CA2024879C - Neutron-absorbing materials - Google Patents

Neutron-absorbing materials

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Publication number
CA2024879C
CA2024879C CA002024879A CA2024879A CA2024879C CA 2024879 C CA2024879 C CA 2024879C CA 002024879 A CA002024879 A CA 002024879A CA 2024879 A CA2024879 A CA 2024879A CA 2024879 C CA2024879 C CA 2024879C
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CA
Canada
Prior art keywords
neutron
absorbing material
boron
polyethylene
boron carbide
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 - Fee Related
Application number
CA002024879A
Other languages
French (fr)
Other versions
CA2024879A1 (en
Inventor
Josef Berzen
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.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Publication of CA2024879A1 publication Critical patent/CA2024879A1/en
Application granted granted Critical
Publication of CA2024879C publication Critical patent/CA2024879C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F1/00Shielding characterised by the composition of the materials
    • G21F1/02Selection of uniform shielding materials
    • G21F1/10Organic substances; Dispersions in organic carriers
    • G21F1/103Dispersions in organic carriers
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21CNUCLEAR REACTORS
    • G21C5/00Moderator or core structure; Selection of materials for use as moderator
    • G21C5/12Moderator or core structure; Selection of materials for use as moderator characterised by composition, e.g. the moderator containing additional substances which ensure improved heat resistance of the moderator
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/38Boron-containing compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00Energy generation of nuclear origin
    • Y02E30/30Nuclear fission reactors

Abstract

The invention relates to boron-containing polyethylene having a mean molecular mass of at least 2.5 x 106 g/mol as a neutron-absorbing material.

Description

Neutron-absorbinq materials The invention relates to a neutron-absorbing material. It is composed of ultrahigh molecular weight polyethylene in which a boron compound, preferably boron carbide B4C, is embedded.

In contrast to alpha- and beta-particles, neutrons do not have a charge and therefore cannot lose energy by ener-gization on passing through matter. Consequently, their penetration power is extremely high. Neutrons are subject exclusively to the action of the nuclear forces and are scattered on atomic nuclei. According to the collision laws, the energy releases to the body undergoing a collision are the greater in such scattering processes, the more similar the mass thereof is to the mass of the colliding body. Therefore, a bundle of neutron beams, which penetrates lead plates of several meters thickness without significant attenuation, is very greatly attenu-ated when passing through hydrogen-contAining substances of a few cm thickness. On average, the energy is reduced to l/e on collision with a proton, whereas the energy release to atomic nuclei of higher mass is less, due to inelastic collision. It is known from the literature that on average 18 collisions are necessary in hydrogen and on average 114 collisions are necessary in carbon in order to brake a neutron down to thermal energy. ,hese thermal, i.e. slow neutrons can then be completely absorbed by elements of high cross-section, such as cadmium or boron.

In neutron absorption, binding energy is released in the form of secondary gamma-radiation. It depends on the absorber material and can be of considerable magnitude.
Thus, the gamma-radiation energy is 6 MeV in the absorp-tion of neutrons by cadmium, 2.2 MeV in that by hydrogen and only 0.5 MeV in that by boron.

- As the materials which protect against neutron radiation, especially water and paraffins as well as plastics cont~in;ng significant quantities of hydrogen, such as polyethylene, polyesters and polyamides, are used.

Thus, according to the teaching of German Auslegeschrift 1,297,869, moldings of thermoplastic or thermosetting plastics, in which the carbon/hydrogen ratio or the residual atom/hydrogen ratio is in the range from 1 : 2.1 to 2 : 1 and the molecular weight of which is less than 200,000, are used for protection against gamma-radiation and neutron radiation. Such plastics can be from the classes of high- and low-pressure polyethylenes, poly-propylenes, alkylene/propylene or alkylene/butylenecopolymers, polyamides and polyesters.

In German Auslegeschrift 1,162,694, a neutron-absorbing material is described, in which granulated polyethylene is embedded in a hydrogen-cont~ining liquid which remains liquid or cures to give a plastic.

However, the known neutron-absorbing materials have properties which restrict their applicability. Thus, although plastics have a low density, their processibil-ity frequently causes difficulties. Moreover, their mechanical behavior does not always meet all requirements and their heat resistances are frequently unsatisfactory.

The invention is based on the object of providing a neutron-absorbing material which cannot only be processed by conventional methods but is also mechanically strong and resistant to thermal influences and has a low density.

This object is achieved by a neutron-absorbing material, in which boron is embedded in polyethylene. It is defined by a mean molecular mass, measured by viscometry, of the predominantly linear polyethylene of at least 2.5 x 106 g/mol.

ri ne~r polyethylenes having a mean molecular mass of at least 2.5 x 106 g/mol and up to 1 x 107 g/mol are also `~ ~ 3 ~ 202487 q described as ultrahigh molecular-weight polyethylenes (PE-UHMW). The molecular mass quantified above is under-stood to mean the values determined by viscometry. A
method for measuring them is described, for example, in CZ-Chemietechnik 4 (1974), 129 et seq.

