CN103556308B - A kind of radiation shield fibre and preparation method thereof - Google Patents
A kind of radiation shield fibre and preparation method thereof Download PDFInfo
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- SWUMLOXBPGDJOR-UHFFFAOYSA-N 2-methylidenebutanedioic acid;prop-2-enenitrile Chemical compound C=CC#N.OC(=O)CC(=C)C(O)=O SWUMLOXBPGDJOR-UHFFFAOYSA-N 0.000 claims description 2
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- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
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- Chemical Or Physical Treatment Of Fibers (AREA)
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Abstract
The present invention relates to a kind of radiation shield fibre and preparation method thereof, the raw material components of this radiation shield fibre comprises by weight percentage: the wolframic acid ammonium salt of 1 ~ 10%, the polyacrylonitrile copolymer of 5 ~ 20%, the DMF of 70 ~ 95%; The preparation method of this radiation shield fibre is equipped with raw material in proportion, and feeds intake according to sequencing, thus obtains the mixed solution of pale yellow transparent clarification homogeneous phase, ultrasonic standing and defoaming, namely obtain spinning solution, then by dry spinning process, prepare fibrillation; The fibrillation obtained is carried out drying, under air existent condition, dried fibrillation is made pre-oxidation treatment; Fibrillation pre-oxidation treatment crossed carries out carbonization treatment in the atmosphere of nitrogen, namely obtains the radiation shield fibre of containing metal tungsten nano particle.Implement beneficial effect of the present invention: the performance both with fibre object, there is again the radiation-resisting functional of tungsten simultaneously, and the product of different densities can be produced according to different proportionings.
Description
Technical field
The present invention relates to radiation protection material field, particularly relate to and a kind of there is radiation shield fibre of ionization radiation protection function and preparation method thereof.
Background technology
Along with the fast development of modern science and technology, various high-energy ray (as X-ray) obtains applying more and more widely in the field such as industry, agricultural, medical science, national defence.While bringing tremendous economic and social benefit, the injury of these high-energy rays to human body and the destruction to environment also become and are on the rise.That is familiar with the biological effects of radiation due to people deepens continuously, and the protection of high-energy ray has caused the great attention of people.X-ray is a kind of ionisation radiation, and it is different from general electromagnetic radiation, and it has larger destructiveness to human body.X-ray is classified as carcinogen by ICRP (ICRP), it causes appreciable impact to the various metabolism of human body, hematopoiesis function, immune system, reproductive system and central nervous system, can cause microcirculation disorder, canceration, chromosome aberration etc. simultaneously.Think prevention radiation carcinogenesis and the hereditary effect that causes because of cytometaplasia, very urgent to the protection of X-ray.The protection of X-ray can adopt 3 kinds of modes such as protection of time, distance protection and shielding protection.And shielding protection is exactly use between radioactive source and personnel or arrange a kind of shielding material that effectively can absorb X-ray, thus weakens or eliminate the harm of X-ray to human body.
At present for x ray protection material and prior art, the large metal material of density is mainly adopted to shield, protect the ionisation radiation of X-ray, as the compound etc. with stereotype, plumbous rubber and containing metal lead, as patent CN200420114740.X, CN200620081066.9 and CN201220320504.8 etc.Although these materials can reach the effect of protection, these leadwork comfortablenesses are poor after all, and the oxide of lead still has toxicity, has pollution to environment.Develop a kind of fiber with X-ray proof environmental protection again for this reason and there is very large application prospect.
Tungsten is rare refractory metal, and chemical property is very stable.Compared with metallic lead, its density (19.3g/cm3) is higher than plumbous (11.3g/cm3), and shielding ionisation radiation effect is better than lead, and it is to human non-toxic simultaneously, can not cause the pollution of environment.But metal tungsten material difficult forming, can only simply be processed into tungsten plate, can not be processed into protector or the barrier of complicated shape.Chinese patent CN200710023999.1 reports the preparation method of a kind of metal and plastic composite material, carries out blended injection mo(u)lding, thus obtain radiation-resistant glass composite by metal tungsten powder and plastics.
At present, there is not yet the patent report about the fiber with x ray protection function containing metal tungsten.
Summary of the invention
The technical problem to be solved in the present invention is, for the above-mentioned defect of prior art, provides a kind of radiation shield fibre and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is: a kind of radiation shield fibre, and the raw material components of this radiation shield fibre comprises by weight percentage: wolframic acid ammonium salt: 1 ~ 10%; Polyacrylonitrile copolymer: 5 ~ 20%; DMF:70 ~ 95%.
Preferably, described wolframic acid ammonium salt comprises at least one in positive ammonium tungstate, ammonium paratungstate, ammonium metatungstate.
