FR2546331A1 - Improvements to hydrogen-containing materials for antineutron protection - Google Patents

Improvements to hydrogen-containing materials for antineutron protection Download PDF

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Publication number
FR2546331A1
FR2546331A1 FR8308667A FR8308667A FR2546331A1 FR 2546331 A1 FR2546331 A1 FR 2546331A1 FR 8308667 A FR8308667 A FR 8308667A FR 8308667 A FR8308667 A FR 8308667A FR 2546331 A1 FR2546331 A1 FR 2546331A1
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FR
France
Prior art keywords
binder
material according
hydrate
protection
hydrogen
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.)
Pending
Application number
FR8308667A
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French (fr)
Inventor
Camille Bochard
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.)
Robatel SLPI SA
Original Assignee
Robatel SLPI 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 Robatel SLPI SA filed Critical Robatel SLPI SA
Priority to FR8308667A priority Critical patent/FR2546331A1/en
Publication of FR2546331A1 publication Critical patent/FR2546331A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/30—Oxides other than silica
    • C04B14/303—Alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/18—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • 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
    • G21F1/04—Concretes; Other hydraulic hardening materials
    • G21F1/042—Concretes combined with other materials dispersed in the carrier

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention consists essentially in incorporating into a binder (Ciment Fondu or polyester resin) including, besides a boron-containing product, beads or granules of a highly hydrogenated product (polyethylene or polypropylene), a stable hydrate, especially alumina trihydrate, capable of increasing the mechanical strength of the material.

Description

La présente invention a trait aux matériaux de protection antineutronique, destinés notamment à être utilisés pour la réalisation des écrans anti-rayonnement de cellules de travail, emballages du transport ou châteaux de stockage. The present invention relates to antineutronic protection materials, intended in particular to be used for the production of radiation shields for working cells, transport packaging or storage castles.

Les propriétés les plus intéressantes que doit présenter un matériau de protection anti-neutronique peuvent être énumérées de la manière suivante
1. Efficacité maximale
2. Faible densité
3. Facilité de mise en oeuvre
4. Coût réduit
5. Bonne tenue mécanique
6. Bonne tenue thermique
La propriété 1. visant l'efficacité est évidemment essentielle il est indispensable que le matériau retenu soit capable de ralentir les neutrons rapides et de les absorber. Il y a cependant lieu de souligner que le choix d'un matériau implique toujours un compromis entre ses différentes propriétés, en fonction de l'utilisation particuliere envisagée.The most interesting properties that an anti-neutron protective material must have can be listed as follows
1. Maximum efficiency
2. Low density
3. Ease of implementation
4. Reduced cost
5. Good mechanical strength
6. Good thermal resistance
The property 1. aiming at efficiency is obviously essential it is essential that the selected material is capable of slowing down the fast neutrons and of absorbing them. It should however be emphasized that the choice of a material always implies a compromise between its different properties, depending on the particular use envisaged.

L'expérience démontre que les qualités d'un matériau de protection anti-neutronique sont étroitement liées a la densité d'atomes légers présents dans ce matériau. C'est la raison pour laquelle l'on a naturellement eu recours à l'eau, au polyéthylène, a la paraffine, aux bectons, etc... Toutefois aucun de ces matériaux classiques ne réunit l'ensemble des qualités souhaites pour une protection optimale. Experience shows that the qualities of an anti-neutron protective material are closely linked to the density of light atoms present in this material. This is the reason why we naturally resorted to water, polyethylene, paraffin, bectons, etc. However, none of these classic materials meets all the desired qualities for protection optimal.

Un matériau réunissant dans une bonne mesure les six propriétés recherchées telles qu'énumérées ci-dessus a StE décrit dans le brevet français N 1 534 032 du 14 Juin 1967 appartenant à la présente Demanderesse. On rappelera succinctement que la matériau décrit est composé de billes ou granules d'un produit très hydrogéné (polyéthylène ou polypropylène) retenues dans un liant constitué par du pitre et additionné d'un produit borE. A material combining to a good extent the six desired properties as listed above in StE described in French patent N 1,534,032 of June 14, 1967 belonging to the present Applicant. It will be briefly recalled that the material described is composed of beads or granules of a highly hydrogenated product (polyethylene or polypropylene) retained in a binder consisting of claw and added with a borE product.

