CN102995389A - 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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- CN102995389A CN102995389A CN2012105348553A CN201210534855A CN102995389A CN 102995389 A CN102995389 A CN 102995389A CN 2012105348553 A CN2012105348553 A CN 2012105348553A CN 201210534855 A CN201210534855 A CN 201210534855A CN 102995389 A CN102995389 A CN 102995389A
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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 the NEUTRON PROTECTION fabric, refer to particularly a kind of method that obtains the NEUTRON PROTECTION fabric by doped with rare-earth elements.
Background technology
In the situation that day by day crisis of fossil energy, the cry of development clean energy resource is more and more higher.Yet the clean energy resourcies such as tide energy, solar energy, wind energy, biomass energy are the energy as a supplement.Nuclear energy is only following main energy sources.Therefore, the nuclear energy protection, particularly personnel protection is an important job.In the protection of radiation, the protection of neutron is relatively more difficult technology, and reason is that neutron is not charged, acts on hardly with electronics, is not easy to be stopped by material the protection difficulty.
The research of fabric type shielding material starts from 20 century 70s, nowadays has the dry goods shielding material of number of different types, and multiplex in preparation 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 the polyacrylonitrile grafting, then process graft copolymerization material with sodium sulfide solution, the fabric that is modified with the lead acetate solution-treated is at last made protective clothing, this protective clothing shield effectiveness is good, but technique is complicated, produces difficulty large.
The ion-exchange type properties that Japan is developed into be ionic adsorption with boron, lithium or other shielding material on fiber, thereby make fiber have the neutron irradiation function of shielding.Because adsorbance is limited and washing the time very easily comes off, therefore shield effectiveness is relatively 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, take the Development Level of toray company as best.It adopts the composite spinning method to produce anti-neutron irradiation composite fibre.Specific practice be neutron absorber material and high polymer after melting mixing on the kneader as core layer component, carry out melt composite spinning take pure high polymer as cortex, the 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 complicated, invests 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 fibre strength is low, and extension at break is larger, is difficult for processing.The fiber that this method makes is exposed to fiber surface owing to neutron absorber material, thereby is washing, very easily losing when being rubbed, and the neutron-absorbing performance is reduced.Behind the Japanese also compound powder and polyvinyl resin copolymerization with lithium and boron, adopt melting core-sheath spinning technique to develop the properties material.Can be processed into woven fabric and non-weaving cloth, fixed heavily is 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 U.S. Miami works out a kind of technology, and polyethylene (PE) and polyvinyl chloride (PVC) are carried out modification, to form a kind of material that can prevent nuclear radiation.With 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 the 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 is Demron, and the Georgia Institute of Technology in Columbia University, New York and Atlanta tests respectively, and high energy β particle is had fabulous shield effectiveness, can mask 50% at least 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 preferably gamma ray shielding function.Melt-spun has been made the anti-neutron of core-skin type, Effect of X-Ray Shielding Fibre after the blend such as domestic employing boron compound, heavy metal compound and polypropylene.Boron carbide content is up to 35% in the fiber, 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 the atomic reactor, and the neutron shielding shielding rate is reached more than 44%.
The boron carbide micro powder of the employing polypropylene such as Wang Xuechen and Different Weight is raw material, inquired into the feasibility by melt blending spinning technique development properties and fabric, and the rheological property of co-mixing system and the factor that affects rheological property have been discussed.Prepared material is suitable for protective ware, curtain for door or window and covering packing etc.
Shandongs etc. utilize dynamic viscoelastometer etc. to test and use B
4The properties of C/PP composite spinning and the dynamic mechanical after as-spun fibre and the stretching thereof.Research is found, prevents neutron irradiation as-spun fibre [E] value behind glass transition region． than the height of PP fiber, and heat resistance increases.The fracture strength of fiber and [E] value raises in drawing process, and extension at break descends.Fault of construction in the fiber reduces, and can keep skin-core structure.When surpassing 415 times of stretchings, [E] of fiber value reduces again.