The preparation of PE-UHMW is known. It can be carried out by various processes. A proven process, which is operated under low pressure with mixed catalysts of titanium(III) halides and aluminum-organic compounds, is described in German Auslegeschrift 2,361,508.

Ultrahigh molecular-weight polyethylene is distinguished by a number of advantageous physical properties. Its high wear resistance, its low coefficient of fraction against other materials, its excellent toughness behavior and its remarkable resistance to numerous chemicals should be singled out.

PE-UHMW having molecular masses of between 2.5 x Io6 g/mol and 8 x 106 g/mol, especially 3 x 106 g/mol and 6 x 106 g/mol has proven particularly suitable for the neutron-absorbing material according to the invention.

In order to ensure that no long-lived radioactive iso-topes are formed by the nuclear process taking place on neutron capture, the polyethylene must be substantially free of impurities. In particular, the compounds still present from the preparation, which were used as cata-lysts or constituents of catalysts, must not exceed a content of 200 ppm by weight, preferably 150 ppm by weight, relative to the polymer.

Furthermore, it is advisable to protect the PE-UHMW from effects of heat, light and oxidation. Examples of com-pounds, alone or in combination, which have proven suitable as stabilizers are as follows: 4,4'-thiobis-(3-methyl-6-tertiary-butyl-1-phenol), dilauryl thiodipropionate, distearyl thiodipropionate, tetrakis-[methylene-(3,5-ditertiary-butyl-4-hydroxy-hydro-cinn~m~to)]-methane, n-octadecyl-~-(4~-hydroxy-3,5~-ditertiary-butylphenyl)-propionate and glycol bis-[3~3-bis-(4'-hydroxy-3'-tertiary-butylphenyl)-butanoate~. They are in general added in quantities of from 0.1 to 0.2 %
by weight, relative to the total mixture. The addition of antioxidants is important for the reason that polyethyl-ene is oxidized in the presence of oxygen under the action of gamma-radiation. It is then transformed into low molecular-weight, waxy products, embrittles and loses its extensibility.

As a further constituent, the novel material contains boron in the form of boron compounds such as boric acid (H3BO3). Boron carbide B4C has proven particularly suit-able. Boron nitride is less suitable because of its thermal properties. Mixtures of different boron compounds can also be used, but a chemically homogeneous substance is preferred. Boron carbide is used in the commercially available purity. For use of the novel neutron-absorbing material in practice, it is essential that it is homo-geneous. It is therefore advisable to incorporate boron carbide, which is as finely dispersed as possible, into the polyethylene, i.e. boron carbide of a particle size which corresponds to the size of the polyethylene particles. It has proven advantageous to use boron carbide of a particle size of from 10 to 200 ~m and especially from 20 to 80 ~m. This has the result that no segregation of the components occurs during the process-ing of the material and no irregularities arise in itsstructure. Surprisingly, the outstanding mechanical properties of PE-UHMW are hardly impaired by the addition of boron carbide, and certain physical features, e.g. the attrition behavior, are even improved.

The boron carbide content in the novel material depends on the layer thickness in which it is used. It has been found that, in the case of thin thicknesses of material, i.e. at layer thicknesses of up to 5 mm, the screening properties are markedly improved with increasing B4C
content. At layer thicknesses above about 20 mm, an increase in the B4C concentration in the material to more than 1 %, relative to the material, hardly has any further effect on the absorption behavior. At a given degree of attenuation, the required layer thickness for absorption of thermal neutrons can therefore be deter-mined via the B4C content.

Allowing for the desired material properties, the prepar-ation and the processibility of the novel material, it is advisable to adjust the B4C concentration to values of from 5 to 50 % by weight, preferably from 10 to 40 % by weight and especially from 20 to 30 % by weight, each relative to polyethylene cont~ining boron carbide.

The neutron-absorbing material of the invention is prepared by homogeneously ~ixing the starting materials PE-UHMW, boron compound and, if desired, additives in a suitable mixer and subsequently sintering the mixture under pressure at temperatures of from 180 to 250C, especially from 200 to 230C. The sintering pressure is from 5 to 10 MPa, especially from 8 to 10 MPa. Cooling is also carried out under pressure, and 3 to 5 MPa, prefer-ably 4 to 5 MPa, have proven suitable. The sintering and cooling times depend on the thickness of the material and on the filler content. Thus, the sintering time is, for example, 5 hours for plates of 60 mm thickness, which are composed of 70 % by weight of polyethylene and 30 % by weight of B4C.

