CN115537967A - Magnetic adjustable polymer/ferrite hybrid fiber and preparation method thereof - Google Patents
Magnetic adjustable polymer/ferrite hybrid fiber and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
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- 238000002074 melt spinning Methods 0.000 claims abstract description 18
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- 238000012986 modification Methods 0.000 claims abstract description 14
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 239000006228 supernatant Substances 0.000 claims description 27
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 26
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 20
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- 238000005119 centrifugation Methods 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 10
- 108090000623 proteins and genes Proteins 0.000 claims description 10
- 102000004169 proteins and genes Human genes 0.000 claims description 10
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- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 3
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 229920001184 polypeptide Polymers 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 3
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- IXCAKLICAHRVSL-UHFFFAOYSA-N [O--].[O--].[O--].[Fe+6] Chemical class [O--].[O--].[O--].[Fe+6] IXCAKLICAHRVSL-UHFFFAOYSA-N 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 230000033558 biomineral tissue development Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- 230000003592 biomimetic effect Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920006253 high performance fiber Polymers 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 108010022355 Fibroins Proteins 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
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- 230000018109 developmental process Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
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- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- DRECBBFIAREDAS-UHFFFAOYSA-N methoxymethane;hydrate Chemical compound O.COC DRECBBFIAREDAS-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
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- 210000000513 rotator cuff Anatomy 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides a magnetic adjustable polymer/ferrite hybrid fiber and a preparation method thereof, belonging to the technical field of functional hybrid fibers, wherein the polymer/ferrite hybrid fiber comprises 98-99.9% of polymer and 0.1-2.0% of ferrite by mass. The size, the appearance and the pore structure of the bionical ferric oxide nano-filler of the magnetic adjustable high-performance polymer ferrite hybrid fiber provided by the invention are uniform and controllable; under the modification effect of biomolecules, the polymer has excellent compatibility with a polymer matrix, and the uniform dispersion of the polymer in the polymer matrix is realized; the ferric oxide filler is not easy to aggregate due to electromagnetic action in the subsequent melt spinning process, and has good spinnability; after the hybrid fiber is melted and formed, a continuous subsequent heat treatment process is applied, the ferrite crystal form in the fiber can be controllably converted from ferric oxide to magnetic tetraoxide, the magnetic property of the magnetic fiber is effectively controlled, and meanwhile, the industrial large-scale production of the magnetic fiber is realized.
Description
Technical Field
The invention belongs to the technical field of functional hybrid fibers, and particularly relates to a magnetic adjustable polymer/ferrite hybrid fiber and a preparation method thereof.
Background
As a special functional fiber, the magnetic fiber has irreplaceable application in the civil fields of medical care and the like and the high-end fields of microwave communication, electronic countermeasure, aerospace and the like in recent years. With the development of advanced nanometer preparation technology and fiber melt spinning forming technology, hybrid polymer-based magnetic fibers gradually become the mainstream of magnetic fibers. At present, magnetic fibers taking chemical fibers such as terylene, chinlon and the like as matrixes have wide application in civil medical care because of the advantages of simple operation, low cost, easy large-scale production and easier processing of products compared with metal magnetic fibers. However, the current magnetic nano ferrite filler is subject to various factors such as large size distribution, strong self-aggregation, poor compatibility with polymer matrix, and easy influence of electromagnetic heating equipment, which results in uneven distribution of magnetic ferrite in polymer matrix, poor fiber spinnability, and uncontrollable and unstable quality of the obtained magnetic fiber, thus failing to meet the requirements of national defense, military industry, medical treatment and other high-end applications.
Disclosure of Invention
In view of the above, the present invention aims to provide a magnetically tunable polymer/ferrite hybrid fiber and a preparation method thereof. The magnetic adjustable fiber provided by the invention has strong quality controllability, unique and advanced technology; meanwhile, the method has the advantages of simple operation, low cost and high feasibility of large-scale production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a magnetic adjustable polymer/ferrite hybrid fiber, which comprises 98-99.9% of polymer and 0.1-2.0% of ferrite by mass.
Preferably, the polymer comprises polyphenylene sulfide slices and/or polyetheretherketone slices.
