CN1084517C - Wide-temp. neutron and gamma ray shielding material - Google Patents
Wide-temp. neutron and gamma ray shielding material Download PDFInfo
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- CN1084517C CN1084517C CN96114166A CN96114166A CN1084517C CN 1084517 C CN1084517 C CN 1084517C CN 96114166 A CN96114166 A CN 96114166A CN 96114166 A CN96114166 A CN 96114166A CN 1084517 C CN1084517 C CN 1084517C
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- ray shielding
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The present invention relates to a neutron and gamma ray shielding material which is characterized in that the material comprises the following substances: heat-resistant polymers, shielding materials, silicane coupling agents, anti-oxidant, cross-linking agents and reinforcement fibers, which respectively accounts for 16 to 60 wt%, 30 to 80 wt%, 0.1 to 1.3 wt%, 0.03 to 0.7 wt%, 0.1 to 1 wt% and 2 to 15 wt% of the mixture, wherein the average grain size of the shielding materials is 1 to 40 mu m. The shaping body of the material of the present invention does not distort within-25 to 190 DEG C, and is shock and vibration resistant; the screening factor of the present invention to thermal neutrons reaches 80 to 98%, and secondary radiation does not exist; the present invention is especially applicable to shield pads used in logging instruments.
Description
The present invention relates to a kind of neutron and gamma ray shielding material.
Existing neutron and gamma ray polymerization thing shielding material (hereinafter to be referred as shielding material), general with polymkeric substance such as tygon, polypropylene, polyoxyethylene, polyurethane with make after neutron and gamma ray shielding material mix, open as the Jap.P. spy and just reported among the clear 56-131649 that the use Corvic mixes the method for shielding material as described in the manufacturing with inorganic boride.The serviceability temperature scope of application of this shielding material is narrow, fusing point is on the low side, about 150 ℃, promptly take place softening, and in hardening and crisp below 0 ℃, not shock resistance and vibration can not be satisfied the needs in the practical application, as the shield that uses on the well logger, requirement is used in-25-180 ℃ scope, and certain shock resistance and anti-vibration performance will be arranged.For solving high temperature resistant problem, have the human inorganics to make shielding material, as Japanese patent laid-open 4-143696 reported a kind of use inorganic silicic acid calcium as cementing agent with add after metal oxide mixes water more evenly mixing produce the method for high temperature shielding material.Though this inorganic material is high temperature resistant but do not have calenderability, anti-vibration and shock resistance are still poor.
The purpose of this invention is to provide and a kind of neutron and gamma-rays are not reduced shield effectiveness, neutron that Applicable temperature is wideer and gamma ray shielding material, wide temperature neutron and gamma ray shielding material are called in letter, its moulded products is indeformable in-25-190 ℃ temperature range, and has certain shock resistance and anti-vibration performance.
The objective of the invention is following realization: described wide temperature (Applicable temperature is--25-190 ℃) neutron and gamma ray shielding material comprise that following substances forms:
Heat-resistant polymer accounts for the 16-60% of mixture weight (together following);
Neutron and gamma ray shielding material, mean grain size are 1-40 μ m, account for 30-80%, and wherein the gamma ray shielding material should account for neutron and gamma ray shielding material 10-33.3%;
Silane coupling agent accounts for 0.1-1.3%;
Antioxidant accounts for 0.03-0.7%;
Crosslinking chemical accounts for 0.1-1%;
Fortifying fibre accounts for 2-15%,
Described heat-resistant polymer is a kind of in polyphenylene sulfide, polyetheretherketone, polyethersulfone, polyarylsulfone, the polyimide.
The base-material of shielding material of the present invention adopts heat-resistant polymer.These heat-resistant polymers have good thermal adaptability, use heat-resistant polymer to make base-material and lay a good foundation for preparing wide temperature neutron and gamma ray shielding material.For the compatibility of improving itself and neutron and gamma ray shielding material (hereinafter to be referred as shielding material) and dispersed, prevent its oxidation and degraded in process, selected suitable silane coupling agent and antioxidant respectively for use, guaranteed that shielding material has than the prior art temperature applicability of wide region more under not reducing neutron and gamma ray shielding effect situation; Also add fortifying fibre and crosslinking chemical in the mixture simultaneously, strengthened the shock resistance and the freedom from vibration of shielding material effectively; For making shielding material moulding facility, also added proper amount of lubricating agent in the mixture, can make shielding material make the shield of the multiple shape that is suitable in the reality.Prove through actual measurement: the straight shield through 52mm length 90mm that the present invention makes can reach 80-98% to thermal neutron shield ratio, and does not have secondary radiation behind the intercept neutrons; Gamma ray shielding rate to 0.5-0.9mw can reach 20-65%; Temperature applicable range (formed body is indeformable) is-25-190 ℃, shock resistance preferably and anti-vibration performance are arranged simultaneously.
