EP1446808B1 - Material zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität mit ungesättigtem polyester als ausgangsmaterial - Google Patents

Material zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität mit ungesättigtem polyester als ausgangsmaterial Download PDF

Info

Publication number
EP1446808B1
EP1446808B1 EP02785511A EP02785511A EP1446808B1 EP 1446808 B1 EP1446808 B1 EP 1446808B1 EP 02785511 A EP02785511 A EP 02785511A EP 02785511 A EP02785511 A EP 02785511A EP 1446808 B1 EP1446808 B1 EP 1446808B1
Authority
EP
European Patent Office
Prior art keywords
boron
material according
inorganic compound
hydrogenated
atoms per
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.)
Expired - Lifetime
Application number
EP02785511A
Other languages
English (en)
French (fr)
Other versions
EP1446808A2 (de
Inventor
Pierre Malalel
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
TN International 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 TN International SA filed Critical TN International SA
Publication of EP1446808A2 publication Critical patent/EP1446808A2/de
Application granted granted Critical
Publication of EP1446808B1 publication Critical patent/EP1446808B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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 maintaining sub-criticality.
  • Such materials are useful in nuclear energy to protect operators from neutron radiation emitted by radioactive products and to prevent runaway neutron formation chain reaction, especially when these products contain fissile material.
  • They can be used in particular as a neutron screen in transport and / or storage packages of radioactive products, for example nuclear fuel assemblies.
  • thermosetting resin may be an unsaturated polyester resin and the inorganic fillers may be heavy metals or compounds thereof. Thus, this document does not provide for the addition of boron compounds.
  • the preferred thermosetting resin is an epoxy resin.
  • the document GB-A-1,049,890 [2] discloses 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 an unsaturated monomer in which either the acidic component of the polyester is derived in part from boric acid, or the polymerizable monomer is in part a boric acid ester.
  • the boron content is 0.3 to 5% by weight. This boron content remains insufficient to ensure effective absorption of neutrons. Moreover, this material does not have self-extinguishing.
  • the document JP-A-55 119099 [3] describes neutron protection materials. Such a material has a density in hydrogen atoms of 6.1 x 10 22 hydrogen atoms per cm 3 , but it does not include a neutron absorber. Also, it does not make it possible to maintain the sub-criticality of a nuclear fuel transport package.
  • the subject of the present invention is precisely a neutron shielding material which makes it possible to ensure the maintenance of subcriticality by virtue of the presence of a boron compound in a sufficient quantity.
  • the neutron shielding and subcriticality maintaining material comprises an unsaturated polyester resin, at least one inorganic boron compound, and at least one hydrogenated inorganic compound in amounts such that the boron concentration is 21 to 25.10 21 , preferably 9.10 21 to 15.10 21 atoms per cm 3 and that the hydrogen concentration is from 3.10 22 to 5.5.10 22 , preferably from 4.10 22 to 5.10 22 atoms per cm 3 .
  • the unsaturated polyester resin can be of different types.
  • resins obtained by polycondensation of one or more diacids with one or more glycols are used, at least one of the constituents containing an ethylenic double bond capable of reacting subsequently with a vinyl, acrylic or allylic compound.
  • resins obtained from common polyols such as propylene glycol, dipropylene glycol, diethylene glycol and oxyethylated or oxypropylated polyols of ethylene glycol oxyethylenated type and unsaturated diacids such as maleic anhydride, citraconic, metaconic acid and itaconic acid, or saturated diacids such as phthalic anhydride and its chlorinated or brominated derivatives.
  • these resins have been converted into a thermoset material by reaction with a copolymerizable monomer such as styrene and styrene derivatives such as methylstyrene, and divinylbenzene.
  • a copolymerizable monomer such as styrene and styrene derivatives such as methylstyrene, and divinylbenzene.
  • the inorganic boron compound and the hydrogenated inorganic compound and their amounts are chosen so as to obtain concentrations of boron and hydrogen in the ranges indicated above.
  • the boron compounds which may be used belong to the group comprising boric acid H 3 BO 3, colemanite Ca 2 O 14 B 6 H 10 , zinc borates Zn 2 O 14 , 5 H 7 B 6 , Zn 4 O 8 B 2 H 2 and Zn 2 O 11 B 6 , boron carbide B 4 C, boron nitride BN and boron oxide B 2 O 3 .
  • the composite material of the invention comprises two inorganic boron compounds, one of which is hydrogenated, for example zinc borate.
  • the hydrogenated inorganic compounds which may be used preferably belong to the group of hydrates of alumina and of magnesium hydroxide.
  • Alumina hydrate A1 (OH) 3 is preferably used.
  • the material of the invention may further comprise polyvinyl acetate to impart to the material an anti-shrinkage character.
