EP1454327A2 - Werkstoff auf basis von vinylesterharz zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität - Google Patents

Werkstoff auf basis von vinylesterharz zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität

Info

Publication number
EP1454327A2
EP1454327A2 EP02804603A EP02804603A EP1454327A2 EP 1454327 A2 EP1454327 A2 EP 1454327A2 EP 02804603 A EP02804603 A EP 02804603A EP 02804603 A EP02804603 A EP 02804603A EP 1454327 A2 EP1454327 A2 EP 1454327A2
Authority
EP
European Patent Office
Prior art keywords
material according
resin
boron
inorganic
resins
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02804603A
Other languages
English (en)
French (fr)
Other versions
EP1454327B1 (de
Inventor
Martine Valiere
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TN International SA
Original Assignee
Cogema Logistics SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cogema Logistics SA filed Critical Cogema Logistics SA
Publication of EP1454327A2 publication Critical patent/EP1454327A2/de
Application granted granted Critical
Publication of EP1454327B1 publication Critical patent/EP1454327B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F1/00—Shielding characterised by the composition of the materials
    • G21F1/02—Selection of uniform shielding materials
    • G21F1/10—Organic substances; Dispersions in organic carriers
    • 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

Definitions

  • the present invention relates to a neutron shielding material and for maintaining the subcriticality.
  • a neutron shielding material are useful in nuclear energy to protect operators from neutron radiation emitted by radioactive products and to prevent the runaway reaction of the neutron formation chain, more particularly when these products contain fissile materials. They can be used in particular as a neutron screen in transport and / or storage packaging for radioactive products, for example nuclear fuel assemblies.
  • thermosetting resin can be an unsaturated polyester resin and the inorganic fillers can be heavy metals or compounds thereof.
  • GB-A-1 049 890 [2] describes molded articles or neutron absorbing coatings comprising at least 0.3% by weight of boron obtained from a copolymerizable mixture of an unsaturated polyester and a an unsaturated monomer in which either the acid component of the polyester is derived in part from boric acid, or the polymerizable monomer is in part an ester of boric acid.
  • Document JP-A-55 119099 [3] describes materials for protection against neutrons also based on unsaturated polyester resin. Such a material has a density of hydrogen atoms of 6.1 ⁇ 10 22 hydrogen atoms per cm 3 , but it does not contain a neutron absorber. Also, it does not ensure the maintenance of the subcriticality of a nuclear fuel transport packaging.
  • the present invention specifically relates to a neutron shielding material and for maintaining the subcriticality which has a better corrosion resistance than that of materials based on unsaturated polyester.
  • the composite material for neutron shielding and for maintaining the subcriticality comprises a matrix based on vinylester resin and an inorganic filler capable of slowing down and absorbing the neutrons.
  • the vinylester resin can be of different types.
  • resins obtained by adding a carboxylic acid to an epoxy resin are used.
  • the epoxy resins used have a macromolecular pattern of two possible types:
  • the carboxylic acid can in particular be acrylic acid or methacrylic acid. Preferably, methacrylic acid is used.
  • the vinylester resin is preferably chosen from the group consisting of epoxyacrylate resins, epoxymethacrylate resins, bisphenol A type resins, novolak type resins and halogenated bisphenol A based resins.
  • Bisphenol A type epoxyacrylate and epoxymethacrylate resins can correspond to the formula:
  • R represents H or CH 3 .
  • Novolak type vinyl ester resins can meet the formula:
  • non-epoxy vinyl ester resins obtained from isophthalic polyester and urethane, corresponding for example to the formula:
  • R is as defined above and U represents a urethane group.
  • the composite material of the invention has the following advantages.
  • the material is easy to produce because the vinyl ester resin can be poured directly into the mold which will constitute the transport or storage packaging for radioactive products.
  • the mass loss of the shielding materials produced with these vinyl ester resins is low at high temperature.
  • the vinyl ester resins were transformed into a thermoset material by reaction with a copolymerizable monomer such as styrene and styrene derivatives such as methylstyrene and divinylbenzene, vinyltoluene, methyl methacrylate and the derivatives allylics like diallyl phthalate.