Preferably, described polyacrylonitrile copolymer is at least one in acrlylonitrile-acrylate polymer, acrylonitrile-methacrylate polymer, acrylonitrile-acrylic acid polymer, acrylonitrile itaconic acid polymer, acrylonitrile-maleic acid polymers.
A preparation method for radiation shield fibre, comprises the following steps:
S1, be 1 ~ 10% wolframic acid ammonium salt with percentage by weight, percentage by weight be 5 ~ 20% polyacrylonitrile copolymer and percentage by weight be that the DMF of 70 ~ 95% is for raw material, above-mentioned raw materials is mixed with mixed solution, ultrasonic standing and defoaming is carried out to described mixed solution, namely spinning solution is obtained, then to described spinning solution by dry spinning process, make fibrillation;
S2, described fibrillation carried out to drying process, then in atmosphere pre-oxidation treatment is done to dried fibrillation;
S3, fibrillation pre-oxidation treatment crossed carry out carbonization treatment in nitrogen, namely obtain the radiation shield fibre of containing metal tungsten nano particle.
Preferably, the method preparing described mixed solution in described step S1 is: first polyacrylonitrile copolymer is dissolved in DMF the DMF solution forming polyacrylonitrile copolymer, then in the DMF solution of polyacrylonitrile copolymer, wolframic acid ammonium salt is added, mechanical agitation is carried out at the temperature of 25 ~ 100oC, until wolframic acid ammonium salt dissolves completely, and the polyacrylonitrile copolymer formed and the mixed solution of wolframic acid ammonium salt in DMF present transparent homogeneous phase, this presents the polyacrylonitrile copolymer of transparent homogeneous phase and the mixed solution of wolframic acid ammonium salt in DMF is the mixed solution that can carry out follow-up ultrasonic standing and defoaming and operate.
Preferably, described in described step S1, the method for dry spinning process is: use dry spinning device to carry out dry spinning process, and the running parameter of dry spinning process is: measuring pump extruded velocity 20-80ml/r, measuring pump pressure is less than 5.0MPa, hot path spinning temperature 100-400oC, nitrogen circulation amount 20-100ml/min, spinning speed 150-400m/min, washing temperature 60-90oC, draw ratio 3.3-6 are doubly.
Preferably, in described step S2, the described drying process carried out described fibrillation carries out under temperature is the environment of 70 ~ 120oC.
Preferably, in described step S2, to the method for the described pre-oxidation treatment that described dried fibrillation carries out be: described dried fibrillation is carried out heat treated in the temperature range of 180 ~ 300oC, the processing time is 20 ~ 90 minutes.
Preferably, the method for the carbonization treatment described in described step S3 is: fibrillation pre-oxidation treatment crossed, and heats in nitrogen, and heating-up temperature is between 400 ~ 1300oC, and the processing time is 9-15 minute.
Implement beneficial effect of the present invention: raw material sources is convenient, process stabilizing is reliable, the existing spinning of overall employing and carbonizing apparatus, products application safety non-toxic, compared to stereotype, and tungsten plate etc., the features such as this fiber has light, environmental protection; Obtain the whole bundle or single fiber with ionization radiation protection effect, in this material, tungsten is nano particle and is combined with fibre compact, can not come off from fiber, both there is the performance of fibre object, there is again the radiation-resisting functional of tungsten simultaneously, and can produce the product of different densities according to different proportionings, developing metal tungsten material is in the application of fabric arts.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the flow chart of the embodiment of the method 1 of the preparation method of a kind of radiation shield fibre of the present invention;
Fig. 2 is the structural representation of dry spinning device in the embodiment of the method 1 of the preparation method of a kind of radiation shield fibre of the present invention.
Detailed description of the invention
Product embodiments 1
A kind of radiation shield fibre, the raw material components of this radiation shield fibre comprises by weight percentage:
Wolframic acid ammonium salt: 1 ~ 10%; Polyacrylonitrile copolymer: 5-20%; DMF(N, dinethylformamide): 70-95%.
In the present embodiment, wolframic acid ammonium salt refers to ammonium metatungstate.
In the present embodiment, polyacrylonitrile copolymer refers to acrylonitrile-methylacrylate polymer (P(AN-MA)).
P(AN-MA) with the ratio of DMF weight ratio 1:4; Ammonium metatungstate and P(AN-MA) weight ratio is 1:3, concrete weight percentage data is: ammonium metatungstate: 6.25%; P(AN-MA) 18.75%; DMF:75.00%.