  • It may also further comprise a hydrogenated organic filler such as melanin, to improve its self-extinguishing properties.
  • a hydrogenated organic filler such as melanin
  • the amounts of the various constituents are also selected in order to obtain characteristics of density, self-extinguishing and thermal conductivity suitable for use in a transport packaging and / or storage of radioactive materials.
  • the material has a fire resistance, which supposes that it is self-extinguishing, that is to say that the fire stops when the flame is removed; it does not fuel the fire.
  • this self-extinguishing property is conferred in particular by the presence of hydrogenated and / or borated inorganic compounds, for example alumina hydrate or borate borate. zinc.
  • the self-extinguishing character can also be conferred by the presence of melanin.
  • the material should have a low thermal conductivity but sufficient to remove 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 can be cast.
  • thermoset unsaturated polyester resin that is to say including the vinylic diluent, for example styrene.
  • the material has a density equal to or greater than 1.7, for example from 1.7 to 1.85.
  • the boron content is preferably at least 9.4 ⁇ 10 21 boron atoms per cm 3 .
  • the material of the invention may be prepared by curing a mixture of the components in the unsaturated polyester resin dissolved in a vinylic diluent.
  • the invention also relates to a process for preparing the neutron shielding material described above, which consists in preparing a mixture of the unsaturated polyester resin in solution. in a vinyl diluent with the inorganic boron compound (s) and the hydrogenated inorganic compound (s), to add a catalyst and a hardening accelerator to the mixture, pour the mixture into a mold and let it harden in the mold.
  • the vinyl diluent may be for example styrene, vinyltoluene, divinylbenzene, methylstyrene, methyl acrylate, methyl methacrylate or an allyl derivative such as diallyl phthalate.
  • styrene is used which both dissolves the unsaturated polyester resin and ensures its hardening by copolymerization.
  • the catalysts and curing accelerators used are chosen from compounds usually used for the curing of unsaturated polyesters.
  • the accelerators used most often are divalent cobalt salts such as naphthenate or cobalt octoate, and aromatic tertiary amines such as dimethylaniline, dimethylparatoluidine and diethylaniline.
  • One or more additives such as crosslinking inhibitors, surfactants and anti-shrinkage agents can be added to the mixture.
  • the mold used for the curing of the resin can be constituted directly by the packaging for transporting and / or storing radioactive products.
  • the packaging may comprise two concentric walls, for example two steel rings, between which the mixture is cast before curing.
  • the packaging may also include peripheral housing in which the mixture is poured.
  • the curing of the resin is then carried out. For this purpose, it is necessary to preheat the mixture to 45 ° C.
  • the mixture is then degassed under vacuum for 4 min and then the mixture is poured into a mold heated to 100 ° C. and set under vacuum (-0.3 bar) to facilitate filling and decrease casting time.
  • the space between the two concentric shells is intended for casting the polymerizable mixture.
  • This closed space at its upper end has on this end two diametrically opposed holes.
  • One of the holes is connected to a tundish and the other hole is connected to a vacuum pump to create a negative pressure of -0.3 bar during casting.
  • the mold After filling, the mold is placed in an oven at 100 ° C. for 4 hours.
  • Example 1 The same procedure as in Example 1 is followed using the constituents and proportions given in Table 1.
  • the material obtained has satisfactory thermal properties.
  • Tg glass transition temperature
  • the glass transition temperature has a significant influence on the thermomechanical behavior because beyond this temperature the material has a rubbery behavior.
  • Thermal conductivity measurements are also performed for temperatures between 20 ° C and 185 ° C. Over this temperature range, the value of the thermal conductivity of the resin is close to 0.55 W / mK. The values obtained are given in Table 3. ⁇ b> Table 3 ⁇ / b> Conductivity at different temperatures Temperature (° C) ⁇ (W / mK) 25 0.531 30 0,540 50 0.564 75 0,590 100 0.623 125 0.641 150 0.646 170 0,632 185 0.629
  • the figure 2 illustrates the loss of mass (in%) of this material, at 150 ° C, as a function of time (in hours).
  • a half-hour fire test at 800 ° C was also performed on two blocks of 240 mm in diameter and 60 mm in height.
  • the flame was in direct contact with the material while the second block was protected by a steel sheet 1 mm thick.
  • the self-extinguishing resin is immediate after removal of the torch.
  • the thickness of carbonized material is 9 mm.
  • the thickness of charred material is 2 mm.
  • the material of the invention has very interesting properties for the neutron shielding and the maintenance of sub-criticality during the assembly transport of irradiated nuclear fuels.