The base-material of shielding material of the present invention adopts heat-resistant polymer.The heat-resistant polymer glass transition temperature is than higher, and thermal change type temperature is also very high, and what have reaches more than 200 ℃, has higher serviceability temperature, and can be low temperature resistant, still keeps certain structure intensity about-100 ℃.Because these heat-resistant polymers have good thermal adaptability, use them to make base-material and lay a good foundation for preparing wide temperature neutron and gamma ray shielding material.Described heat-resistant polymer is a kind of in polyphenylene sulfide, polyetheretherketone, polyethersulfone, polyarylsulfone, the polyimide.
The mean grain size of neutron that the present invention uses and gamma ray shielding material is 1-40 μ m, and it accounts for the 30-80% of mixture weight, and wherein the gamma ray shielding material accounts for the 10-50% of neutron and gamma ray shielding substance weight.Described neutron ray shielding material is any one in boron carbide, boron nitride, boric acid, the boron oxide, and described gamma ray shielding material is a kind of in plumbous plumbate, lead chloride, lead acetate, bismuth chloride, bismuth oxide, tungsten powder, the barium sulphate.
The present invention has used the compatibility and the dispersiveness of coupling agents to improve heat-resistant polymer and described shielding material, makes it have uniform radiation proof function.Described coupling agent is a silane coupling agent, as choosing a kind of in γ-glycidoxypropyltrimewasxysilane, γ-methacryloxy trimethoxy silane, N-β-(the amino-ethyl)-gamma-amino propyl trimethoxy silicane etc.Coupling agent shared weight in mixture is 0.1-1.3%.
The present invention is for preventing that high temperature polymer from process oxidation taking place and antioxidant has been added in degraded.The antioxidant that uses is 4,4 '-Ding fork two (3-methyl-6 tert-butyl phenol), 2,6-BHT (antioxidant 264), styrenated phenol, 1,1,3-three (2 methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA), 1,3,5-trimethyl-2,4,6--three (3,5-di-t-butyl-44-hydroxybenzyl) benzene (antioxidant 330), 4, two (4 hydroxyls 3,5-di-t-butyl phenoxy group) the 2 n-octyl sulfo-s-1,3 of 6-, a kind of in the 5-triazine etc., the addition of antioxidant is 0.03-1%.
The present invention has also added crosslinking chemical for further improving through the cohesiveness of shielding material, fortifying fibre and heat-resistant polymer after the coupling agent treatment.The crosslinking chemical that uses is 4,4 '-diaminodiphenylmethane bismaleimides (BMI), m-phenylene diamine, right-benzene dimethylamine, 4,4 '-diaminodiphenyl-methane, 4,4 '--diamino-diphenyl sulfone, 1, two (aminomethyl) cyclohexanes of 3-, 3,3 '-two chloro-3,4 '-diaminodiphenyl-methane, 2,4, a kind of in 6-three (dimethylamino methyl) phenol etc.The ratio that crosslinking chemical uses is 0.1-1%.
The present invention has added fortifying fibre especially for the serviceability temperature scope that improves shielding material and shock resistance, anti-vibration performance.The fortifying fibre that uses is a kind of in glass fibre or the carbon fiber.The addition of fortifying fibre accounts for the 2-15% of mixture weight; Fibre length is used with after should cutting into 5-10mm.Fibre length is too short, and humidification is lower; Long, then unfavorable mixing.
The present invention fully mixes for making heat-resistant polymer and shielding material, and the easy demoulding when making shield, has also added lubricant.The lubricant that uses is N, a kind of in N '-ethylene bis stearamide, oleamide, stearic acid, lithium stearate, calcium stearate, the solid paraffin etc.The addition of lubricant accounts for the 0.1--0.6% of mixture weight.
The manufacture method of wide temperature neutron of the present invention and gamma ray shielding material is: at first heat-resistant polymer, neutron and gamma ray shielding material are carried out desiccant dehumidification, it is standby that fortifying fibre is cut into 5-10mm; The neutron and gamma ray shielding material, fortifying fibre, the coupling agent that take by weighing are in proportion put into the mixer high-speed stirred in the lump and mixed; Put into heat-resistant polymer, antioxidant, crosslinking chemical and lubricant high-speed stirred after material to be mixed is static to mixing; The mixture that mixes is put into the vacuum drying box drying, and the control water cut is less than 0.1%; The mixture of oven dry is put into the dual-screw-stem machine banburying, is extruded and pelletizing, makes shielding material of the present invention.