Preferably, the ferrite comprises biomacromolecule mineralized or modified ferric oxide nanoparticles.
Preferably, the preparation method of the biomacromolecule mineralized iron sesquioxide nano particles comprises the following steps: mixing the biomacromolecule solution with the iron source precursor solution, carrying out hydrothermal reaction, removing supernatant after the reaction is finished, centrifuging the precipitate, taking the supernatant after centrifugation, and drying to obtain the biomacromolecule mineralized iron trioxide nanoparticles.
Preferably, the preparation method of the biomacromolecule modified ferric oxide nanoparticles comprises the following steps: mixing the iron source precursor solution with a diethanolmethyl ether-water mixed solvent, carrying out hydrothermal reaction, removing supernatant after the reaction is finished, centrifuging the precipitate, and drying the precipitate after centrifugation to obtain high-concentration spherical ferric oxide nano ferrite; and mixing the obtained high-concentration spherical ferric oxide nano ferrite with a biomacromolecule solution for modification, removing supernatant after the modification is finished, centrifuging the precipitate, taking the supernatant after the centrifugation, and drying to obtain the biomacromolecule modified ferric oxide nano particles.
Preferably, the biological macromolecule comprises at least one of mulberry silk protein, tussah silk protein, polypeptide, polysaccharide or amino acid; the iron source comprises at least one of ferric trichloride, ferric sulfate or ferric nitrate.
Preferably, the temperature of the hydrothermal reaction is 130-180 ℃, and the reaction time is 3-24h.
The invention also provides a preparation method of the polymer/ferrite hybrid fiber, which comprises the following steps:
(1) Mixing the polymer with ferrite, and granulating to obtain a hybrid polymer;
(2) Compounding and drying the hybridized polymer and a pure polymer, and then carrying out melt spinning to obtain a hybrid fiber;
(3) And carrying out continuous or discontinuous heat treatment on the hybrid fiber to obtain the magnetic adjustable polymer/ferrite hybrid fiber.
Preferably, the granulation in the step (1) is performed by adopting a double-screw extruder, wherein the temperature of each heating section is 280-335 ℃ in the first section, 300-355 ℃ in the second section, 300-355 ℃ in the third section, 300-355 ℃ in the fourth section and 300-355 ℃ in the fifth section; the rotating speed of the screw is 80-120r/min.
Preferably, the temperature of the heat treatment in the step (3) is 220-300 ℃, and the treatment time is 5-24h.
Compared with the prior art, the invention has the beneficial effects that:
the size, the shape and the pore structure of the bionical ferric oxide nano filler of the magnetically adjustable high-performance polymer ferrite hybrid fiber are uniform and controllable; under the modification effect of biomolecules, the polymer has excellent compatibility with a polymer matrix, and uniform dispersion of the polymer in the polymer matrix is realized; in addition, the ferric oxide filler is not easy to be aggregated by electromagnetic action in the subsequent melt spinning process, and has good spinnability; in addition, after the hybrid fiber is melted and formed, a continuous subsequent heat treatment process is applied, so that the ferrite crystal form in the fiber can be controllably converted from ferric oxide to magnetic tetraoxide, the magnetic property of the magnetic fiber is effectively controlled, and meanwhile, the industrial large-scale production of the magnetic fiber is realized; in a word, the magnetic fiber prepared by the invention has strong quality controllability, unique and advanced technology; meanwhile, the method has the advantages of simple operation, low cost and high feasibility of large-scale production. In addition, in the application of matching with an external magnetic field for use, such as in vivo nuclear magnetic imaging, magnetic induction heating and the like, the magnetism of the material can be adjusted according to the requirement so as to match with the parameters of the external magnetic field, and obtain clear imaging effect or proper maximum heating temperature and the like.
Detailed Description
The invention provides a magnetic adjustable polymer/ferrite hybrid fiber, which comprises 98-99.9% of polymer and 0.1-2.0% of ferrite by mass.
In the present invention, the polymer preferably comprises special high performance fiber polyphenylene sulfide chips and/or polyetheretherketone chips. In the present invention, the source of the polymer is not particularly limited, and a commercially available material can be used. In the present invention, the mass fraction of the polymer in the polymer/ferrite hybrid fiber is preferably 98 to 99.9%, more preferably 99%.