  • the material also comprises an inorganic filler capable of slowing down and absorbing neutrons, for example metals, metal compounds, boron, boron compounds.
  • this inorganic filler can in particular comprise at least one inorganic boron compound and at least one hydrogenated inorganic compound.
  • the boron compounds which can be used belong to the group comprising boric acid H 3 B0 3 , colemanite Ca 2 O ⁇ B 6 H ⁇ 0 , zinc borates Zn 2 O ⁇ 4 , 5 H 7 B 6 , Zn 4 0 8 B 2 H 2 and Zn 2 0nB 6 , boron carbide B 4 C, boron nitride BN and boron oxide B 2 0 3 .
  • the composite material of the invention comprises at least one boron compound chosen from zinc borate Zn 2 0 14 ⁇ 5H 7 B6 and boron carbide B 4 C.
  • the hydrogenated inorganic compounds which can be used preferably belong to the group of alumina hydrates and magnesium hydroxide.
  • the material of the invention can also comprise poly (vinyl acetate) to give the material an anti-shrinkage character.
  • This material can also further comprise a hydrogenated organic filler such as melamine, to improve its self-extinguishing properties.
  • a hydrogenated organic filler such as melamine
  • the inorganic boron compound and the hydrogenated inorganic compound are preferably chosen and their quantities so as to obtain a boron concentration of the material from 8.10 20 to 15.10 21 boron atoms per cm 3 and a hydrogen concentration of 4.10 22 to 6.10 22 atoms per cm 3 .
  • the quantities of the various constituents are also chosen in order to obtain characteristics of density, self-extinguishing and thermal conductivity suitable for use in a packaging for transport and / or storage of materials. radioactive.
  • this self-extinguishing property is conferred in particular by the presence of hydrogenated and / or boron inorganic compounds, for example alumina hydrate or zinc borate.
  • the material should have a low thermal conductivity but sufficient to dissipate the heat from the transported elements such as irradiated fuel elements.
  • this material is obtained by casting a mixture of the various constituents and a vinyl diluent, it is important that the amounts of the various constituents are such that the mixture has the property of be able to be cast. Generally, the viscosity of the mixture should not exceed 300 Poises.
  • thermosetting vinyl ester resin that is to say including the vinyl diluent, for example styrene.
  • the material has a density equal to or greater than 1.6, for example from 1.65 to 1.9.
  • the materials of the invention can withstand a minimum use temperature of 160 ° C.
  • the material of the invention can be prepared by curing a mixture of the constituents in the vinyl ester resin in solution in a vinyl diluent.
  • the subject of the invention is also a process for preparing the composite material described above, which comprises the following steps:
  • the vinyl diluent can be, for example, styrene, vinyltoluene, divinylbenzene, methylstyrene, methyl acrylate, methyl methacrylate or an allylic derivative such as diallyl phthalate.
  • styrene is used which makes it possible both to dissolve the vinyl ester resin and to ensure its hardening by copolymerization.
  • the curing catalysts and accelerators used are chosen from the compounds usually used for curing vinyl ester resins.
  • the catalysts can in particular be organic peroxides, for example: - peroxides derived from ketones such as methyl ethyl ketone peroxide, acetylacetone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide and cumene hydroperoxide;
  • diacyl peroxides for example benzoyl peroxide optionally in combination with aromatic tertiary amines such as dimethylaniline, diethylaniline and dimethylparatoluidine; and
  • dialkyl peroxides such as dicumyl peroxide and ditertiobutyl peroxide.
  • the most commonly used accelerators are divalent cobalt salts such as cobalt naphthenate or octoate, and aromatic tertiary amines such as dimethylaniline, dimethylparatoluidine and diethylaniline.
  • additives such as crosslinking inhibitors, surfactants and anti-shrinkage agents.
  • the procedure is as follows:
  • the vinyl ester resin prepolymer + vinyl diluent
  • the percentage of charges can range from 60 to 75%. These charges can also play a fire-fighting role.
  • the whole is kneaded so as to obtain a mixture perfectly homogeneous.
  • the catalyst is added last.
  • the homogeneous mixture is then degassed under vacuum (less than 0.01 MPa).
  • the viscosity of the mixture must not exceed 300 Poises (the mixture must be pourable).
  • the mixture After degassing, the mixture is poured into the desired mold where it is crosslinked to form an insoluble thermosetting material.
  • the reaction mechanism is radical, and the reaction is strongly exothermic.
  • the hardening time can vary depending on the casting conditions (temperature, catalyst, accelerator and inhibitor ratio). Thus, the gel time can be adjusted by varying the percentages of catalyst and accelerators.