L'utilisation pratique d'un tel matériau hydrogéné a permis de vérifier que toutes les propriétés complementaires dépendaient en fait de la qualité du liant. Dans ces conditions la présente invention a pour objet une famille de matériaux de protection anti-neutronique du type de celui qui fait l'objet du brevet français sus-mentionné, réalisés avec des liants bores prehydrates aptes à améliorer encore l'efficacité anti-neutronique et à assurer une meilleure tenue mécanique tout en conservant les autres qualités déjà acquises. The practical use of such a hydrogenated material made it possible to verify that all of the complementary properties actually depended on the quality of the binder. Under these conditions, the present invention relates to a family of anti-neutron protection materials of the type which is the subject of the above-mentioned French patent, produced with boron prehydrate binders capable of further improving the anti-neutron efficiency and to ensure better mechanical strength while retaining the other qualities already acquired.

L'invention consiste essentiellement à incorporer au liant un hydrate stable qui est compatible avec l'agent de solidification et qui complète celui-ci afin d'accroître la résistance mecanique de l'ensemble. The invention essentially consists in incorporating into the binder a stable hydrate which is compatible with the solidifying agent and which supplements it in order to increase the mechanical strength of the whole.

Parmi les hydrates susceptibles de convenir, on citera les aluminates de calcium hydratés et les hydrates d'alumine, tout particulièrement le tri-hydrate d'alumine (Al2 03, 3 H20). En pareil cas on aura avantageusement recours pour le liant, non plus au plâtre, mais à un ciment alumineux du type ciment fondu", ou à une résine polyester. Among the hydrates which may be suitable, mention will be made of hydrated calcium aluminates and alumina hydrates, most particularly alumina trihydrate (Al2 03, 3 H 2 O). In such a case, the binder will advantageously be used, no longer plaster, but an aluminous cement of the molten cement type ", or a polyester resin.

Pour ce qui est du bore, celui-ci sera apporté sous la forme de minerais (colémanite standard, par exemple) ou de composés industriels tels que le carbure de bore (B4C). Comme dans le cas du brevet antérieur l 534 032 le bore est destiné à absorber les neutrons qui ont été ralentis par les autres constituants à atomes légers du mélange qui forme le matériau suivant l'invention.Afin de faciliter leur dispersion dans la masse, les grains qui constituent le produit boré ont des dinensions de l'ordre de 50 à 200
On donnera ci-apres deux types de compositions, correspondant l'une à un liant à l'eau, l'autre à un liant résine
Composés Liants à l'eau Liant résine
Alumine hydratez 40 à 60% 40 à 55%
Ciment fondu 15 à 25% O
Eau 20 à 30% 0
Résine synthétique 0 35 à 45% Colemanite 10 à 15% 10 à 15%
ou
Carbure de bore 1 à 3% 1 à 3%
Sur le plan pratique de la mise en oeuvre, on commence par mélanger intimement à sec les poudres constituant le liant, on ajoute l'eau ou la résine (avec dans ce dernier cas addition de l'agent catalyseur), et lorsque le me lange est homogène on incorpore les granulés de polyétylène ou de polypropylène, de la mime manière que dans le brevet français antérieur de la Demanderesse ; la proportion des ces granulés par rapport au liant peut varier de 34 à 42%.As for boron, this will be provided in the form of ores (standard colemanite, for example) or industrial compounds such as boron carbide (B4C). As in the case of the prior patent 1 534 032 boron is intended to absorb the neutrons which have been slowed down by the other constituents with light atoms of the mixture which forms the material according to the invention. In order to facilitate their dispersion in the mass, grains which constitute the borated product have dinensions of the order of 50 to 200
Two types of compositions will be given below, one corresponding to a water binder, the other to a resin binder
Compounds Water binders Resin binder
Alumina hydrate 40 to 60% 40 to 55%
Melted cement 15 to 25% O
Water 20 to 30% 0
Synthetic resin 0 35 to 45% Colemanite 10 to 15% 10 to 15%
or
Boron carbide 1 to 3% 1 to 3%
On the practical level of implementation, we start by intimately dry mixing the powders constituting the binder, we add water or resin (with in the latter case addition of the catalyst agent), and when the mixture is homogeneous, the polyethylene or polypropylene granules are incorporated, in the same manner as in the prior French patent of the Applicant; the proportion of these granules relative to the binder can vary from 34 to 42%.

Les essais ont démontré que le matériau obtenu conformément à l'invention présentait une haute résistance mécanique et des qualités d'efficacité de protection anti-neutronique très élevées. Il convient d'observer que le tri-hydrate d'alumine commence à perdre son eau à partir de 2200C, ce qui assure une grande stabilité de protection. Par ailleurs les réactions de déshydratation sont de nature très endothermique, ce qui confère au matériau une excellente tenue au feu ; cet avantage est particulièrement intéressant dans le cas des écrans ou blindages pour châteaux de transport de matibre radioactives. The tests demonstrated that the material obtained in accordance with the invention exhibited high mechanical strength and very high anti-neutron protection efficiency qualities. It should be noted that the alumina tri-hydrate begins to lose its water from 2200C, which ensures high protection stability. Furthermore, the dehydration reactions are very endothermic in nature, which gives the material excellent resistance to fire; this advantage is particularly advantageous in the case of screens or shields for transport casks of radioactive material.