In the present invention, the ferrite preferably comprises biomacromolecule mineralized or modified ferric oxide nanoparticles. In the present invention, the mass fraction of ferrite in the polymer/ferrite hybrid fiber is preferably 0.1 to 2.0%, more preferably 1.0%.
In the present invention, the preparation method of the biomacromolecule mineralized iron sesquioxide nanoparticles preferably comprises: mixing the biomacromolecule solution with the iron source precursor solution, carrying out hydrothermal reaction, removing supernatant after the reaction is finished, centrifuging the precipitate, taking the supernatant after centrifugation, and drying to obtain the biomacromolecule mineralized iron trioxide nanoparticles.
In the present invention, the biological macromolecule preferably includes at least one of mulberry silk protein, tussah silk protein, polypeptide, polysaccharide or amino acid, more preferably mulberry silk protein; the iron source preferably comprises at least one of ferric chloride, ferric sulfate, or ferric nitrate, and more preferably ferric chloride.
In the present invention, the concentration of the biomacromolecule is preferably 0.01wt% to 1.0wt%, more preferably 0.1wt% to 0.5wt%.
In the present invention, the concentration of the iron source is preferably 0.01M to 0.2M, more preferably 0.07M to 0.1M.
In the invention, the mixing mode of the biomacromolecule solution and the iron source precursor solution is preferably to dropwise add the biomacromolecule solution into the stirring iron source precursor solution, stir until the biomacromolecule solution is uniform and transparent, and then carry out hydrothermal reaction.
In the invention, the hydrothermal reaction is preferably carried out in a hydrothermal reaction kettle, and the temperature of the hydrothermal reaction is preferably 130-180 ℃, and more preferably 150 ℃; the reaction time is preferably 3 to 24 hours, more preferably 12 hours.
In the invention, after the hydrothermal reaction is finished, preferably removing supernatant liquid in a product after the reaction, transferring red turbid liquid and precipitate to a centrifuge tube for centrifugation, taking out the supernatant liquid, and then drying to obtain the high-concentration and uniformly-dispersible biomineralization ferric oxide nanofiller.
In the present invention, the preparation method of the biomacromolecule modified ferric oxide nanoparticles preferably comprises: mixing the iron source precursor solution with a diethanolmethyl ether-water mixed solvent, carrying out hydrothermal reaction, removing supernatant after the reaction is finished, centrifuging the precipitate, and drying the precipitate after centrifugation to obtain high-concentration spherical ferric oxide nano ferrite; and mixing the obtained high-concentration spherical ferric oxide nano ferrite with a biomacromolecule solution for modification, removing supernatant after the modification is finished, centrifuging the precipitate, taking the supernatant after the centrifugation, and drying to obtain the biomacromolecule-modified ferric oxide nano particles.
In the present invention, the volume ratio of diethanol methyl ether to water in the diethanol methyl ether-water mixed solvent is preferably 6.
In the invention, after the hydrothermal reaction is finished, preferably removing supernatant in a product after the reaction, transferring the red turbid liquid and the precipitate to a centrifuge tube for centrifugation, respectively washing with ethanol and water for three times, taking out the red precipitate product after centrifugation, and then drying to obtain the high-concentration spherical ferric oxide nano ferrite.
In the invention, the high-concentration spherical ferric oxide nano ferrite and the biomacromolecule solution are preferably mixed by heating, magnetic stirring and blending.
In the invention, after finishing modification, supernatant in the product after reaction is preferably removed, red turbid liquid and precipitate are transferred to a centrifuge tube for centrifugation, and the supernatant is taken out and then dried, thus obtaining the high-concentration and uniformly-dispersible biomacromolecule-modified ferric oxide nanofiller.
The invention also provides a preparation method of the polymer/ferrite hybrid fiber, which comprises the following steps:
(1) Mixing the polymer with ferrite and then granulating to obtain a hybrid polymer;
(2) Compounding and drying the hybrid polymer and the pure polymer, and then carrying out melt spinning to obtain hybrid fiber;
(3) And carrying out continuous or discontinuous heat treatment on the hybrid fiber to obtain the magnetic adjustable polymer/ferrite hybrid fiber.
