequel l'initiateur de polymérisation est un peroxyde qui est liquide à une température comprise entre 0° C et 50 °C, avantageusement un peroxyde organique comprenant de 2 à 30 atomes de carbone et, préférentiellement, un hydroperoxyde choisi parmi l'hydroperoxyde de te/t-butyle, le monohydroperoxyde, l'hydroperoxyde de para-méthane, l'hydroperoxyde de te/t-amyle et l'hydroperoxyde de cumène. 9. Composite material according to any one of claims 1 to 8, in which the polymerization initiator is a peroxide which is liquid at a temperature between 0 ° C and 50 ° C, advantageously an organic peroxide comprising from 2 to 30 carbon atoms and, preferably, a hydroperoxide chosen from te / t-butyl hydroperoxide, monohydroperoxide, para-methane hydroperoxide, te / t-amyl hydroperoxide and cumene hydroperoxide.
10. Matériau composite selon l'une quelconque des revendications 1 à 9, dans lequel la formulation comprend : 10. Composite material according to any one of claims 1 to 9, in which the formulation comprises:
. de 2 % en poids à 45 % en poids de composé(s) de bore, et  . from 2% by weight to 45% by weight of boron compound (s), and
. de 30 % en poids à 73 % en poids de composé(s) hydrogéné(s),  . from 30% by weight to 73% by weight of hydrogenated compound (s),
11. Matériau composite selon l'une quelconque des revendications 1 à 10, dans lequel 11. Composite material according to any one of claims 1 to 10, in which
le ou les composés du bore sont choisis parmi H3BO3, Ca20i4B6Hio, les borates de zinc, B4C, BN et B2O3, et/ou - le ou les composés hydrogénés sont choisis parmi les hydroxydes, par exemple AI(OH)3 et Mg(OH)2, et les polyoléfines, par exemple le polyéthylène. the boron compound (s) are chosen from H3BO3, Ca 2 0i 4 B 6 Hio, zinc borates, B 4 C, BN and B2O3, and / or - The hydrogenated compound (s) are chosen from hydroxides, for example AI (OH) 3 and Mg (OH) 2 , and polyolefins, for example polyethylene.
12. Matériau composite selon l'une quelconque des revendications 1 à 11, dans lequel le ou les composés du bore comprennent de l'hydrogène et sont avantageusement choisis parmi les borates de zinc hydratés tels que 4Zn0,6B203,7H20 ou 4ZnO,B2Û3, H20. 12. Composite material according to any one of claims 1 to 11, in which the boron compound (s) comprise hydrogen and are advantageously chosen from hydrated zinc borates such as 4Zn0.6B 2 0 3 , 7H 2 0 or 4ZnO, B 2Û3 , H 2 0.
13. Procédé de fabrication d'un matériau composite de blindage neutronique et de maintien de la sous-criticité selon l'une quelconque des revendications 1 à 12, ce procédé comprenant les étapes successives suivantes : 13. A method of manufacturing a composite neutron shielding material and of maintaining the subcriticality according to any one of claims 1 to 12, this method comprising the following successive steps:
(1) le mélange des composés suivants :  (1) the mixture of the following compounds:
(A) de 20 % en poids à 65 % en poids, avantageusement de 25% en poids à 60% en poids, d'une composition (méth)acrylique comprenant :  (A) from 20% by weight to 65% by weight, advantageously from 25% by weight to 60% by weight, of a (meth) acrylic composition comprising:
(a) 100 parties en poids d'un sirop (méth)acrylique liquide comprenant :  (a) 100 parts by weight of a liquid (meth) acrylic syrup comprising:
(ai) de 10 % en poids à 50 % en poids d'un polymère (méth)acrylique PI, et (a2) de 50 % en poids à 90 % en poids d'un monomère (méth)acrylique Ml ne comprenant qu'une fonction (méth)acrylique, (ai) from 10% by weight to 50% by weight of a (meth) acrylic polymer PI, and (a 2 ) from 50% by weight to 90% by weight of a (meth) acrylic monomer Ml comprising only 'a (meth) acrylic function,
(b) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids d'un monomère (méth)acrylique M2 comprenant au moins deux fonctions (méth)acryliques,  (b) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 parts by weight to 10 parts by weight of a (meth) acrylic monomer M2 comprising at least two (meth) acrylic functions,
(c) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un monomère (méth)acrylique M3 ne comprenant qu'une fonction (méth)acrylique, le monomère M3 étant différent du monomère (méth)acrylique Ml,  (c) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of a (meth) acrylic monomer M3 comprising only one (meth) acrylic function, the monomer M3 being different from the (meth) acrylic monomer Ml,
(d) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un composé métallique,  (d) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 part by weight to 10 parts by weight, of a metallic compound,
(e) de 0 partie en poids à 10 parties en poids, avantageusement de 0,01 partie en poids à 10 parties en poids, d'un agent réducteur, (f) de 0 ppm à 20 000 ppm, avantageusement de 1 000 ppm à 10 000 ppm, d'une amine tertiaire, (e) from 0 parts by weight to 10 parts by weight, advantageously from 0.01 parts by weight to 10 parts by weight, of a reducing agent, (f) from 0 ppm to 20,000 ppm, advantageously from 1,000 ppm to 10,000 ppm, of a tertiary amine,
(g) de 0,1 partie en poids à 5 parties en poids d'un initiateur de polymérisation,  (g) from 0.1 part by weight to 5 parts by weight of a polymerization initiator,
(h) de 0 ppm à 10 000 ppm d'un agent de transfert,  (h) from 0 ppm to 10,000 ppm of a transfer agent,
(i) de 0 ppm à 10 000 ppm d'un antioxydant,  (i) from 0 ppm to 10,000 ppm of an antioxidant,
(j) de 0 ppm à 1 000 ppm d'un agent piégeur de radicaux libres,  (j) from 0 ppm to 1000 ppm of a free radical scavenger,
(k) de 0 ppm à 10 000 ppm d'un stabilisant thermique, et  (k) from 0 ppm to 10,000 ppm of a thermal stabilizer, and
(L) de 0 ppm à 10 000 ppm d'un stabilisant à la lumière ; et  (L) from 0 ppm to 10,000 ppm of a light stabilizer; and
(B) de 35 % en poids à 80 % en poids, avantageusement de 40 % en poids à 75 % en poids, d'une ou plusieurs charges, la ou les charges comprenant :  (B) from 35% by weight to 80% by weight, advantageously from 40% by weight to 75% by weight, of one or more fillers, the charge or fillers comprising:
. au moins un composé de bore, et  . at least one boron compound, and
. au moins un composé hydrogéné.  . at least one hydrogenated compound.
le sirop (méth)acrylique liquide étant préparé en premier et l'initiateur de polymérisation étant introduit en dernier dans la formulation, et the liquid (meth) acrylic syrup being prepared first and the polymerization initiator being introduced last into the formulation, and
(2) le moulage à la température ambiante de la formulation obtenue à l'étape (1).  (2) molding at room temperature the formulation obtained in step (1).
14. Utilisation d'un matériau composite de blindage neutronique et de maintien de la sous-criticité selon l'une quelconque des revendications 1 à 12 pour la fabrication d'une pièce d'un emballage destiné à l'entreposage, le stockage et/ou le transport de matière radioactive. 14. Use of a composite material for neutron shielding and for maintaining the subcriticality according to any one of claims 1 to 12 for the manufacture of a part of a packaging intended for warehousing, storage and / or the transport of radioactive material.
15. Emballage d'entreposage, de stockage et/ou de transport de matière radioactive comprenant un matériau composite de blindage neutronique et de maintien de la sous-criticité selon l'une quelconque des revendications 1 à 12. 15. Packaging for storing, storing and / or transporting radioactive material comprising a composite material for neutron shielding and for maintaining sub-criticality according to any one of claims 1 to 12.
PCT/FR2019/052409 2018-10-15 2019-10-10 Composite material for neutron shielding and for maintaining subcriticality, the manufacturing process and uses thereof WO2020079352A1 (en)