Yin Jin sources etc. are prepared a kind of properties take 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.The result of study demonstration, properties has very strong thermal neutron function of shielding, and intermediate neutron is also had certain function of shielding, and its protection effect has reached external similar research level.
Wenjun YANGs etc. have prepared NdFeB/PE rare earth high polymer shielding composite, wherein the NdFeB powder is submicron order, its shielding properties has entrusted Chinese Nuclear Power Design Academy to detect, the 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 the protection of hot fast neutron or dosage is not reached people far away to the requirement of NEUTRON PROTECTION, and best also only has about 44%.
Current, the application of rare earths scope is very wide, but still few in the application of radiation protection field, rare earth compound is grafted to the fabric that obtains anti-neutron on the fabric and there is not yet report.
Summary of the invention
Purpose of the present invention will overcome the existing deficiency of prior art exactly, and a kind of method that obtains the 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 may further comprise the steps:
(1) a, first textiles is processed through electron beam or plasma pre-irradiation, again the rare earth nano powder is grafted on the textiles of processing;
Or b, with rare earth doped nano-powder or rare earth salts in the textiles, through on electron beam or the 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) bake at last and can obtain the NEUTRON PROTECTION fabric.
The preparation of the rare earth nano powder described in the step 1) of the present invention takes first the precipitation method or spray heating decomposition to make the rare earth nano powder,
0.2 ~ 0.8% the dispersant account for rare earth nano powder weight will be added again in the rare earth nano powder, described dispersant is sodium phosphate trimer, calgon or sodium pyrophosphate, carries out surface modification in mechanical milling process, removes surface energy, eliminate surface electrostatic, improve its dispersiveness;
Or in the rare earth nano powder, add 0.4 ~ 1% the surface modifier account 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, rare earth nano powder granule modifying surface is processed, improve its dispersiveness;
To obtain required rare earth nano powder.
The energy of the generation of the accelerator that pre-irradiation or mutual radiation are used is 5 ~ 10Mev, and radiation dose rate is 80 ~ 100Gy.
Rare earth element kind and consumption among 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) be totally 17 elements.Rare earth element is owing to having larger absorption cross-section to neutron, so rare earth element is one as NEUTRON PROTECTION and well selects.Rare earth element is used 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.The rare earth powder is high owing to containing rare earth composition, makes nano-powder, is grafted on the textiles, then 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 the textiles, realizes flexible NEUTRON PROTECTION, and is all significant to solving neutron shielding problem and lifting textiles and rare earth added value.
The specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
(1) take first the precipitation method to make the lanthana nano-powder, 0.2% the sodium pyrophosphate account for lanthana nano-powder weight will be added again in the lanthana nano-powder, in mechanical milling process, carry out surface modification, remove surface energy, eliminate surface electrostatic, improve its dispersiveness, to obtain required lanthana nano-powder;
(2) first textiles is processed through electron beam or plasma pre-irradiation, again the lanthana nano-powder that makes is grafted on the textiles of processing; The energy of the generation of the accelerator that irradiation is used is 5Mev, and radiation dose rate is 80Gy/s;
(3) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 2
(1) take first the precipitation method to make yttrium oxide nano-powder, 0.4% the sodium phosphate trimer account for yttrium oxide nano-powder weight will be added again in the yttrium oxide nano-powder, in mechanical milling process, carry out surface modification, remove surface energy, eliminate surface electrostatic, improve its dispersiveness, to obtain required yttrium oxide nano-powder;
(2) first textiles is processed through electron beam or plasma pre-irradiation, again the yttrium oxide nano-powder that makes is grafted on the textiles of processing; The energy of the generation of the accelerator that irradiation is used is 5Mev, and radiation dose rate is 80Gy/s;
(3) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 3
(1) take first the precipitation method to make the neodymia nano-powder, 0.8% the calgon account for neodymia nano-powder weight will be added again in the neodymia nano-powder, in mechanical milling process, carry out surface modification, remove surface energy, eliminate surface electrostatic, improve its dispersiveness, to obtain required neodymia nano-powder;