Landscapes

  • Dispersion Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Measurement Of Radiation (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Sealing Material Composition (AREA)
  • Polymerisation Methods In General (AREA)

Claims (15)

  1. Material zur Neutronenabschirmung und zur Beibehaltung der Unterkritikalifiät, umfassend ein ungesättigtes Polyester-Harz, wenigstens eine anorganische Bor-Verbindung sowie wenigstens eine anorganische Wasserstoff-Verbindung in derartigen Mengen, dass die Bor-Konzentration 4x1021 bis 25x1021 Atome/cm3 und die Wasserstoff-Konzentration 3x1022 bis 5,5x1022 Atome/cm3 beträgt.
  2. Material nach Anspruch 1, bei dem die Mengen der anorganischen Bor-Verbindung und der anorganischen Wasserstoff-Verbindung derart sind, dass die Bor-Konzentration 9x1021 bis 15x1021 Atome/cm3 und die Wasserstoff-Konzentration 4x1022 bis 5x1022 Atome/cm3 beträgt.
  3. Material nach Anspruch 1, bei dem die anorganische Bor-Verbindung ausgewählt ist aus der Gruppe gebildet durch Borsäure H3BO3, Zinkborate Zn2O14,5H7B6, Zn4O8B2H2 und Zn2O11B6, Kolemanit Ca2O14B6H10, Borkarbid B4C, Bornitrid BN und Boroxid B2O3.
  4. Material nach Anspruch 1 oder 2, umfassend zwei anorganische Bor-Verbindungen, gebildet durch ein Zinkborat und Borkarbid.
  5. Material nach einem der Ansprüche 1 bis 4, bei dem die anorganische Wasserstoff-Verbindung ausgewählt ist aus der Gruppe der Aluminiumoxidhydrate und des Magnesiumhydroxids.
  6. Material nach Anspruch 5, bei dem die anorganische Wasserstoff-Verbindung ein Aluminiumoxidhydrat ist.
  7. Material nach einem der Ansprüche 1 bis 6, ferner umfassend Poly(vinylacetat).
  8. Material nach einem der Ansprüche 1 bis 7, ferner umfassend eine organische Wasserstoff-Charge zur Verbesserung der Selbstverlöschungseigenschaften des Materials.
  9. Material nach einem der Ansprüche 1 bis 8, umfassend 25 bis 40 Gewichtsprozent des wärmeausgehärteten ungesättigen Polyester-Harzes, umfassend einen Vinyl-Verdünner.
  10. Material nach einem der Ansprüche 1 bis 9, das eine Dichte ≥ 1,7 aufweist, vorzugsweise von 1,7 bis 1,85.
  11. Material nach einem der Ansprüche 1 bis 10, das wenigstens 9,4x1021 Bor-Atome pro cm3 umfaßt.
  12. Verfahren zur Herstellung eines Materials zur Neutronenabschirmung nach einem der Ansprüche 1 bis 11, das darin besteht, eine Mischung des ungesättigten Polyester-Harzes in Lötung in einem Vinyl-Verdünner mit der/den anorganischen Bor-Verbindung(en) und der/den anorganischen Wasserstoff-Verbindung(en) herzustellen, einen Katalysator und einen Aushärtungsbeschietaniger zu der Mischung hinzuzufügen, die Mischung in eine Form zu gießen und sie in der Form aushärten zu lassen.
  13. Verfahren nach Anspruch 12, bei dem der Vinyl-Verdünner Styrol ist.
  14. Verfahren nach Anspruch 12 oder 13, bei dem die Form eine Verbackung für den Transport und/oder die Lagerung von radioaktiven Produkten ist.
  15. Verpackung für den Transport oder die Lagerung von radioaktiven Produkten, umfassend eine Neutronenabschirmung aus einem Material nach einem der Ansprüche 1 bis 11.
EP02785511A 2001-10-01 2002-09-27 Material zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität mit ungesättigtem polyester als ausgangsmaterial Expired - Lifetime EP1446808B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0112592A FR2830367B1 (fr) 2001-10-01 2001-10-01 Materiau de blindage neutronique et de maintien de la sous-criticite a base de polyester insature
FR0112592 2001-10-01
PCT/FR2002/003307 WO2003030183A2 (fr) 2001-10-01 2002-09-27 Materiau de blindage neutronique et de maintien de la sous-criticite a base de polyester insature

