CN102995389B - Method for acquiring neutron protective fabric by doping rare earth element - Google Patents
Method for acquiring neutron protective fabric by doping rare earth element Download PDFInfo
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- CN102995389B CN102995389B CN201210534855.3A CN201210534855A CN102995389B CN 102995389 B CN102995389 B CN 102995389B CN 201210534855 A CN201210534855 A CN 201210534855A CN 102995389 B CN102995389 B CN 102995389B
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Abstract
The invention discloses a method for acquiring a neutron protective fabric by doping rare earth element. The method comprises the following steps: (1) a, conducting pre-irradiation treatment on a textile by electron beam or plasma, and grafting the rare earth nanometer powder to the treated textile; or b, doping a rare-earth nanometer powder or rare earth salt into the textile, and conducting co-irradiation on the textile by electron beam or plasma; and (2) finally baking to obtain the neutron protective fabric. The invention acquires the flexible neutron protective fabric by doping rare earth element; the neutron protective fabric can effectively prevent slow neutron, thermal neutron and intermediate neutron, and especially shows obvious effect on fast neutron protection. According to the invention, rare earth element is grafted onto the textile to realize the flexible neutron prevention; and the method has great significance to solve a problem of neutron radiation protection and improve the added value of textile and rare earth.
Description
Technical field
The present invention relates to NEUTRON PROTECTION fabric, refer to particularly a kind of method that obtains NEUTRON PROTECTION fabric by doped with rare-earth elements.
Background technology
In fossil energy, day by day crisis in the situation that, the cry of development clean energy resource is more and more higher.But the clean energy resource energy as a supplement such as tide energy, solar energy, wind energy, biomass energy.Nuclear energy is only following main energy sources.Therefore, nuclear energy protection, particularly personnel protection is an important job.In the protection of radiation, the protection of neutron is more difficult technology, and reason is that neutron is not charged, acts on hardly with electronics, is not easy to be stopped by material protection difficulty.
The research of fabric type shielding material starts from 20 century 70s, the nowadays dry goods shielding material of existing number of different types, and be used for preparing radiation protection clothes.The beginning of the eighties in last century, the scientific research personnel of the former Soviet Union is object with viscose fiber fabric, by to polyacrylonitrile grafting, then process graft copolymerization material with sodium sulfide solution, finally make protective clothing with the fabric that lead acetate solution-treated is modified, this protective clothing shield effectiveness is good, but technique is more complicated, produces difficulty large.
The ion-exchange type properties that Japan is developed into be by the ionic adsorption of boron, lithium or other shielding material on fiber, thereby make fiber there is neutron irradiation function of shielding.Because adsorbance is limited and washing time very easily comes off, therefore shield effectiveness is poor.Japan improved original technology again afterwards, made the compound of ion-exchange fibre absorption lithium or boron, thereby had improved fabric neutron shield rate.
In known external various properties, taking the Development Level of toray company as best.It adopts composite spinning method to produce anti-neutron irradiation composite fibre.Specific practice be neutron absorber material and high polymer on kneader after melting mixing as core layer component, carry out melt composite spinning taking pure high polymer as cortex, gained fiber is skin-core structure, makes the fiber with some strength through xeothermic or damp and hot stretching.But this fibre spinning equipment is more complicated, invest larger.
Japan has also reported the preparation method of another kind of fibrous NEUTRON PROTECTION thing.The high polymeric solution that contains neutron absorber material under high pressure sprays spinning fibre, has improved the thermal neutron shielding rate of properties.But this kind of fibre strength is low, and extension at break is larger, be difficult for processing.The fiber that this method makes is because neutron absorber material is exposed to fiber surface, thereby very easily loses in washing, while being rubbed, and neutron-absorbing performance is reduced.Japan, also by after the compound powder of lithium and boron and polyvinyl resin copolymerization, adopts melting core-sheath spinning technique to develop properties material.Can be processed into woven fabric and non-weaving cloth, fixed is heavily 430 g/m
2the thermal neutron shielding rate of woven fabric can reach 40%, be usually used in the indoor doctor of hospital's radiotherapy and patient's protection.