In the invention, the polymer and the biomacromolecule mineralized or modified ferric oxide nano-filler are preferably put into a double-screw extruder for granulation after being mixed.
In the invention, the screw rotating speed is preferably 80-120r/min, and the temperature of each heating section of the twin-screw extruder is preferably as follows: the first section is 280-335 deg.C, the second section is 300-355 deg.C, the third section is 300-355 deg.C, the fourth section is 300-355 deg.C, and the fifth section is 300-355 deg.C.
In the invention, the hybrid polymer and the pure polymer are compounded and dried, and then melt spinning is carried out, preferably, an oven is adopted for drying until the water content is 20-30ppm.
In the present invention, the spinning process of the melt spinning is preferably: screw extrusion temperature: 315-420 ℃, winding speed: 500-3000m/min, draft multiple: 2-3 times.
In the present invention, the process of the continuous heat treatment is preferably: the subsequent heat treatment is carried out on the fiber by a continuous heat treatment device, the treatment temperature is preferably 220-300 ℃, and the treatment time is preferably 5-24h.
In the present invention, the discontinuous heat treatment process preferably comprises: winding the fiber in a cylindrical mold with smooth surface or spiral grains, fixing the fiber by clamps at two ends or knotting the fiber, and then placing the fiber in a vacuum oven or a nitrogen atmosphere tube furnace at 220-300 ℃ for treatment for 5-24h; the material of the die is preferably high-temperature resistant materials such as quartz, ceramics, metal and the like.
The nanometer ferrite particles prepared by biomacromolecule biomimetic mineralization, provided by the invention, have the advantages that the sub-nanometer units are doped and modified by biomolecules, compared with the nanometer ferrite prepared by other traditional methods, the nanometer ferrite particles prepared by the biomacromolecule biomimetic mineralization method have the following advantages: the nano ferrite prepared by bionics has uniform, stable and controllable size, shape and pore structure; the nano ferrite doped with biomacromolecules can improve the compatibility of the nano ferrite with polymers, and is beneficial to uniform dispersion of the nano ferrite in polymer matrixes and subsequent spinning forming of fibers; in addition, the biological molecules can generate carbonization under certain high-temperature inert atmosphere conditions (200 ℃), and simultaneously, the ferric oxide nano units are reduced to ferroferric oxide with stronger magnetism in situ; the controllable adjustment of the magnetic characteristics of the ferrite can be realized by controlling the reduction process; in addition, the magnetism can be effectively and controllably improved through simple post-treatment after the fiber is melt-spun and formed, so that the characteristics and the quality of the magnetic fiber can be regulated and controlled in situ on the basis of not influencing the spinnability of the fiber.
Polyphenylene Sulfide (PPS) and polyether ether ketone (PEEK) fibers belong to special high-performance fibers, have excellent corrosion resistance, high temperature resistance and flame retardance, are relatively low in industrial cost, and meet the use requirements of extreme conditions such as high altitude, space and seabed. PPS and PEEK are used as polymer matrixes of high-performance fibers, and can be well compatible with ferric oxide nano-filler prepared by biomimetic mineralization and loaded with the nano-filler, so that good spinnability can be kept; meanwhile, a subsequent heat treatment process is simply applied, the PPS or PEEK polymer matrix can endure a certain high temperature, and the change of the ferrite crystal structure at the temperature of more than 200 ℃ is realized, so that the magnetic property of the ferrite hybrid fiber is effectively regulated and controlled. In addition, the PEEK serving as a biocompatible material can be used as an implanting instrument, and the PEEK is used as a carrier to construct a fiber-based material with adjustable magnetism, can be matched with an induction magnetic field device, and is used for functional repair and service effect monitoring of organs such as digestive tracts, blood vessels, rotator cuff, ligaments and the like, and can be used for killing cancer cells by local heating of anticancer drugs or in coordination.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The magnetic adjustable PPS/ferrite melt spinning hybrid fiber consists of 99.9wt% of high-performance polymer slices and 0.1wt% of nano ferrite; wherein the high-performance polymer slice is a spinning grade PPS slice.