Publications (2)

Publication Number Publication Date
EP1446808A2 EP1446808A2 (de) 2004-08-18
EP1446808B1 true EP1446808B1 (de) 2009-03-25

Family

ID=8867790

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02785511A Expired - Lifetime EP1446808B1 (de) 2001-10-01 2002-09-27 Material zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität mit ungesättigtem polyester als ausgangsmaterial

Country Status (10)

Country Link
US (1) US7524438B2 (de)
EP (1) EP1446808B1 (de)
JP (1) JP2005521859A (de)
KR (1) KR100901151B1 (de)
AT (1) ATE426900T1 (de)
DE (1) DE60231735D1 (de)
ES (1) ES2324904T3 (de)
FR (1) FR2830367B1 (de)
WO (1) WO2003030183A2 (de)
ZA (1) ZA200402341B (de)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2833402B1 (fr) * 2001-12-12 2004-03-12 Transnucleaire Materiau de blindage neutronique et de maintien de la sous- criticite a base de resine vinylester
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
EP2489064A4 (de) 2009-10-13 2014-02-19 Nat Inst Aerospace Associates Mit boronnitrid-nanoröhrchen hergestellte energieumwandlungsmaterialien und boronnitrid-nanoröhrchen-polymer-verbundstoffe
KR101192901B1 (ko) 2010-06-04 2012-10-18 강우석 유연성 및 복원성을 갖는 중성자 방사선 흡수시트, 이로 만든 의복 및 그 제조방법
FR2961940B1 (fr) 2010-06-28 2016-07-29 Constructions Ind De La Mediterranee Cnim Materiau de blindage neutronique, dispositif de stockage et de transport de produits radioactifs et procede de fabrication
US8664630B1 (en) * 2011-03-22 2014-03-04 Jefferson Science Associates, Llc Thermal neutron shield and method of manufacture
WO2013074134A1 (en) * 2011-11-17 2013-05-23 National Institute Of Aerospace Associates Radiation shielding materials containing hydrogen, boron and nitrogen
JP6408392B2 (ja) * 2014-02-28 2018-10-17 三洋化成工業株式会社 中性子線遮へい材用ポリウレタン樹脂形成性組成物
JP6480663B2 (ja) * 2014-02-28 2019-03-13 善則 菅野 中性子遮蔽材
US10026513B2 (en) 2014-06-02 2018-07-17 Turner Innovations, Llc. Radiation shielding and processes for producing and using the same
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
CN104965337A (zh) 2015-07-21 2015-10-07 深圳市华星光电技术有限公司 彩色滤光片的制备方法
JP6935154B2 (ja) * 2019-08-21 2021-09-15 日東電工株式会社 放射線透過抑制フィルム、ならびに該放射線透過抑制フィルムを用いた放射線透過抑制フィルターおよび撮影装置
WO2021252112A1 (en) 2020-05-20 2021-12-16 Neutroelectric, Llc Neutron shielding and radiation absorbing compositions
WO2023125468A1 (zh) * 2021-12-31 2023-07-06 中硼(厦门)医疗器械有限公司 含硼树脂组合物、含硼纤维树脂复合材料及其应用