  • the freezing time varies from 20 min to 2 h.
  • the mold used for curing the resin can be formed directly by the packaging for transporting and / or storing radioactive products.
  • the packaging may include peripheral housings in which the mixture is poured.
  • Another subject of the invention is a packaging for transporting and / or storing radioactive products comprising a screen formed from the composite material described above.
  • Figure 1 shows the mass losses (in%) at 160 and 170 ° C of two materials according to the invention as a function of time (in days).
  • a polymerizable mixture is prepared from the vinyl ester resin Dérakane Momentum 470-300, styrene, zinc borate Zn 2 0 ⁇ 4/5 H 7 B 6 and magnesium hydroxide using the proportions given in table 1 appended .
  • the following constituents are added to the mixture: - 1% by weight, relative to the mass of resin + styrene, of the accelerator 55028 sold by Akzo, and - 2% by weight, relative to the mass of resin + styrene, of the Butanox M50 catalyst (methyl ethyl ketone peroxide) sold by Akzo.
  • a composite material is thus obtained having the following properties:
  • the material obtained has satisfactory thermal properties.
  • the specific heat Cp is measured by differential enthalpy analysis (DSC 30, METTLER), with a temperature rise rate of 10 ° C / min, over a temperature range from 30 to 200 ° C.
  • Cp values are between 1.19 Jg ⁇ . o C "1 and 1.89 Jg " 1 . 0 ⁇ 1 for temperatures between 40 ° C and 180 ° C.
  • Thermal conductivity measurements are also carried out for temperatures ranging from 25 ° C to 180 ° C. Values range from 0.75 to 0.91 .m ⁇ K "1 .
  • the mechanical properties of the material are also determined by carrying out compression tests at 23 ° C, on test pieces 10 mm in diameter and 20 mm in height, with a Adamel Lhomargy DY26 dynamometer and a test speed of 1 mm / min. The results obtained are as follows:
  • the mixture also comprises: 0.9% by weight, relative to the mass of resin, of the NL 49P accelerator sold by Akzo, and
  • the hardening is carried out at ambient temperature and a material having the following characteristics is obtained after 25 minutes:
  • the material obtained has satisfactory thermal properties.
  • the specific heat Cp is measured by differential enthalpy analysis (DSC30, METTLER), with a temperature rise rate of 10 ° C / min, over a temperature range from 40 ° C to 180 ° C. Cp values are between 1.07 and 1.65 Jg "1. O C " 1 .
  • the mechanical properties of the material are also determined by carrying out compression tests at 23 ° C. We can thus determine the compression modulus of the material which is 4299 ⁇ 276 MPa.
  • Example 2 Given the hydrogen content, the material of Example 2 is particularly suitable for an application in radiation protection.
  • the aging tests over 6 months consist in placing samples of the material of dimensions 35 x 25 x 95 mm in an oven at 160 ° C and 170 ° C and monitoring the loss of mass of these samples over time.
  • the curves for the evolution of the mass loss of materials (in%) as a function of time (in days) are shown in Figure 1. Fire behavior tests of the materials of Examples 1 and 2 were also carried out.
  • Each half-hour fire test at 800 ° C. was carried out on two blocks 240 mm in diameter and 60 mm in height from the materials of Examples 1 and 2.
  • the flame was directly in contact with the material while the second blocks were protected by a steel sheet 1 mm thick. In both cases, and for both materials, self-extinguishing is immediate after removal of the torch.
  • Example 3 The same procedure is followed as in Example 1 to prepare a neutron shielding material and to maintain the subcriticality from the following mixture:
  • the mixture also includes:
  • Example 3 Given its high boron content, the material of Example 3 has excellent efficiency in maintaining subcriticality.
  • the material of the invention has very advantageous properties for neutron shielding and the maintenance of subcriticality during the transport of nuclear fuel assemblies.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Sealing Material Composition (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Organic Insulating Materials (AREA)
EP02804603A 2001-12-12 2002-12-10 Werkstoff auf basis von vinylesterharz zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität Expired - Lifetime EP1454327B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0116036 2001-12-12
FR0116036A FR2833402B1 (fr) 2001-12-12 2001-12-12 Materiau de blindage neutronique et de maintien de la sous- criticite a base de resine vinylester
PCT/FR2002/004255 WO2003050822A2 (fr) 2001-12-12 2002-12-10 Materiau de blindage neutronique et de maintien de la sous-criticite a base de resine vinylester