The preparation method of the magnetic adjustable PPS/ferrite melt-spun hybrid fiber mainly comprises the following steps:
(1) Preparing nano ferrite by biobiomimetic mineralization:
firstly, preparing aqueous solutions with the concentrations of ferric trichloride and mulberry silk protein of 0.06M and 0.1wt%, then dropwise adding the biomacromolecule solution into the stirred iron source precursor solution, stirring for a certain time till the solution is uniform and transparent, transferring the mixed solution into a hydrothermal reaction kettle, applying a heating device, and then carrying out hydrothermal biomimetic mineralization reaction at the reaction temperature of 130 ℃ for 24 hours. And after the reaction is finished, removing supernatant in the product after the reaction, transferring the red turbid liquid and the precipitate to a centrifugal tube for centrifugation, taking out the supernatant, and then drying to obtain the high-concentration uniformly-dispersible biomineralized ferric oxide nanofiller (500 +/-50 nm).
(2) Preparing the fiber by blending PPS and ferrite nano-filler with a double screw and carrying out melt spinning:
uniformly mixing the powder and pure PPS slices, and then putting the mixture into a double-screw extruder for granulation, wherein the mass fraction of the iron trioxide nano-filler prepared by bionics is 10.0wt%, and the mass fraction of PPS is 90.0wt%; the rotating speed of the screw is 120r/min, and the temperature of each heating section of the double-screw extruder is as follows: the first stage (feeding zone) was 280 ℃, the second stage (extrusion zone) 300 ℃, the third stage (metering zone) 300 ℃, the fourth stage (homogenization zone) 300 ℃ and the fifth stage (outlet zone) 300 ℃.
And compounding the hybrid PPS slice prepared in the steps with pure PPS to form a mixed material with the ferrite content of 0.1%, and drying by using an oven until the water content is 20-30ppm.
And 5kg of the dried PPS material is added into melt spinning equipment to prepare the hybrid fiber. The spinning process of melt spinning is as follows:
screw extrusion temperature: 315 deg.C
The temperature of the box body is as follows: 310 deg.C
Winding speed: 3000m/min
Draft multiple: 2 times of
(3) High temperature thermal post-treatment regulating fiber magnetism
And (3) carrying out heat treatment on the hybrid PPS fiber prepared in the step through continuous heat treatment equipment in a nitrogen atmosphere, wherein the heat treatment temperature is 240 ℃, and the heat treatment time is 72 hours. The mechanical properties and magnetic properties of the hybrid fiber obtained by the above process were measured, and it was found that the tensile strength was 3.32cN/dtex, the elongation at break was 30.7%, and the saturation magnetization was 0.1emu/g.
Example 2
A magnetic adjustable PEEK/ferrite melt spinning hybrid fiber is composed of 99.0wt% of high-performance polymer slices and 1.0wt% of nano ferrite; wherein the high-performance polymer chip is a spinning-grade PEEK chip.
The preparation method of the magnetic adjustable PEEK/ferrite hybrid fiber comprises the following steps:
(1) Preparing nano ferrite by biobiomimetic mineralization:
firstly, preparing aqueous solutions with the concentrations of ferric trichloride and mulberry silk protein of 0.1M and 0.5wt%, then dropwise adding the biomacromolecule solution into the stirred iron source precursor solution, stirring for a certain time till the solution is uniform and transparent, transferring the mixed solution into a hydrothermal reaction kettle, applying a heating device, and then carrying out hydrothermal biomimetic mineralization reaction at the reaction temperature of 150 ℃ for 12 hours. And after the reaction is finished, removing supernatant in the product after the reaction, transferring the red turbid liquid and the precipitate to a centrifugal tube for centrifugation, taking out the supernatant, and then drying to obtain the high-concentration uniformly-dispersible biomineralized ferric oxide nanofiller (800 +/-100 nm).