(2) with the neodymia nano-powder that mixes and make in the textiles, on plasma mutual radiation textiles; The energy of the generation of the accelerator that irradiation is used is 8Mev, and radiation dose rate is 90Gy/s;
(3) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 4
(1) take first spray heating decomposition to make the praseodymium oxide nano-powder, 0.7% the calgon account for praseodymium oxide nano-powder weight will be added again in the praseodymium oxide nano-powder, in mechanical milling process, carry out surface modification, remove surface energy, eliminate surface electrostatic, improve its dispersiveness, to obtain required praseodymium oxide nano-powder;
(2) with the praseodymium oxide nano-powder that mixes and make in the textiles, on plasma mutual radiation textiles; The energy of the generation of the accelerator that irradiation is used is 8Mev, and radiation dose rate is 90Gy/s;
(3) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 5
(1) take first spray heating decomposition to make the gadolinium oxide nano-powder, 0.3% the sodium pyrophosphate account for gadolinium oxide nano-powder weight will be added again in the gadolinium oxide nano-powder, in mechanical milling process, carry out surface modification, remove surface energy, eliminate surface electrostatic, improve its dispersiveness, to obtain required praseodymium oxide nano-powder;
(2) with the gadolinium oxide nano-powder that mixes and make in the textiles, on plasma mutual radiation textiles; The energy of the generation of the accelerator that irradiation is used is 8Mev, and radiation dose rate is 90Gy/s;
(3) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 6
(1) take first spray heating decomposition to make yttrium oxide nano-powder, in yttrium oxide nano-powder, add again 0.6% the titanate coupling agent account for yttrium oxide nano-powder weight, grinding distribution by mechanical milling process, the yttrium oxide nano-powder particle surface is carried out modification, improve its dispersiveness, to obtain required yttrium oxide nano-powder;
(2) with the yttrium oxide nano-powder that mixes and make in the textiles, on plasma mutual radiation textiles; The energy of the generation of the accelerator that irradiation is used is 8Mev, and radiation dose rate is 90Gy/s;
(3) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 7
(1) take first spray heating decomposition to make the praseodymium oxide nano-powder, in the praseodymium oxide nano-powder, add again 0.4% the aluminate coupling agent account for praseodymium oxide nano-powder weight, grinding distribution by mechanical milling process, praseodymium oxide nano-powder particle surface is carried out modification, improve its dispersiveness, to obtain required praseodymium oxide nano-powder;
(2) with the praseodymium oxide nano-powder that mixes and make in the textiles, on plasma mutual radiation textiles; The energy of the generation of the accelerator that irradiation is used is 8Mev, and radiation dose rate is 90Gy/s;
(3) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 8
(1) take first the precipitation method to make the neodymia nano-powder, in the neodymia nano-powder, add again 1% the aluminate coupling agent account for neodymia nano-powder weight, grinding distribution by mechanical milling process, neodymia nano-powder particle surface is carried out modification, improve its dispersiveness, to obtain required neodymia nano-powder;
(2) with the neodymia nano-powder that mixes and make in the textiles, on plasma mutual radiation textiles; The energy of the generation of the accelerator that irradiation is used is 8Mev, and radiation dose rate is 90Gy/s;
(3) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 9
(1) with doped sulfuric acid gadolinium in the textiles, on electron beam mutual radiation textiles; The beam energy of the generation of the accelerator that irradiation is used is 4Mev, and line is 2 * 10
-6A, radiation dose rate are 100Gy/s;
(2) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 10
(1) with doped sulfuric acid lanthanum in the textiles, on electron beam mutual radiation textiles; The beam energy of the generation of the accelerator that irradiation is used is 4Mev, and line is 2 * 10
-6A, radiation dose rate are 100Gy/s;
(2) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 11
(1) with doped sulfuric acid yttrium in the textiles, on electron beam mutual radiation textiles; The beam energy of the generation of the accelerator that irradiation is used is 4Mev, and line is 2 * 10
-6A, radiation dose rate are 100Gy/s;
(2) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 12
(1) with the neodymium nitrate that mixes in the textiles, on electron beam mutual radiation textiles; The beam energy of the generation of the accelerator that irradiation is used is 4Mev, and line is 2 * 10
-6A, radiation dose rate are 100Gy/s;
(2) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 13
(1) with the praseodymium nitrate that mixes in the textiles, on electron beam mutual radiation textiles; The beam energy of the generation of the accelerator that irradiation is used is 4Mev, and line is 2 * 10
-6A, radiation dose rate are 100Gy/s;
(2) bake at last and can obtain the NEUTRON PROTECTION fabric.