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FR1859522A FR3087293B1 (en) 2018-10-15 2018-10-15 COMPOSITE MATERIAL FOR NEUTRONIC SHIELDING AND SUB-CRITICALITY MAINTAINING, ITS MANUFACTURING PROCESS AND ITS USES
FR1859522 2018-10-15

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CN111732775A (en) * 2020-07-02 2020-10-02 北京科技大学 Polymer composite material for space neutron shielding and preparation method thereof
CN112745550A (en) * 2020-12-18 2021-05-04 北京科技大学 Neutron-shielding polymer composite material, preparation method, wire and application
WO2022258927A1 (en) * 2021-06-10 2022-12-15 Orano Nuclear Packages And Services Composite material for neutron shielding and for maintaining subcriticality, method for manufacturing same and uses thereof

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US7160486B2 (en) 2001-12-12 2007-01-09 Cogema Logistics Material based on vinylester resin for neutron shielding and maintenance of sub-criticality
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US7160486B2 (en) 2001-12-12 2007-01-09 Cogema Logistics Material based on vinylester resin for neutron shielding and maintenance of sub-criticality
EP1418593A1 (en) * 2002-10-25 2004-05-12 Cogema Logistics Neutron shielding material for subcritical maintenance and its production and applications
FR3030547A1 (en) * 2014-12-22 2016-06-24 Arkema France LIQUID (METH) ACRYLIC SYRUP, PROCESS FOR THE IMPREGNATION OF A FIBROUS SUBSTRATE BY THE SAME, AND COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF THE IMPREGNATION SYRUP

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CN111732775A (en) * 2020-07-02 2020-10-02 北京科技大学 Polymer composite material for space neutron shielding and preparation method thereof
CN112745550A (en) * 2020-12-18 2021-05-04 北京科技大学 Neutron-shielding polymer composite material, preparation method, wire and application
WO2022258927A1 (en) * 2021-06-10 2022-12-15 Orano Nuclear Packages And Services Composite material for neutron shielding and for maintaining subcriticality, method for manufacturing same and uses thereof
FR3124018A1 (en) * 2021-06-10 2022-12-16 Orano Nuclear Packages And Services Composite material for neutron shielding and maintaining subcriticality, process for its manufacture and uses thereof

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