The novel material can be mechanically worked in a conventional manner, for example drilled, milled and sawn, and allowance must of course be made here for the properties of the boron carbide, in particular its hardness; it can be formed by pressing.

The invention is explained in more detail in the - 6 - 202487~
following example.

ExamPle For the irradiation tests, laboratory plates of PE-UHMW, having a molecular mass of about 3 x 106 g/mol ~R~(Hostalen GUR 412) with 1, 5, 10, 20 and 30 % by weight of boron carbide were prepared in different thicknesses of 1,5,20 and 60 mm under standard conditions (pressure on sintering 5 MPa, pressure on cooling 10 MPa, sintering and/or cooling time depending on the thickness of mater-ial and on the filler content). Unfilled PE-UHMW of the same molecular mass and in the same dimensions was used as a comparison.

-~3 The boron carbide used was the commercial product TETRABOR F 280 from Elektroschmelzwerk Kempten GmbH, ~, having a particle size of 22-59 ~m.

For preparing the laboratory plates, the particular components were homogeneously mixed in a laboratory mixer.

The samples were irradiated with thermal neutrons of an energy less than 1 eV.

The neutron absorption coefficients were calculated by the following equation:

~ tot X
o where:
X thickness of the sample ~tot total absorption coefficient which contains all the absorption components and scattering components in PE and boron.

* ~e.--~A~

Io counting rate of the neutron beam, measured before the use of every sample thickness, in order to eliminate changes in the reactor power.

I attenuated counting rate at layer thickness X of the sample.

The measured results show that, at low layer thicknesses, the screening of thermal neutrons by the novel material increases with increasing B4C content. At large layer thicknesses, B4C concentrations above about 1 % by weight (relative to the PE-UHMW filled with B4C) do not lead to any improvement in the absorption behavior. Thus, the attenuation is then independent of the boron carbide concentration.

~ - 8 - 2024879 Material Zero Counting ~tot thickness counting rate I (mm~l) (mm) rate I~ with S (particles/ sample second) (parti-cles/sec.) Hostalen GUR 1.08 5270 4172 0.2164 5.25 5302 1881 0.1974 20.1 5269 264.3 0.1489 60.2 5243 11.303 0.1020 + 1 % B4C 1.11 5263 4100 0.2250 5.24 5244 1490 0.2401 20.3 5309 73.15 0.2111 60.2 5249 1.155 0.1399 + S % B4C 1.06 5252 3654 0.3424 4.76 5237 792.7 0.3967 19.8 5229 5.497 0.3464 58.8 5284 1.021 0.1454 + 10 % B4C 1.16 5248 3029 0.4736 4.95 5276 357.1 0.5440 19.7 5236 1.573 0.4117 60.1 5298 0.919 0.1441 + 20 % B4C 1.00 5270 2484 0.7522 5.02 5257 83.44 0.8253 21.2 5225 0.986 0.4045 60.3 5247 0.862 0.1445 + 30 % B4C 1.03 5297 1904 0.9934 5.07 5202 28.87 1.0245 20.7 5231 0.966 0.4153 60.9 5298 0.856 0.1434 A comparison of the measured value shows that the absorp-tion coefficients at small thicknesses are considerablyhigher than those at thicknesses of > 20 mm. This be-havior can be explained by the fact that the thermal neutrons are almost completely absorbed in thinn~r layers and a small proportion of fast neutrons cont~ine~ in the bundle of neutron beams is braked in thicker layers of material to lower speeds and then absorbed. A substan-tially small absorption coefficient must be expected for these thermallized, originally fast neutrons.

In the table which follows, the particular material thickness, at which 95 % of the thermal neutrons are absorbed, is indicated in accordance with the equation for calculating the absorption coefficients. This cal-culation was based on the averages of the absorptioncoefficients for thin material thicknesse (s 5 mm) from the absorption measurements for each B4C content.

Layer thickness~tot (mm~l) (mm) at 95 absorption PE-UHMW 13.6 0.22 (Molecular mass:
about 4 x 106 mol/g) + 1 % B4C 12.0 0.25 + 5 % B4C 7-7 0 39 + 10 % B4C 5.7 0.53 + 20 % B4C 3.8 0.80 + 30 % B4C 3.0 1.02 It will be clearly seen that the layer thickness is considerably reduced with increasing B4C content.