Embodiment 14
(1) with the yttrium nitrate that mixes in the textiles, on electron beam mutual radiation textiles; The beam energy of the generation of the accelerator that irradiation is used is 4Mev, and line is 2 * 10
-6A, radiation dose rate are 100Gy/s;
(2) bake at last and can obtain the NEUTRON PROTECTION fabric.
Effect
The prepared NEUTRON PROTECTION fabric of the present invention is carried out the NEUTRON PROTECTION test, and the NEUTRON PROTECTION fabric is made the fabric of 1 millimeters thick of doped with rare-earth elements.Utilize fast neutron (the fast neutron energy reaches more than the million electro-volt) irradiation NEUTRON PROTECTION fabric, obtained the protection effect near 10%.
That is to say, as long as thickening and optimization grafted rare earth powder scheme, the protection effect to fast neutron that obtains to be better than more than 50% is feasible.
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 (3)
1. a method that obtains the NEUTRON PROTECTION fabric by doped with rare-earth elements is characterized in that, it may further comprise the steps:
(1) a, first textiles is processed through electron beam or plasma pre-irradiation, again the rare earth nano powder is grafted on the textiles of processing;
Or b, with rare earth doped nano-powder or rare earth salts in the textiles, through on electron beam or the 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) bake at last and can obtain the NEUTRON PROTECTION fabric.
2. the described method that obtains the NEUTRON PROTECTION fabric by doped with rare-earth elements according to claim 1 is characterized in that: the preparation of the rare earth nano powder described in the step 1), and take first the precipitation method or spray heating decomposition to make the rare earth nano powder,
0.2 ~ 0.8% the dispersant account for rare earth nano powder weight will be added again in the rare earth nano powder, described dispersant is sodium phosphate trimer, calgon or sodium pyrophosphate, carries out surface modification in mechanical milling process, removes surface energy, eliminate surface electrostatic, improve its dispersiveness;
Or in the rare earth nano powder, add 0.4 ~ 1% the surface modifier account 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, rare earth nano powder granule modifying surface is processed, improve its dispersiveness;
To obtain required rare earth nano powder.
3. the described method that obtains the NEUTRON PROTECTION fabric by doped with rare-earth elements according to claim 1 is characterized in that: the energy of the generation of the used accelerator of pre-irradiation or mutual radiation is 5 ~ 10Mev in the step 1), and radiation dose rate is 80 ~ 100Gy.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806273A (en) * | 2014-02-13 | 2014-05-21 | 北京化工大学常州先进材料研究院 | Method for preparing fluorescent nanofibers based on photo-grafting surface modification |
| CN104032403A (en) * | 2014-06-19 | 2014-09-10 | 宜春学院 | Rare-earth metal oxide/polyacrylonitrile (PAN) 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 |
| CN116001393A (en) * | 2023-03-24 | 2023-04-25 | 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 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806273A (en) * | 2014-02-13 | 2014-05-21 | 北京化工大学常州先进材料研究院 | Method for preparing fluorescent nanofibers based on photo-grafting surface modification |
| 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 |
| CN104032403A (en) * | 2014-06-19 | 2014-09-10 | 宜春学院 | Rare-earth metal oxide/polyacrylonitrile (PAN) composite fiber and preparation method thereof |
| 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 |
| CN116001393A (en) * | 2023-03-24 | 2023-04-25 | 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 |
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