The radiation protection technology company (RST) of Miami of the U.S. works out a kind of technology, and polyethylene (PE) and polyvinyl chloride (PVC) are carried out to modification, to form a kind of material that can prevent nuclear radiation.By certain untold process, polymer substrate is processed, made it to produce a kind of electron resonance effect that can radiation-absorbing.Treated matrix sticks between natural or synthetic two-layer nonwoven, and the radiation proof safety clothes of making like this take light and handy more than 5 times than traditional lead.The trade name of this cloth, Demron, is tested respectively in the Georgia Institute of Technology of New York Columbia University and Atlanta, and high energy β particle is had to fabulous shield effectiveness, at least can mask 50% for the gamma-rays of 130 keV.
China is since the research of the anti-neutron macromolecular material seventies in last century, and Tianjin was spun institute and succeeded in developing properties in May, 1987.This fiber has good gamma ray shielding function.After the blend such as domestic employing boron compound, heavy metal compound and polypropylene, melt-spun has been made the anti-neutron of core-skin type, Effect of X-Ray Shielding Fibre.In fiber, boron carbide content is up to 35%, and fibre strength can reach 23～27CN/tex, and elongation at break reaches 20～40%, can be processed into knitted fabric, woven fabric and non-weaving cloth, is used in around atomic reactor, can make neutron shielding shielding rate reach more than 44%.
The boron carbide micro powder of the employing polypropylene such as Wang Xuechen and Different Weight is raw material, inquired into by the feasibility of melt blending spinning technique development properties and fabric, and rheological property on co-mixing system and the factor that affects rheological property are discussed.Prepared material is suitable for protective ware, curtain for door or window and covering packaging etc.
Shandongs etc. utilize dynamic viscoelastometer etc. to test and use B
4dynamic mechanical after properties and as-spun fibre and the stretching of C/PP composite spinning.Research discovery, [E] of anti-neutron irradiation as-spun fibre behind glass transition region． is worth than the height of PP fiber, and heat resistance increases.In drawing process, the fracture strength of fiber and [E] value raise, and extension at break declines.Fault of construction in fiber reduces, and can keep skin-core structure.While exceeding 415 times of stretchings, [E] value of fiber reduces again.
Yin Jin sources etc. are prepared a kind of properties taking polyvinyl alcohol and boron carbide as main raw material adopts wet spinning technology.They have studied the processing molding method of this fiber, and have tested the performance of fiber.Result of study demonstration, properties has very strong thermal neutron function of shielding, and intermediate neutron is also had to certain function of shielding, and its protection effect has reached external similar research level.
Wenjun YANGs etc. have been prepared NdFeB/PE rare earth high polymer shielding composite, wherein NdFeB powder is submicron order, its shielding properties has entrusted Chinese Nuclear Power Design Academy to detect, result shows has good shield effectiveness to neutron and gamma-rays, particularly remarkable to the assimilation effect of thermal neutron.
At present, neutron radiation protective clothing still rests in the protection of centering low energy neutron, and the protection efficiency of the larger neutron current of protection to hot fast neutron or dosage does not reach the requirement of people to NEUTRON PROTECTION far away, and best also only have 44% left and right.
Current, the range of application of rare earth is very wide, but still few in radiation protection field application, and rare earth compound is grafted to the fabric that obtains anti-neutron on fabric and there is not yet report.
Summary of the invention
Object of the present invention will overcome the existing deficiency of prior art exactly, and a kind of method that obtains NEUTRON PROTECTION fabric by doped with rare-earth elements is provided.
For achieving the above object, the present invention obtains the method for NEUTRON PROTECTION fabric by doped with rare-earth elements, and it comprises the following steps:
(1) a, first by textiles through electron beam or the processing of plasma pre-irradiation, then rare earth nano powder is grafted on the textiles of processing;
Or b, by rare earth doped nano-powder or rare earth salts in textiles, through on electron beam or plasma mutual radiation textiles;
Described rare earth nano powder is the nano-powder of lanthana, yittrium oxide, neodymia, praseodymium oxide or gadolinium oxide, and described rare earth salts is sulfate or the nitrate of lanthanum, yttrium, neodymium, praseodymium, gadolinium;
(2) finally bake and can obtain NEUTRON PROTECTION fabric.