(2) Blending ferrite nano filler and PEEK double screws and preparing fibers by melt spinning:
uniformly mixing the bionically prepared ferric oxide nano powder and pure PEEK slices, and then putting the mixture into a double-screw extruder for granulation, wherein the mass fraction of the ferrite is 1.0%, and the mass fraction of the PEEK is 99.0%; the rotating speed of the screw is 80r/min, and the temperature of each heating section of the double-screw extruder is as follows: the first section (feed zone) was 335 ℃, the second section (extrusion zone) was 355 ℃, the third section (metering zone) was 355 ℃, the fourth section (homogenization zone) was 355 ℃ and the fifth section (outlet zone) was 355 ℃.
And (3) drying the hybrid PEEK slices and the pure PEEK slices prepared in the steps by using an oven until the water content is 20-30ppm.
And (3) mixing the dried hybrid PEEK slices and pure PEEK slices according to the weight ratio of 1:19, and adding 5kg of the mixture into melt spinning equipment to obtain the hybrid fiber. The spinning process of melt spinning is as follows:
screw extrusion temperature: 420 deg.C
The temperature of the box body is as follows: 415 deg.C
Winding speed: 600m/min
Draft multiple: 2.5 times of
(3) High temperature thermal post-treatment regulating fiber magnetism
And (3) carrying out heat treatment on the hybrid PEEK fiber prepared in the step through continuous heat treatment equipment in a nitrogen atmosphere, wherein the heat treatment temperature is 280 ℃, and the heat treatment time is 20 hours. The mechanical properties and magnetic properties of the hybrid fiber obtained by the above process were measured, and it was found that the tensile strength was 4.43cN/dtex, the elongation at break was 18.6%, and the saturation magnetization was 0.9emu/g. When the fiber profile is placed in animal tissues, the fiber profile can present clear and artifact-free fiber profiles under 3T magnetic resonance imaging equipment, and the fiber profile can be used for constructing medical implantation instruments for radiography.
Example 3
A PPS hybridized magnetic fiber based on biological protein modified ferric oxide consists of 99.0wt% of high-performance polymer slices and 1.0wt% of nano ferrite; wherein the high-performance polymer slice is a spinning grade PPS slice.
The preparation method of the magnetic adjustable PPS/ferrite melt-spun hybrid fiber mainly comprises the following steps:
(1) Preparation of ferrite and biomolecule post-modification:
1. preparing spherical ferric oxide nano ferrite: firstly, preparing a mixed solvent with the volume ratio of diethanol methyl ether to water being 6, then adding ferric trichloride according to the amount of 0.07M, stirring for a certain time till the mixed solution is uniform and transparent, transferring the mixed solution into a hydrothermal reaction kettle, applying a heating device, and then carrying out hydrothermal reaction at the reaction temperature of 180 ℃ for 48 hours. And after the reaction is finished, removing supernatant in the product after the reaction, transferring the red turbid liquid and the precipitate to a centrifugal tube for centrifugation, washing the centrifugal tube with ethanol and water for three times respectively, taking out the red precipitate product after the centrifugation, and then drying the red precipitate product to obtain the high-concentration spherical ferric oxide nano ferrite (500 +/-50 nm).
2. Modification of biological molecules: and (2) heating (1.0 wt%) iron ball nano components and a fibroin solution (130 ℃), magnetically stirring (200 r/min), blending for 10h, modifying the fibroin biomacromolecules on the iron sesquioxide ball nano particles, removing supernatant in a product after the modification, transferring red turbid liquid and precipitate to a centrifuge tube for centrifugation, taking out the supernatant, and then drying to obtain the high-concentration uniformly-dispersible biomacromolecule-modified ferric oxide nano filler.
(2) PPS and ferrite nanofiller are blended and melt spun together to prepare the fiber:
uniformly mixing the powder and pure PPS slices, and then putting the mixture into a double-screw extruder for granulation, wherein the mass fraction of the biomacromolecule modified ferric oxide nano filler is 1.0wt%, and the mass fraction of the PPS is 99.0wt%; the rotating speed of the screw is 120r/min, and the temperature of each heating section of the double-screw extruder is as follows: the first stage (feed zone) was 280 ℃, the second stage (extrusion zone) 300 ℃, the third stage (metering zone) 300 ℃, the fourth stage (homogenization zone) 300 ℃ and the fifth stage (outlet zone) 300 ℃.