If moulding after can the material pelletizing of the present invention that above-mentioned manufacturing is good putting into vacuum drying chamber and carrying out dried, is put into single-screw extrusion machine again and is melt extruded; Extruded stock injects mould according to actual needs, and mould is filled to finish and is placed on extrusion forming on the pressing machine; Cooling and demolding after the shield moulding.
The formed body of material of the present invention is specially adapted to make the shield that uses on the well logger, can use down in temperature range of its requirement (--25--180 ℃) and condition of work (shock-resistant and vibration), has good shielding neutron and gamma-ray effect.
Provide several embodiments of the present invention below:
Embodiment 1:
After mean grain size 2 μ m account for the plumbous plumbate drying that the boron carbide of mixture 28% weight and mean grain size 20 μ m account for mixture weight 4% (account for shielding material 12.5%), add 0.2% weight γ-glycidoxypropyl trimethoxy silane, and the long glass fibre compound of 13% weight 8mm, mixed 15 minutes in airtight high-speed mixer high speed, after static 5 minutes, after adding the crosslinking chemical m-phenylene diamine and 0.4% weight lubricant stearic acid of polyphenylene sulfide, 0.6% antioxidant 264,0.8% weight of 53% weight drying; High-speed stirred was mixed 15 minutes once more, after mixed material places the vacuum drying box drying, put into diameter 30mm parallel double-screw extruder banburying extruding pelletization, pelletizing is placed the vacuum drying box drying again, the control water cut is less than after 0.1%, putting into single screw extrusion machine again melt extrudes, extruded stock injects the mould that basic configuration is of a size of straight 52mm length 90mm (using the physical size of shield basic configuration on the aforementioned well logger), treating that mould fills up is placed on moulding on the pressing machine, cooling and demolding after the moulding obtains well logger and uses shield.After tested, this shield is 85% to the thermal neutron shielding rate axially, is 20% to 0.5-0.8mw gamma ray shielding rate, does not have secondary radiation behind the intercept neutrons, and indeformable in-25-190 ℃ scope, has shock resistance preferably and freedom from vibration simultaneously.
Embodiment 2:
Mean grain size is the 36% weight boron nitride of 35 μ m, after mean grain size is 10% weight (account for shielding material 21.7%) the bismuth oxide drying of 2 μ m, γ-methacryloxy trimethoxy silane and 5.7% weight 5mm long carbon fiber with 0.4% weight, after mixing by the condition of embodiment 1 and step, add 47% weight polyether sulfone powder, 0.3% weight antioxidant CA, 0.4% weight is right-benzene dimethylamine and lithium stearate 0.2%, condition and step by embodiment 1 mix, and mix the back material and make described shield by condition and the step of embodiment 1.After tested, the shield that makes is 90% to the thermal neutron shielding rate axially, is 48% to 0.5-0.8mw gamma ray shielding rate, does not have secondary radiation behind the intercept neutrons, and indeformable in-25-190 ℃ scope, has shock resistance preferably and freedom from vibration simultaneously.
Embodiment 3:
After mean grain size is the 50% weight boron oxide of 10 μ m and 25% weight that mean grain size is 5 μ m (account for shielding material 33.3%) bismuth oxide drying, with 1.2% weight N-B (amino-ethyl)-γ--the glass fibre that TSL 8330 and 3% weight 5mm are long, condition and step by embodiment 1 mix it, add 20% weight polyarylsulfone again, 0.05% weight antioxidant 330,0.2% weight 4,4 '-diaminodiphenylmethane bismaleimides (BMI), 0.55% weight calcium stearate is made described shield by embodiment 1 and condition and step.After tested, the shield that makes is 98% to the thermal neutron shielding rate axially, is 65% to 0.5-0.8mw gamma ray shielding rate, and indeformable in-25-190 ℃ scope, has shock resistance preferably and freedom from vibration simultaneously.
Claims (8)
1. one kind is added neutron and the gamma ray shielding material that neutron and gamma ray shielding material are formed in polymkeric substance, it is characterized in that it is a kind of Applicable temperature and is-25-190 ℃ wide temperature neutron and gamma ray shielding material, comprises following substances:
Heat-resistant polymer accounts for the 16-60% of mixture weight (together following);
Neutron and gamma ray shielding material, mean grain size are 1-40 μ m, account for 30-80%, and wherein the gamma ray shielding material should account for the 10-33.3% of neutron and gamma ray shielding substance weight;
Silane coupling agent accounts for 0.1-1.3%;
Antioxidant accounts for 0.03-0.7%;
Crosslinking chemical accounts for 0.1-1%;
Fortifying fibre accounts for 2-15%,
Described heat-resistant polymer is a kind of in polyphenylene sulfide, polyetheretherketone, polyethersulfone, polyarylsulfone, the polyimide.