Les formules du genre de celles sus-indiquas permettent de réaliser des matériaux de protection comportant un nombre d'atomes d'hydrogène par unité de volume supérieur à celui de l'eau. On indiquera ci-après une composition atomique élémentaire an g/dt3 susceptible d' & re obtenue
Aluminium 189,6
Bore 10,4
Calcium 47,7
Carbone 454,2
Fer 21,6
Hydrogène 113,4
Oxygène 506,0
Divers 7,1 entant bien noté qu'il s'agit d'un simple exemple non limitatif.The formulas of the kind of those indicated above make it possible to produce protective materials comprising a number of hydrogen atoms per unit of volume greater than that of water. An elementary atomic composition an g / dt3 capable of being obtained will be indicated below
Aluminum 189.6
Boron 10.4
Calcium 47.7
Carbon 454.2
Iron 21.6
Hydrogen 113.4
Oxygen 506.0
Miscellaneous 7.1 being noted that this is a simple non-limiting example.

Il doit d'ailleurs être entendu que la description qui prEcade n'a été donnée qu'à titre d'exemple et qu'elle ne limite nullement le domaine de l'invention dont on ne sortirait pas en remplaçant les détails d'exécution décrits par tous autres équivalents.  It should moreover be understood that the description which precedes has been given only by way of example and that it in no way limits the field of the invention from which one would not depart by replacing the execution details described by all other equivalents.

Claims (6)

REVENDICATIONS 1. Matériau de protection anti-neutronique, du genre comprenant des billes ou granules d'un produit très hydrogEnd retenues dans un liant additionné d'un produit boré, caractérisE en ce que le liant incorpore un hydrate stable compatible avec l'agent de solidification et propre à compléter celui-ci pour accroître la résistance mécanique de l'ensemble. 1. Anti-neutron protection material, of the type comprising beads or granules of a highly hydrogEnd product retained in a binder added with a boron product, characterized in that the binder incorporates a stable hydrate compatible with the solidifying agent and suitable for completing it to increase the mechanical strength of the assembly. 2. Matériau suivant la revendication 1, caractérise an ce que l'hydrata est constitué par un aluminate de calcium hydrate. 2. Material according to claim 1, characterized in that the hydrata consists of a hydrated calcium aluminate. 3. Matériau suivant la revendication 1, caractérisé en ce que l'hydrate est constitué par un hydrate d'alumine. 3. Material according to claim 1, characterized in that the hydrate consists of an alumina hydrate. 4. Matériau suivant la revendication 3, caractérisE en ce que l'hydrata est constitué par le tri-hydrate d'alumine. 4. Material according to claim 3, characterized in that the hydrata consists of the alumina trihydrate. 5. Matériau suivant l'une quelconque des revendications 1 à 4, caractérisé en ce que le liant est constitué par un ciment alumineux du type "ciment fondu". 5. Material according to any one of claims 1 to 4, characterized in that the binder consists of an aluminous cement of the "molten cement" type. 6. Matériau suivant l'une quelconque des revendications 2 à 4, caractérisé en ce que le liant est constitué par une résine polyester.  6. Material according to any one of claims 2 to 4, characterized in that the binder consists of a polyester resin.
FR8308667A 1983-05-20 1983-05-20 Improvements to hydrogen-containing materials for antineutron protection Pending FR2546331A1 (en)

Priority Applications (1)

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FR8308667A FR2546331A1 (en) 1983-05-20 1983-05-20 Improvements to hydrogen-containing materials for antineutron protection

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0773555A1 (en) * 1995-11-13 1997-05-14 Doryokuro Kakunenryo Kaihatsu Jigyodan Neutron-shielding hydraulic hardening material and method of manufacturing neutron shields using the same
FR2830367A1 (en) * 2001-10-01 2003-04-04 Transnucleaire NEUTRONIC SHIELDING AND SUB-CRITICALITY MAINTENANCE MATERIAL BASED ON INSATURE POLYESTER
FR2846467A1 (en) * 2002-10-25 2004-04-30 Cogema Logistics Neutron screening material, for use in protecting radioactive materials, e.g. fuel rods during transport and storage, comprises vinylester resin matrix, one or more polyamides and neutron slowing and absorbing inorganic filler
EP2544189A1 (en) * 2011-07-08 2013-01-09 Arraela S.L. Material for absorption and attenuation of neutrons
EP3750857A1 (en) * 2019-06-14 2020-12-16 Sika Technology Ag Method for the kinetic regulation of cementitious binders