And (3) drying the hybrid PPS slices prepared in the steps until the water content is 20-30ppm by using an oven.
And 5kg of the dried hybrid PPS slices are added into melt spinning equipment to prepare the hybrid fiber. The spinning process of melt spinning is as follows:
screw extrusion temperature: 315 deg.C
The temperature of the box body is as follows: 310 deg.C
Winding speed: 3000m/min
Draft multiple: 2 times of
(4) High temperature thermal post-treatment regulating fiber magnetism
And (3) carrying out heat treatment on the hybrid PPS fiber prepared in the step through continuous heat treatment equipment in a nitrogen atmosphere, wherein the heat treatment temperature is 220 ℃, and the heat treatment time is 72 hours. The mechanical properties and magnetic properties of the hybrid fiber obtained by the above process were measured, and it was found that the tensile strength was 2.79cN/dtex, the elongation at break was 27.6%, and the saturation magnetization was 0.5emu/g.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A magnetically tunable polymer/ferrite hybrid fiber comprising, in mass percent, 98-99.9% polymer and 0.1-2.0% ferrite.
2. The polymer/ferrite hybrid fiber according to claim 1, characterized in that the polymer comprises polyphenylene sulfide chips and/or polyetheretherketone chips.
3. The polymer/ferrite hybrid fiber according to claim 1, wherein the ferrite comprises biomacromolecule mineralized or modified iron trioxide nanoparticles.
4. The polymer/ferrite hybrid fiber according to claim 3, wherein the biomacromolecule mineralized iron trioxide nanoparticles are prepared by a method comprising: mixing the biomacromolecule solution with the iron source precursor solution, carrying out hydrothermal reaction, removing supernatant after the reaction is finished, centrifuging the precipitate, taking the supernatant after centrifugation, and drying to obtain the biomacromolecule mineralized iron trioxide nanoparticles.
5. The polymer/ferrite hybrid fiber according to claim 3, wherein the preparation method of the biomacromolecule modified ferric oxide nanoparticles comprises: mixing the iron source precursor solution with a diethanolmethyl ether-water mixed solvent, carrying out hydrothermal reaction, removing supernatant after the reaction is finished, centrifuging the precipitate, and drying the precipitate after centrifugation to obtain high-concentration spherical ferric oxide nano ferrite; and mixing the obtained high-concentration spherical ferric oxide nano ferrite with a biomacromolecule solution for modification, removing supernatant after the modification is finished, centrifuging the precipitate, taking the supernatant after the centrifugation, and drying to obtain the biomacromolecule-modified ferric oxide nano particles.
6. The polymer/ferrite hybrid fiber according to claim 4 or 5, wherein the biological macromolecule comprises at least one of mulberry silk protein, tussah silk protein, polypeptide, polysaccharide or amino acid; the iron source comprises at least one of ferric trichloride, ferric sulfate or ferric nitrate.
7. The polymer/ferrite hybrid fiber according to claim 4 or 5, wherein the hydrothermal reaction temperature is 130-180 ℃ and the reaction time is 3-24h.
8. A method of preparing the polymer/ferrite hybrid fiber according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing the polymer with ferrite, and granulating to obtain a hybrid polymer;
(2) Compounding and drying the hybrid polymer and the pure polymer, and then carrying out melt spinning to obtain hybrid fiber;
(3) And carrying out continuous or discontinuous heat treatment on the hybrid fiber to obtain the magnetic adjustable polymer/ferrite hybrid fiber.
9. The method for preparing the polymer/ferrite hybrid fiber according to claim 8, wherein the granulation in the step (1) is performed by using a twin-screw extruder, wherein the temperature of each heating section is 280-335 ℃, 300-355 ℃ in the first section, 300-355 ℃ in the second section, 300-355 ℃ in the third section, 300-355 ℃ in the fourth section, and 300-355 ℃ in the fifth section; the rotating speed of the screw is 80-120r/min.
10. The preparation method of the polymer/ferrite hybrid fiber according to claim 8, wherein the temperature of the heat treatment in the step (3) is 220-300 ℃ and the treatment time is 5-24h.
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