Publications (2)

Publication Number Publication Date
EP1454327A2 true EP1454327A2 (de) 2004-09-08
EP1454327B1 EP1454327B1 (de) 2010-06-30

Family

ID=8870372

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02804603A Expired - Lifetime EP1454327B1 (de) 2001-12-12 2002-12-10 Werkstoff auf basis von vinylesterharz zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität

Country Status (11)

Country Link
US (1) US7160486B2 (de)
EP (1) EP1454327B1 (de)
JP (1) JP4732689B2 (de)
KR (1) KR100947528B1 (de)
AT (1) ATE472806T1 (de)
AU (1) AU2002366643A1 (de)
DE (1) DE60236890D1 (de)
ES (1) ES2348387T3 (de)
FR (1) FR2833402B1 (de)
WO (1) WO2003050822A2 (de)
ZA (1) ZA200403576B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ306407B6 (cs) * 2014-02-19 2017-01-11 Petr Kraus Způsob výroby tvarovaného dílu z materiálu odstiňujícího radioaktivní záření a tvarovaný díl vyrobený tímto způsobem

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FR2830367B1 (fr) * 2001-10-01 2003-12-19 Transnucleaire Materiau de blindage neutronique et de maintien de la sous-criticite a base de polyester insature
FR2846467B1 (fr) * 2002-10-25 2005-01-28 Cogema Logistics Materiau de blindage neutronique et de maintien de la sous-criticite, son procede de preparation et ses applications
KR100706012B1 (ko) * 2003-03-03 2007-04-11 미츠비시 쥬고교 가부시키가이샤 캐스크, 중성자 차폐체용 조성물 및 중성자 차폐체 제조법
US8664630B1 (en) * 2011-03-22 2014-03-04 Jefferson Science Associates, Llc Thermal neutron shield and method of manufacture
FR3030865A1 (fr) 2014-12-23 2016-06-24 Commissariat Energie Atomique Utilisation d'un materiau comprenant une matrice solide a base d'un polymere silicone et des charges inorganiques comme materiau neutrophage
FR3087293B1 (fr) 2018-10-15 2020-10-09 Tn Int Materiau composite de blindage neutronique et de maintien de la sous-criticite, son procede de fabrication et ses utilisations
WO2021252112A1 (en) 2020-05-20 2021-12-16 Neutroelectric, Llc Neutron shielding and radiation absorbing compositions
US12051516B1 (en) * 2020-09-01 2024-07-30 GeoPlasma, LLC Method of manufacturing advanced composites and coatings for radiation environment shielding
FR3124018B1 (fr) * 2021-06-10 2024-07-05 Orano Nuclear Packages And Services Matériau composite de blindage neutronique et de maintien de la sous-criticité, son procédé de fabrication et ses utilisations
CN113773651A (zh) * 2021-09-02 2021-12-10 中海油常州涂料化工研究院有限公司 一种常温固化的中子屏蔽材料及其制备方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ306407B6 (cs) * 2014-02-19 2017-01-11 Petr Kraus Způsob výroby tvarovaného dílu z materiálu odstiňujícího radioaktivní záření a tvarovaný díl vyrobený tímto způsobem

Also Published As

Publication number Publication date
WO2003050822A2 (fr) 2003-06-19
FR2833402A1 (fr) 2003-06-13
JP4732689B2 (ja) 2011-07-27
DE60236890D1 (de) 2010-08-12
AU2002366643A1 (en) 2003-06-23
ATE472806T1 (de) 2010-07-15
US20050012054A1 (en) 2005-01-20
US7160486B2 (en) 2007-01-09
JP2005512101A (ja) 2005-04-28
EP1454327B1 (de) 2010-06-30
FR2833402B1 (fr) 2004-03-12
KR100947528B1 (ko) 2010-03-15
ES2348387T3 (es) 2010-12-03
WO2003050822A3 (fr) 2004-02-19
KR20040079904A (ko) 2004-09-16
ZA200403576B (en) 2005-06-29

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