The preparation of the rare earth nano powder described in step 1) of the present invention, first takes the precipitation method or spray heating decomposition to make rare earth nano powder,
0.2 ~ 0.8% the dispersant that accounts for rare earth nano powder weight will be added again in rare earth nano powder, described dispersant is sodium phosphate trimer, calgon or sodium pyrophosphate, carries out surface modification in mechanical milling process, and removing surface can, eliminate surface electrostatic, improve its dispersiveness;
Or in rare earth nano powder, add 0.4 ~ 1% the surface modifier that accounts for rare earth nano powder weight, described surface modifier is titanate coupling agent or aluminate coupling agent, by the grinding distribution of mechanical milling process, to the processing of rare earth nano powder granule modifying surface, improve its dispersiveness;
To obtain required rare earth nano powder.
The energy of the generation of pre-irradiation or mutual radiation accelerator used is 5 ~ 10Mev, and radiation dose rate is 80 ~ 100Gy.
Rare earth element kind and consumption in the present invention are unrestricted, and the kind of textiles and thickness are also unrestricted.
Rare earth element is positioned at the III B family of the periodic table of elements.Comprise scandium (So), yttrium (Y) and lanthanide series (Ln) totally 17 elements.Rare earth element is owing to there being larger absorption cross-section to neutron, therefore rare earth element is a well selection as NEUTRON PROTECTION.Rare earth element, for protective clothing, produces the efficient personnel protection wearing fabric of comparison lightweight, thus the health problem that the radiation of minimizing nuclear technology practitioner and the suffered neutron of the public brings.Rare earth powder, due to high containing rare earth composition, is made nano-powder, is grafted on textiles, can obtain flexible neutron shielding fabric, thereby improves protection effects such as thermal neutron, slow neutron, intermediate neutron, fast neutrons.
Beneficial effect of the present invention is: the present invention obtains flexible rare earth NEUTRON PROTECTION fabric by doped with rare-earth elements, to slow neutron, thermal neutron, intermediate neutron protection effectively, and especially to fast neutron protection significant effective.The present invention is grafted to rare earth element on textiles, realizes flexible NEUTRON PROTECTION, all significant to solving neutron shielding problem and lifting textiles and rare earth added value.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
(1) first take the precipitation method to make lanthana nano-powder, 0.2% the sodium pyrophosphate that accounts for lanthana nano-powder weight will be added again in lanthana nano-powder, in mechanical milling process, carry out surface modification, removing surface can, eliminate surface electrostatic, improve its dispersiveness, to obtain required lanthana nano-powder;
(2) first by textiles process electron beam or the processing of plasma pre-irradiation, then the lanthana nano-powder making is grafted on the textiles of processing; The energy of the generation of irradiation accelerator used is 5Mev, and radiation dose rate is 80Gy/s;
(3) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 2
(1) first take the precipitation method to make yttrium oxide nano-powder, 0.4% the sodium phosphate trimer that accounts for yttrium oxide nano-powder weight will be added again in yttrium oxide nano-powder, in mechanical milling process, carry out surface modification, removing surface can, eliminate surface electrostatic, improve its dispersiveness, to obtain required yttrium oxide nano-powder;
(2) first by textiles process electron beam or the processing of plasma pre-irradiation, then the yttrium oxide nano-powder making is grafted on the textiles of processing; The energy of the generation of irradiation accelerator used is 5Mev, and radiation dose rate is 80Gy/s;
(3) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 3
(1) first take the precipitation method to make neodymia nano-powder, 0.8% the calgon that accounts for neodymia nano-powder weight will be added again in neodymia nano-powder, in mechanical milling process, carry out surface modification, removing surface can, eliminate surface electrostatic, improve its dispersiveness, to obtain required neodymia nano-powder;
(2) neodymia nano-powder doping in textiles being made, on plasma mutual radiation textiles; The energy of the generation of irradiation accelerator used is 8Mev, and radiation dose rate is 90Gy/s;
(3) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 4
(1) first take spray heating decomposition to make praseodymium oxide nano-powder, 0.7% the calgon that accounts for praseodymium oxide nano-powder weight will be added again in praseodymium oxide nano-powder, in mechanical milling process, carry out surface modification, removing surface can, eliminate surface electrostatic, improve its dispersiveness, to obtain required praseodymium oxide nano-powder;