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2796411A (en) * 1947-01-29 1957-06-18 Raymond E Zirkle Radiation shield
BE567962A (de) 1956-11-02
GB929102A (de) * 1958-07-09
US3133887A (en) 1958-10-06 1964-05-19 Norton Co Neutron shields and methods of manufacturing them
US3261800A (en) * 1960-09-08 1966-07-19 Du Pont Boron nitride incorporated in polymer products
GB1049890A (en) * 1962-11-30 1966-11-30 Albert Ag Chem Werke Improvements in or relating to resins
US3609372A (en) * 1963-06-04 1971-09-28 Marxen Friedrich Shaped polymeric shield against neutron and gamma radiation
US3361684A (en) * 1966-01-18 1968-01-02 Werner H Kreidl Thermosetting resin matrix containing boron compounds of specific size distribution and method of making
FR2092848A7 (en) * 1970-06-24 1972-01-28 Calhene Neutron radiation absorber - of boron cpd in polymer matrix
US3829532A (en) * 1971-08-18 1974-08-13 Standard Oil Co Flame-resistant polyester composition
US3879318A (en) * 1972-06-02 1975-04-22 Rohm & Haas Organic amide containing compositions and process for thickening control of polyesters
US4134937A (en) * 1974-06-12 1979-01-16 Monsanto Research Corporation Polyester resin composition
JPS5933874B2 (ja) * 1979-03-09 1984-08-18 三井造船株式会社 中性子遮蔽材
FR2505080B1 (fr) * 1981-04-29 1987-12-18 Marc Robert Parois anti-atomiques, neutroniques et polluants chimiques
EP0108622B1 (de) 1982-11-08 1988-03-02 Mitsubishi Rayon Co., Ltd. Synthetische Harzmasse und Verfahren zu ihrer Herstellung
JPS59126296A (ja) 1983-01-06 1984-07-20 三井・デュポン　ポリケミカル株式会社 積層複合物
EP0119781A1 (de) * 1983-03-04 1984-09-26 KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. Neutronenschutzmaterial
FR2546331A1 (fr) * 1983-05-20 1984-11-23 Robatel Slpi Perfectionnements aux materiaux hydrogenes de protection antineutronique
JPS6065032A (ja) 1983-09-20 1985-04-13 Sumitomo Bakelite Co Ltd 熱硬化性樹脂成形品の製造方法
GB8827531D0 (en) 1988-11-25 1988-12-29 Du Pont Canada Highly filled compositions
JPH06180389A (ja) * 1992-12-11 1994-06-28 Sanoya Sangyo Kk γ線、Ｘ線及び中性子線の同時遮蔽が可能な放射線遮蔽材
PL303058A1 (en) 1994-04-19 1995-10-30 Marceli Cyrkiewicz Method of obtaining plastics of high chemical resistance and mechanical strength as well as plastics of high chemical resistance and mechanical strength
JP3150672B1 (ja) * 1999-10-13 2001-03-26 三菱重工業株式会社 中性子遮蔽体およびこれを用いたキャスク
DE19955192C2 (de) 1999-11-16 2003-04-17 Arntz Beteiligungs Gmbh & Co Verfahren zur Herstellung eines Strahlenschutzmaterials
JP3951685B2 (ja) * 2001-11-30 2007-08-01 株式会社日立製作所 中性子遮蔽材及び使用済み燃料収納容器
FR2833402B1 (fr) * 2001-12-12 2004-03-12 Transnucleaire Materiau de blindage neutronique et de maintien de la sous- criticite a base de resine vinylester
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