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2726339A (en) * 1949-03-03 1955-12-06 Lyle B Borst Concrete radiation shielding means
FR1201635A (en) * 1958-07-07 1960-01-04 Commissariat Energie Atomique Improvements to protective screens against radiation of nuclear origin
US2961415A (en) * 1956-11-02 1960-11-22 Irving R Axelrad Settable neutron radiation shielding material
FR1422349A (en) * 1964-11-13 1965-12-24 Commissariat Energie Atomique Protective material against radiation of nuclear origin
FR1458833A (en) * 1964-11-27 1966-11-10 English Electric Co Ltd Radiation blocking material
FR1534032A (en) * 1967-06-14 1968-07-26 Commissariat Energie Atomique Neutron absorbing material and its manufacturing process
DE2258660A1 (en) * 1972-11-30 1974-06-06 Petrocarbona Gmbh Fire-retardant resin-bound concrete panels prodn. - with good weathering resistance hot dimensional stability using alumina (tri) hydrate as fire retardants
US4123392A (en) * 1972-04-13 1978-10-31 Chemtree Corporation Non-combustible nuclear radiation shields with high hydrogen content

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2726339A (en) * 1949-03-03 1955-12-06 Lyle B Borst Concrete radiation shielding means
US2961415A (en) * 1956-11-02 1960-11-22 Irving R Axelrad Settable neutron radiation shielding material
FR1201635A (en) * 1958-07-07 1960-01-04 Commissariat Energie Atomique Improvements to protective screens against radiation of nuclear origin
FR1422349A (en) * 1964-11-13 1965-12-24 Commissariat Energie Atomique Protective material against radiation of nuclear origin
FR1458833A (en) * 1964-11-27 1966-11-10 English Electric Co Ltd Radiation blocking material
FR1534032A (en) * 1967-06-14 1968-07-26 Commissariat Energie Atomique Neutron absorbing material and its manufacturing process
US4123392A (en) * 1972-04-13 1978-10-31 Chemtree Corporation Non-combustible nuclear radiation shields with high hydrogen content
DE2258660A1 (en) * 1972-11-30 1974-06-06 Petrocarbona Gmbh Fire-retardant resin-bound concrete panels prodn. - with good weathering resistance hot dimensional stability using alumina (tri) hydrate as fire retardants

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0773555A1 (en) * 1995-11-13 1997-05-14 Doryokuro Kakunenryo Kaihatsu Jigyodan Neutron-shielding hydraulic hardening material and method of manufacturing neutron shields using the same
FR2830367A1 (en) * 2001-10-01 2003-04-04 Transnucleaire NEUTRONIC SHIELDING AND SUB-CRITICALITY MAINTENANCE MATERIAL BASED ON INSATURE POLYESTER
WO2003030183A2 (en) * 2001-10-01 2003-04-10 Cogema Logistics Neutron shielding material for maintaining sub-criticality based on unsaturated polymer
WO2003030183A3 (en) * 2001-10-01 2003-12-04 Cogema Logistics Neutron shielding material for maintaining sub-criticality based on unsaturated polymer
KR100901151B1 (en) 2001-10-01 2009-06-04 꼬제마 로지스틱스 에스.아. Neutron shielding material for maintaining sub-criticality based on unsaturated polymer
US7524438B2 (en) 2001-10-01 2009-04-28 Cogema Logistics Unsaturated polyester-based material for neutron-shielding and for maintaining sub-criticality
US7399431B2 (en) 2002-10-25 2008-07-15 Cogema Logistics Material for neutron shielding and for maintaining sub-critically, process for its preparation and its applications
EP1418593A1 (en) * 2002-10-25 2004-05-12 Cogema Logistics Neutron shielding material for subcritical maintenance and its production and applications
FR2846467A1 (en) * 2002-10-25 2004-04-30 Cogema Logistics Neutron screening material, for use in protecting radioactive materials, e.g. fuel rods during transport and storage, comprises vinylester resin matrix, one or more polyamides and neutron slowing and absorbing inorganic filler
EP2544189A1 (en) * 2011-07-08 2013-01-09 Arraela S.L. Material for absorption and attenuation of neutrons
EP3750857A1 (en) * 2019-06-14 2020-12-16 Sika Technology Ag Method for the kinetic regulation of cementitious binders
WO2020249805A1 (en) * 2019-06-14 2020-12-17 Sika Technology Ag Method for the kinetic regulation of cementitious binders
US11912631B2 (en) 2019-06-14 2024-02-27 Sika Technology Ag Method for the kinetic regulation of cementitious binders

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