(2) praseodymium oxide nano-powder doping in textiles being made, on plasma mutual radiation textiles; The energy of the generation of irradiation accelerator used is 8Mev, and radiation dose rate is 90Gy/s;
(3) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 5
(1) first take spray heating decomposition to make gadolinium oxide nano-powder, 0.3% the sodium pyrophosphate that accounts for gadolinium oxide nano-powder weight will be added again in gadolinium oxide nano-powder, in mechanical milling process, carry out surface modification, removing surface can, eliminate surface electrostatic, improve its dispersiveness, to obtain required praseodymium oxide nano-powder;
(2) gadolinium oxide nano-powder doping in textiles being made, on plasma mutual radiation textiles; The energy of the generation of irradiation accelerator used is 8Mev, and radiation dose rate is 90Gy/s;
(3) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 6
(1) first take spray heating decomposition to make yttrium oxide nano-powder, in yttrium oxide nano-powder, add again 0.6% the titanate coupling agent that accounts for yttrium oxide nano-powder weight, by the grinding distribution of mechanical milling process, yttrium oxide nano-powder particle surface is carried out to modification, improve its dispersiveness, to obtain required yttrium oxide nano-powder;
(2) yttrium oxide nano-powder doping in textiles being made, on plasma mutual radiation textiles; The energy of the generation of irradiation accelerator used is 8Mev, and radiation dose rate is 90Gy/s;
(3) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 7
(1) first take spray heating decomposition to make praseodymium oxide nano-powder, in praseodymium oxide nano-powder, add again 0.4% the aluminate coupling agent that accounts for praseodymium oxide nano-powder weight, by the grinding distribution of mechanical milling process, praseodymium oxide nano-powder particle surface is carried out to modification, improve its dispersiveness, to obtain required praseodymium oxide nano-powder;
(2) praseodymium oxide nano-powder doping in textiles being made, on plasma mutual radiation textiles; The energy of the generation of irradiation accelerator used is 8Mev, and radiation dose rate is 90Gy/s;
(3) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 8
(1) first take the precipitation method to make neodymia nano-powder, in neodymia nano-powder, add again 1% the aluminate coupling agent that accounts for neodymia nano-powder weight, by the grinding distribution of mechanical milling process, neodymia nano-powder particle surface is carried out to modification, improve its dispersiveness, to obtain required neodymia nano-powder;
(2) neodymia nano-powder doping in textiles being made, on plasma mutual radiation textiles; The energy of the generation of irradiation accelerator used is 8Mev, and radiation dose rate is 90Gy/s;
(3) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 9
(1) by doped sulfuric acid gadolinium in textiles, on electron beam mutual radiation textiles; The beam energy of the generation of irradiation accelerator used is 4Mev, and line is 2 × 10
-6a, radiation dose rate is 100Gy/s;
(2) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 10
(1) by doped sulfuric acid lanthanum in textiles, on electron beam mutual radiation textiles; The beam energy of the generation of irradiation accelerator used is 4Mev, and line is 2 × 10
-6a, radiation dose rate is 100Gy/s;
(2) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 11
(1) by doped sulfuric acid yttrium in textiles, on electron beam mutual radiation textiles; The beam energy of the generation of irradiation accelerator used is 4Mev, and line is 2 × 10
-6a, radiation dose rate is 100Gy/s;
(2) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 12
(1) by the neodymium nitrate that adulterates in textiles, on electron beam mutual radiation textiles; The beam energy of the generation of irradiation accelerator used is 4Mev, and line is 2 × 10
-6a, radiation dose rate is 100Gy/s;
(2) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 13
(1) by the praseodymium nitrate that adulterates in textiles, on electron beam mutual radiation textiles; The beam energy of the generation of irradiation accelerator used is 4Mev, and line is 2 × 10
-6a, radiation dose rate is 100Gy/s;
(2) finally bake and can obtain NEUTRON PROTECTION fabric.
Embodiment 14
(1) by the yttrium nitrate that adulterates in textiles, on electron beam mutual radiation textiles; The beam energy of the generation of irradiation accelerator used is 4Mev, and line is 2 × 10
-6a, radiation dose rate is 100Gy/s;
(2) finally bake and can obtain NEUTRON PROTECTION fabric.
Effect
Prepared the present invention NEUTRON PROTECTION fabric is carried out to NEUTRON PROTECTION test, and NEUTRON PROTECTION fabric is made the fabric of 1 millimeters thick of doped with rare-earth elements.Utilize fast neutron (fast neutron energy reach million electro-volt more than) irradiation NEUTRON PROTECTION fabric, obtained the protection effect that approaches 10%.