Embodiment of the method 1:
A preparation method for radiation shield fibre, as shown in Figure 1, its preparation process comprises:
S1, be 6.25% wolframic acid ammonium salt with percentage by weight, percentage by weight is the P(AN-MA of 18.75%) and percentage by weight be that the DMF of 75.00% is for raw material, above-mentioned raw materials is mixed with mixed solution, ultrasonic standing and defoaming is carried out to mixed solution, namely spinning solution is obtained, then to spinning solution by dry spinning process, make fibrillation;
S2, fibrillation carried out to drying process, then in atmosphere pre-oxidation treatment is done to dried fibrillation;
S3, fibrillation pre-oxidation treatment crossed carry out carbonization treatment in nitrogen, namely obtain the radiation shield fibre of containing metal tungsten nano particle.
The sequencing that feeds intake in preparation process S1 is: first by P(AN-MA) powder dissolution forms mixed solution in DMF, then in the two mixed solution, wolframic acid ammonium salt is added, mechanical agitation is carried out at the temperature of 70oC, until wolframic acid ammonium salt dissolves completely, and the P(AN-MA formed) presenting transparent homogeneous phase with the mixed solution of wolframic acid ammonium salt in DMF, this mixed solution presenting transparent homogeneous phase is the spinning solution that can carry out follow-up ultrasonic standing and defoaming operation.
Dry spinning process in preparation process S1, the method uses dry spinning device to carry out dry spinning process, as shown in Figure 2, spinning solution 1 is stored in sleeve 6 along A direction, during spinning, spinning solution 1 flows through measuring pump 2, then be extruded to spinning head 3 and carry out spinning, in this process, flow of warm nitrogen gas enters hot path 4 along B direction and flows out from C direction, the silk spun needs the washing through water washing device 5, carry out stretch processing afterwards, the running parameter of dry spinning process is: measuring pump extruded velocity 20-80ml/r, measuring pump pressure is less than 5.0MPa, hot path spinning temperature 100-400oC, nitrogen circulation amount 20-100ml/min, spinning speed 150-400m/min, washing temperature 60-90oC, draw ratio 3.3-6 doubly.In the present embodiment, the preferred 60ml/r of measuring pump extruded velocity, the preferred 4.0MPa of measuring pump pressure, the preferred 350oC of hot path spinning temperature, the preferred 80ml/min of nitrogen circulation amount, the preferred 250m/min of spinning speed, the preferred 85oC of washing temperature, draw ratio preferably 3.8 times.
Drying process in preparation process S2, its baking temperature is 70-120oC, can dispose organic solvent unnecessary in fibrillation.In the present embodiment, baking temperature is preferably 110oC.
Pre-oxidation treatment in preparation process S2, carries out heat treated by dried fibrillation within the scope of temperature 180-300oC, and the processing time is 20-90 minute, obtains the fibrillation with trapezoidal circulus.In the present embodiment, be positioned in Muffle furnace by dried fibrillation and carry out pre-oxidation, the atmosphere of pre-oxidation is air, and the temperature of pre-oxidation is respectively 210,250 and 290oC tri-warm areas, and each warm area stops 20 minutes respectively.
The method of the carbonization treatment described in step S3 is: fibrillation pre-oxidation treatment crossed, and heats in nitrogen, and heating-up temperature is between 400 ~ 1300oC, and the processing time is 9-15 minute.So-called carbonization treatment, by the fibrillation of pre-oxidation, under the protection of nitrogen, heating makes high polymer fiber be transformed into carbon fiber, and the wolframic acid ammonium salt of the inside also decomposites tungsten simultaneously.In the present embodiment, by the fibrillation crossed through pre-oxidation treatment, under the protection of nitrogen atmosphere, carry out carbonization treatment, the flow velocity of nitrogen is 70ml/min; 2 minutes are respectively processed at 415,520,600oC, then 700; 925,1050oC respectively processes 1 minute, thus obtains the fiber with ionizing radiation-resistant.
The fiber obtained obtains calicut through weaving, and preferred weaving is: warp-wise density 60/10cm, and latitudinal density 60/10cm, obtains fabric width 100cm, and thickness is the micron grey cloth of 1mm.
X ray protection assessment of function adopts Siemens Multix radiographic source to run at 70kV, uses Radcal-MDH2025 ionization chamber dosimeter 15 centimeters below sample to measure through dosage, calculates equivalent stereotype thickness.The fiber cumulative thickness that the present embodiment is collected is 0.75mm, and through X-ray evaluation, its equivalent stereotype thickness is 0.35mm.
Carry out conventional subsequent treatment to these calicuts, that namely can prepare radiation-resistant glass function wears clothing etc.