Claims (14)

1. A neutron-absorbing material comprising boron embedded in predominantly linear polyethylene, wherein the mean molecular mass, measured by viscometry, of the predominantly linear polyethylene is at least 2.5 x 106 g/mol.
2. A neutron-absorbing material as claimed in claim 1, wherein the molecular mass of the polyethylene is 2.5 x 106 to 8 x 106 g/mol.
3. A neutron-absorbing material as claimed in claim 1, wherein the molecular mass of the polyethylene is 3 x 106 to 6 x 106 g/mol.
4. A neutron-absorbing material as claimed in claim 1 wherein the polyethylene contains boron in the form of boron carbide B4C.
5. A neutron-absorbing material as claimed in claim 2 wherein the polyethylene contains boron in the form of boron carbide B4C.
6. A neutron-absorbing material as claimed in claim 4 wherein the boron carbide has a particle size of from 10 to 200 µm.
7. A neutron-absorbing material as claimed in claim 5 wherein the boron carbide has a particle size of from 20 to 80 µm.
8. A neutron-absorbing material as claimed in any one of claims 1 to 3, wherein the polyethylene contains boron in the form of boron carbide B4C and the concentration of boron carbide is 5 to 50% by weight relative to the neutron-absorbing material.
9. A neutron-absorbing material as claimed in any one of claims 1 to 3, wherein the polyethylene contains boron in the form of boron carbide B4C and the concentration of boron carbide is 10 to 40% by weight relative to the neutron-absorbing material.
10. A neutron-absorbing material as claimed in any one of claims 1 to 3, wherein the polyethylene contains boron in the form of boron carbide B4C and the concentration of boron carbide is 20 to 30% by weight relative to the neutron-absorbing material.
11. A neutron-absorbing material as claimed in claim 8 which contains a stabilizer.
12. A neutron-absorbing material as claimed in claim 10 which contains a stabilizer.
13. A process for preparing a neutron-absorbing material as claimed in any one of claims 1 to 7, which comprises mixing polyethylene and boron compound, sintering the mixture under pressure at a temperature of from 180 to 250°C, at a pressure of from 5 to 10 MPa, and cooling the sintered product under a pressure of from 3 to 5 MPa.
14. A process according to claim 13 wherein the mixture is sintered at a temperature from 200 to 230°C at a pressure of 8 to 10 MPa and the sintered product is cooled at a pressure of from 4 to 5 MPa.
CA002024879A 1989-09-15 1990-09-07 Neutron-absorbing materials Expired - Fee Related CA2024879C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3930887.1 1989-09-15
DE3930887A DE3930887A1 (en) 1989-09-15 1989-09-15 NEUTRON ABSORBENT MATERIAL

Publications (2)

Publication Number Publication Date
CA2024879A1 CA2024879A1 (en) 1991-03-16
CA2024879C true CA2024879C (en) 1995-02-14

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Family Applications (1)

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CA002024879A Expired - Fee Related CA2024879C (en) 1989-09-15 1990-09-07 Neutron-absorbing materials

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EP (1) EP0417598B1 (en)
JP (1) JPH03107797A (en)
KR (1) KR930011108B1 (en)
AT (1) ATE120300T1 (en)
CA (1) CA2024879C (en)
DE (2) DE3930887A1 (en)
ES (1) ES2071719T3 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4131274C2 (en) * 1991-09-20 1995-05-11 Braas Gmbh Neutron absorbing plastic sheet
KR100395886B1 (en) * 1999-10-29 2003-08-27 한국수력원자력 주식회사 Ultra-Low Level Shielder of External Radiation for a Gamma-ray Spectroscopy System
JP5609048B2 (en) * 2009-09-09 2014-10-22 独立行政法人日本原子力研究開発機構 Neutron beam absorbing sheet
JP2013205359A (en) * 2012-03-29 2013-10-07 Toshiba Corp Gelatinous neutron absorber and molten core recovery method
CN110767340B (en) * 2019-10-10 2023-03-03 中广核研究院有限公司 Novel composite shielding material of tungsten boron crosslinked polyethylene with high tungsten content

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1337399A (en) * 1962-07-30 1963-09-13 Fonderie De Gentilly Protective material against ionizing radiation
DE1297869B (en) * 1963-02-08 1969-06-19 Huels Chemische Werke Ag Manufacture of molded bodies for protection against gamma and neutron radiation
US4123392A (en) * 1972-04-13 1978-10-31 Chemtree Corporation Non-combustible nuclear radiation shields with high hydrogen content
DE3225788A1 (en) * 1982-05-07 1984-01-12 Selim Dipl.-Ing. 8000 München Mourad Building material and process for the manufacture thereof
JPS58201099A (en) * 1982-05-20 1983-11-22 電気化学工業株式会社 Structure for neutron shield
JPS60194394A (en) * 1984-03-15 1985-10-02 三井化学株式会社 Shielding material for neutron

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Publication number Publication date
DE59008749D1 (en) 1995-04-27
ATE120300T1 (en) 1995-04-15
CA2024879A1 (en) 1991-03-16
DE3930887A1 (en) 1991-03-28
EP0417598B1 (en) 1995-03-22
EP0417598A1 (en) 1991-03-20
ES2071719T3 (en) 1995-07-01
JPH03107797A (en) 1991-05-08
KR910007003A (en) 1991-04-30
KR930011108B1 (en) 1993-11-24

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