Also Published As

Publication number Publication date
ES2324904T3 (es) 2009-08-19
FR2830367B1 (fr) 2003-12-19
ZA200402341B (en) 2004-10-07
US7524438B2 (en) 2009-04-28
JP2005521859A (ja) 2005-07-21
EP1446808A2 (de) 2004-08-18
ATE426900T1 (de) 2009-04-15
WO2003030183A3 (fr) 2003-12-04
KR100901151B1 (ko) 2009-06-04
US20050001205A1 (en) 2005-01-06
DE60231735D1 (de) 2009-05-07
WO2003030183A2 (fr) 2003-04-10
FR2830367A1 (fr) 2003-04-04
KR20040068919A (ko) 2004-08-02

Similar Documents

Publication Publication Date Title
EP1446808B1 (de) Material zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität mit ungesättigtem polyester als ausgangsmaterial
CN1133675C (zh) 聚氧亚甲基共聚物及其组合物
EP1454327B1 (de) Werkstoff auf basis von vinylesterharz zur neutronenabschirmung und zur aufrechterhaltung der unterkritikalität
US6606852B1 (en) Rocket motor insulation containing hydrophobic particles
EP1418593B1 (de) Neutronenschutzmaterial für unterkritische Aufbewahrung, seine Herstellung und seine Verwendung
Tang et al. Preparation of microcapsulated ammonium polyphosphate, pentaerythritol with glycidyl methacrylate, butyl methacrylate and their synergistic flame‐retardancy for ethylene vinyl acetate copolymer
WO2020079352A1 (fr) Matériau composite de blindage neutronique et de maintien de la sous-criticité, son procéde de fabrication et ses utilisations
CN108250787A (zh) 一种木塑材料及其制备方法
Zhang et al. Comparative mechanical, fire‐retarding, and morphological properties of high‐density polyethylene/(wood flour) composites with different flame retardants
EP1335143A2 (de) Zusammengesetztes Zapfenlager und Verfahren zur Herstellung desselbigen
Liang et al. Photopolymerization and thermal behavior of phosphate diacrylate and triacrylate used as reactive‐type flame‐retardant monomers in ultraviolet‐curable resins
FR3124018A1 (fr) Matériau composite de blindage neutronique et de maintien de la sous-criticité, son procédé de fabrication et ses utilisations
CN114230860B (zh) 一种阻燃十溴二苯乙烷复合物及其制备方法
KR100635966B1 (ko) 난연성이 향상된 밀봉용 수지조성물
BE719422A (de)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040317

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TN INTERNATIONAL

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REF Corresponds to:

Ref document number: 60231735

Country of ref document: DE

Date of ref document: 20090507

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2324904

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090325

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090901

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090325

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090325

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20091229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090325

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20140915

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20150813

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BG

Payment date: 20150817

Year of fee payment: 14

Ref country code: DE

Payment date: 20150914

Year of fee payment: 14

Ref country code: CH

Payment date: 20150904

Year of fee payment: 14

Ref country code: FI

Payment date: 20150817

Year of fee payment: 14

Ref country code: GB

Payment date: 20150921

Year of fee payment: 14

Ref country code: CZ

Payment date: 20150819

Year of fee payment: 14

Ref country code: ES

Payment date: 20150928

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20150916

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20150915

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20150930

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60231735

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160927

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160928

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20161001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20160927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170401

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160927

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160927

Ref country code: BG

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170406

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150927

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160928

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20180622

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20210930

Year of fee payment: 20