2. neutron according to claim 1 and gamma ray shielding material, it is characterized in that described silane coupling agent is γ-glycidoxypropyltrimewasxysilane, γ-methacryloxy trimethoxy silane, a kind of in the TSL 8330 of N-β-(amino-ethyl)--γ--.
3. neutron according to claim 1 and gamma ray shielding material, it is characterized in that described material antioxidant is 4,4 '-Ding fork two (3-methyl-6 tert-butyl phenol), 2,6 BHT (antioxidant 264), styrenated phenol, 1,1,3-three (2 methyl 4-hydroxyl-5 tert-butyl-phenyl) butane (antioxidant CA), 1,3,5-trimethyl-2,4,6, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (antioxidant 330), 4, two (the 4-hydroxyls-3 of 6-, 5-di-t-butyl phenoxy group)-and 2-n-octyl sulfo--1,3, a kind of in 5 triazines.
4. neutron according to claim 1 and gamma ray shielding material, it is characterized in that described crosslinking chemical is 4,4 '-diaminodiphenylmethane bismaleimides (BMI), m-phenylene diamine, right-benzene dimethylamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl sulfone, 1, two (aminomethyl) cyclohexanes, 3 of 3-, 3 '-diamino 4,4 '-diaminodiphenyl-methane, 2,4, a kind of in 6-three (dimethylamino methyl) phenol.
5. neutron according to claim 1 and gamma ray shielding material is characterized in that described fortifying fibre is a kind of in glass fibre, the carbon fiber, and fibre length is 5-10mm.
6. according to each described neutron and gamma ray shielding material among the claim 1--5, it is characterized in that also being added with in the described mixture a kind of in the following lubricant: N, N '-ethylene bis stearamide, oleamide, stearic acid, lithium stearate, calcium stearate, solid paraffin, described lubricant accounts for the 0.1-0.6% of mixture weight.
7. neutron according to claim 6 and gamma ray shielding material is characterized in that it is exclusively used in the shield that uses on the manufacturing well logger.
8. neutron according to claim 7 and gamma ray shielding material is characterized in that described shield basic configuration is of a size of straight right cylinder through 52mm length 90mm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CN96114166A CN1084517C (en) | 1996-12-30 | 1996-12-30 | Wide-temp. neutron and gamma ray shielding material |
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CN96114166A CN1084517C (en) | 1996-12-30 | 1996-12-30 | Wide-temp. neutron and gamma ray shielding material |
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CN1157461A CN1157461A (en) | 1997-08-20 |
CN1084517C true CN1084517C (en) | 2002-05-08 |
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CN96114166A Expired - Fee Related CN1084517C (en) | 1996-12-30 | 1996-12-30 | Wide-temp. neutron and gamma ray shielding material |
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Families Citing this family (8)
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FR2882461B1 (en) * | 2005-02-21 | 2007-05-18 | Commissariat Energie Atomique | CRACKING CRACKS ON METAL DEVICES FOR CONTAINING ACIDIC AND RADIOACTIVE MATERIALS |
CN104292609A (en) * | 2013-07-15 | 2015-01-21 | 中国核动力研究设计院 | Heat-resistant composite shielding material and preparation method thereof |
CN106280461A (en) * | 2016-09-13 | 2017-01-04 | 北京市射线应用研究中心 | A kind of high temperature resistant neutron and gamma ray shielding composite and preparation method thereof |
CN106810865A (en) * | 2017-01-20 | 2017-06-09 | 镇江亿清复合材料有限公司 | A kind of high temperature resistant composite with nuclear radiation shield effect |
CN107603153B (en) * | 2017-09-18 | 2020-05-26 | 北京市射线应用研究中心 | Graphene/epoxy resin neutron shielding material and preparation method and application thereof |
US20230145719A1 (en) * | 2019-10-18 | 2023-05-11 | Jefferson Science Associates, Llc | Inorganic radiation-hard neutron shielding panels |
CN110861319B (en) * | 2019-11-20 | 2022-04-05 | 中广核高新核材科技(苏州)有限公司 | Radiation-resistant high-temperature-resistant fiber composite material and preparation method thereof |
CN112210148A (en) * | 2020-10-13 | 2021-01-12 | 中广核高新核材科技(苏州)有限公司 | Radiation-proof high-integrity container and preparation method thereof |
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