Implement beneficial effect of the present invention: raw material sources is convenient, process stabilizing is reliable, the existing spinning of overall employing and carbonizing apparatus, products application safety non-toxic, compared to stereotype, and tungsten plate etc., the features such as this fiber has light, environmental protection.Obtain the whole bundle or single fiber with ionization radiation protection effect, in this fibrous material, tungsten is nano particle and is combined with fibre compact, can not come off from fiber.Both had the performance of fibre object, and had again the radiation-resisting functional of tungsten simultaneously, and can produce the product of different densities according to different proportionings, developing metal tungsten material is in the application of fabric arts.
Below in conjunction with specific embodiments, the present invention is set forth further.But these embodiments are only for illustration of the present invention instead of for limiting practical range of the present invention.In addition be also to be understood that relevant technical staff in the field can do various change and amendment to the present invention, and these equivalent form of values fall within the scope appended by the application defined in claim equally after reading content of the present invention.
Claims (9)
1. a preparation method for radiation shield fibre, is characterized in that, comprises the following steps:
S1, be 1 ~ 10% wolframic acid ammonium salt with percentage by weight, percentage by weight be 5 ~ 20% polyacrylonitrile copolymer and percentage by weight be that the DMF of 70 ~ 95% is for raw material, above-mentioned raw materials is mixed with mixed solution, ultrasonic standing and defoaming is carried out to described mixed solution, namely spinning solution is obtained, then to described spinning solution by dry spinning process, make fibrillation;
S2, described fibrillation carried out to drying process, then in atmosphere pre-oxidation treatment is done to dried fibrillation;
S3, fibrillation pre-oxidation treatment crossed carry out carbonization treatment in nitrogen, namely obtain the radiation shield fibre of containing metal tungsten nano particle.
2. the preparation method of radiation shield fibre according to claim 1, it is characterized in that, the method preparing described mixed solution in described step S1 is: first polyacrylonitrile copolymer is dissolved in DMF the DMF solution forming polyacrylonitrile copolymer, then in the DMF solution of polyacrylonitrile copolymer, wolframic acid ammonium salt is added, mechanical agitation is carried out at the temperature of 25 ~ 100 DEG C, until wolframic acid ammonium salt dissolves completely, and the polyacrylonitrile copolymer formed and the mixed solution of wolframic acid ammonium salt in DMF present transparent homogeneous phase, this presents the polyacrylonitrile copolymer of transparent homogeneous phase and the mixed solution of wolframic acid ammonium salt in DMF is the mixed solution that can carry out follow-up ultrasonic standing and defoaming and operate.
3. the preparation method of radiation shield fibre according to claim 1, it is characterized in that, described in described step S1, the method for dry spinning process is: use dry spinning device to carry out dry spinning process, and the running parameter of dry spinning process is: measuring pump extruded velocity 20-80ml/r, measuring pump pressure is less than 5.0MPa, hot path spinning temperature 100-400 DEG C, nitrogen circulation amount 20-100ml/min, spinning speed 150-400m/min, washing temperature 60-90 DEG C, draw ratio 3.3-6 are doubly.
4. the preparation method of radiation shield fibre according to claim 1, is characterized in that, in described step S2, the described drying process carried out described fibrillation carries out under temperature is the environment of 70 ~ 120 DEG C.
5. the preparation method of radiation shield fibre according to claim 1, it is characterized in that, in described step S2, to the method for the described pre-oxidation treatment that described dried fibrillation carries out be: described dried fibrillation is carried out heat treated in the temperature range of 180 ~ 300 DEG C, the processing time is 20 ~ 90 minutes.
6. the preparation method of radiation shield fibre according to claim 1, it is characterized in that, the method for the carbonization treatment described in described step S3 is: fibrillation pre-oxidation treatment crossed, and heats in nitrogen, heating-up temperature is between 400 ~ 1300 DEG C, and the processing time is 9-15 minute.
7. based on the preparation method's of a radiation shield fibre according to claim 1 radiation shield fibre, it is characterized in that, the raw material components of this radiation shield fibre comprises by weight percentage: wolframic acid ammonium salt: 1 ~ 10%; Polyacrylonitrile copolymer: 5 ~ 20%; DMF:70 ~ 95%.
8. radiation shield fibre according to claim 7, is characterized in that, described wolframic acid ammonium salt comprises at least one in positive ammonium tungstate, ammonium paratungstate, ammonium metatungstate.
9. radiation shield fibre according to claim 7, it is characterized in that, described polyacrylonitrile copolymer is at least one in acrlylonitrile-acrylate polymer, acrylonitrile-methacrylate polymer, acrylonitrile-acrylic acid polymer, acrylonitrile itaconic acid polymer, acrylonitrile-maleic acid polymers.
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| CN102534870A (en) * | 2011-12-29 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of grapheme-modified acrylonitrile base carbon fiber |
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