That is to say, as long as thickening and optimization grafted rare earth powder scheme, it is feasible obtaining the protection effect to fast neutron being better than more than 50%.
And the thinner flexible protective of fast neutron was considered to impossible in the past.This shows according to the inventive method is that the fabric that can obtain has good result.
Claims (2)
1. a method that obtains NEUTRON PROTECTION fabric by doped with rare-earth elements, is characterized in that, it comprises the following steps:
(1) a, first by textiles through electron beam or the processing of plasma pre-irradiation, then rare earth nano powder is grafted on the textiles of processing;
Or b, by rare earth doped nano-powder or rare earth salts in textiles, through electron beam or plasma mutual radiation textiles;
Described rare earth nano powder is the nano-powder of lanthana, yittrium oxide, neodymia, praseodymium oxide or gadolinium oxide, and described rare earth salts is sulfate or the nitrate of lanthanum, yttrium, neodymium, praseodymium, gadolinium;
The preparation of described rare earth nano powder: first take the precipitation method or spray heating decomposition to make rare earth nano powder;
In rare earth nano powder, add again 0.2～0.8% the dispersant that accounts for rare earth nano powder weight, described dispersant is sodium phosphate trimer, calgon or sodium pyrophosphate, carries out surface modification in mechanical milling process, and removing surface can, eliminate surface electrostatic, improve its dispersiveness;
Or in rare earth nano powder, add 0.4～1% the surface modifier that accounts for rare earth nano powder weight, described surface modifier is titanate coupling agent or aluminate coupling agent, by the grinding distribution of mechanical milling process, to the processing of rare earth nano powder granule modifying surface, improve its dispersiveness;
To obtain required rare earth nano powder;
(2) finally bake and can obtain NEUTRON PROTECTION fabric.
2. the method that obtains according to claim 1 NEUTRON PROTECTION fabric by doped with rare-earth elements, is characterized in that: step 1) in the energy of generation of pre-irradiation or mutual radiation accelerator used be 5～10Mev, radiation dose rate is 80～100Gy/s.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103806273B (en) * | 2014-02-13 | 2015-12-30 | 北京化工大学常州先进材料研究院 | A kind of method preparing fluorescent nano-fiber based on photo-grafting surface modification |
| CN104032403B (en) * | 2014-06-19 | 2015-12-30 | 宜春学院 | Rare-earth oxide/polyacrylonitrile composite fiber and preparation method thereof |
| CN107338640A (en) * | 2017-06-20 | 2017-11-10 | 江门职业技术学院 | A kind of polyester cotton fabric rare earth multifunctional composite finishing agent and preparation method thereof |
| CN116001393B (en) * | 2023-03-24 | 2023-06-16 | 汕头市金南辉纺织实业有限公司 | Super-soft elastic fabric based on three-dimensional multidirectional knitting and preparation method and application thereof |
Citations (3)
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|---|---|---|---|---|
| CN1088636A (en) * | 1992-12-19 | 1994-06-29 | 天津纺织工学院 | Neutron and gamma ray radiation shield fibre and manufacture method thereof |
| CN1153389A (en) * | 1996-08-13 | 1997-07-02 | 张启馨 | Mixed lanthanide contg. Shield composite material for medical X-ray protection |
| CN102141182A (en) * | 2010-01-28 | 2011-08-03 | 中国核动力研究设计院 | Heat insulation material capable of insulating heat and neutrons |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH02297098A (en) * | 1989-05-11 | 1990-12-07 | Kanebo Ltd | Neutron shieldable acrylic synthetic fiber and production thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088636A (en) * | 1992-12-19 | 1994-06-29 | 天津纺织工学院 | Neutron and gamma ray radiation shield fibre and manufacture method thereof |
| CN1153389A (en) * | 1996-08-13 | 1997-07-02 | 张启馨 | Mixed lanthanide contg. Shield composite material for medical X-ray protection |
| CN102141182A (en) * | 2010-01-28 | 2011-08-03 | 中国核动力研究设计院 | Heat insulation material capable of insulating heat and neutrons |
Non-Patent Citations (1)
| Title |
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| JP平2-297098A 1990.12.07 |
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