CN115679479A - Spinel ferrite hollow fiber and preparation method thereof - Google Patents
Spinel ferrite hollow fiber and preparation method thereof Download PDFInfo
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- CN115679479A CN115679479A CN202211513086.9A CN202211513086A CN115679479A CN 115679479 A CN115679479 A CN 115679479A CN 202211513086 A CN202211513086 A CN 202211513086A CN 115679479 A CN115679479 A CN 115679479A
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 63
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 49
- 239000011029 spinel Substances 0.000 title claims abstract description 49
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000835 fiber Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 150000002505 iron Chemical class 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 24
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 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
- 239000011701 zinc Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 1
- 230000005291 magnetic effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910001053 Nickel-zinc ferrite Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 230000005350 ferromagnetic resonance Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
Dissolving a metal iron salt and two or more than two second metal salts in an organic solvent to obtain a metal salt mixed solution, adding a high molecular polymer into absolute ethyl alcohol, uniformly stirring to obtain a high molecular polymer solution, adding the metal salt mixed solution into the high molecular polymer solution, and continuously stirring to obtain a precursor solution; drawing the precursor solution by using a glass flat plate under a certain humidity to obtain organogel fibers, simultaneously drying by using hot air to remove part of the solvent, collecting the organogel fibers, and putting the organogel fibers into an oven for drying; and putting the dried organogel fiber into a tubular furnace for sintering by a segmented heat treatment process to obtain the spinel ferrite hollow fiber.
Description
Technical Field
The invention relates to the field of magnetic material preparation, in particular to a spinel ferrite hollow fiber and a preparation method thereof.
Background
With the development of science and technology, more and more electronic devices are used in people's lives, and the generated electromagnetic pollution is increased day by day. In the use process of various high-precision informationized instruments and equipment, electromagnetic pollution often influences the operation of the equipment, and excessive high-frequency electromagnetic pollution even can cause long-term harm to the health of human beings. The wave-absorbing material can effectively reduce or eliminate electromagnetic pollution, thereby becoming a research hotspot of experts and scholars of various countries. The ferrite wave-absorbing material has higher resistivity and high-frequency permeability, and the main mechanisms for absorbing electromagnetic wave energy are hysteresis loss, eddy current loss, ferromagnetic resonance and the like.
The ferrite belongs to ferromagnetic materials, and is divided into three types of spinel type, garnet type and magnetoplumbite type according to the difference of structures, and the three types of ferrite can be used in the field of wave absorption. The spinel ferrite fiber has strong magnetism and dielectric property, the saturation magnetization is far greater than the other two types of ferrite, and the structural characteristics of the spinel ferrite fiber are favorable for absorbing waves.
Among spinel ferrites, nickel zinc ferrites, which are typically represented, are widely used in the fields of instruments, radars, electronic countermeasure, etc. because of their advantages such as wide frequency band, light weight, and small volume. The micron-sized conventional ferrite is subjected to nanocrystallization or hollow ferrite is prepared, the specific gravity of the whole ferrite is reduced due to the change of the size and the shape, and the physical properties of the material such as electricity, magnetism, light and the like are influenced, so that the properties of the material are influenced to a certain extent. The ferrite fiber material is lighter in weight compared with powder and thin film materials, and the unique shape can solve the problem of nanoparticle agglomeration, so that the weight of the coating is reduced, and the absorption band of electromagnetic waves is expanded.
Chinese patent ZL 201410314978.5 discloses a template method for preparing a nickel-zinc ferrite material, which is prepared by taking metal nitrate as a raw material and cotton fiber as a template in one step without adding a precipitator and the like by means of a solvothermal method, replicates the micro morphology of the cotton fiber, and has good crystallization property and magnetic property, so that the application range of the nickel-zinc ferrite nano material is effectively expanded, but the method has long time consumption, the structure of the obtained ferrite fiber is incomplete, and the form of a sample has certain influence on the magnetic property. Chinese patent ZL 200510095475.4 discloses a method for preparing spinel ferrite fiber by a sol-gel method, wherein zinc nitrate, ferric nitrate and citric acid are used as raw materials, ammonia water is added to adjust the pH value to 5.7, then dehydration is carried out, traction drawing spinning and drying are carried out, and spinel zinc ferrite fiber with excellent performance is obtained after sintering at 800-1000 ℃, but the method needs to adjust the pH value of gel and the viscosity of a precursor at the same time, so that the process operation difficulty is increased, and the precursor still needs to be sintered at a higher temperature to obtain the ferrite fiber. Chinese patent ZL 201611154343.9 provides a method for drawing a precursor solution containing a ceramic precursor, a polymer and a solvent into nanofibers by a gas flow and collecting the nanofibers with a porous collector; the collected nanofibers are sintered to obtain ceramic nanofibers, the obtained ceramic nanofibers have the characteristics of ultra-light weight, high temperature resistance and the like, and can be effectively used in a plurality of key and important fields, but the method needs complicated equipment, and has the problems of difficult fiber collection, needle blockage, droplet formation and the like caused by solvent evaporation.
Due to the characteristics of the magnetic material, the preparation method has the problems of complex process, difficult control of conditions, high calcination temperature and the like, and the invention aims to provide the preparation method which is economic in raw materials, simple in process conditions, low in sintering temperature and environment-friendly.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a spinel ferrite hollow fiber material with good hysteresis loss and wave absorption performance and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a spinel ferrite hollow fiber comprises the following steps:
1) Dissolving a metal iron salt and two or more than two second metal salts in an organic solvent to obtain a metal salt mixed solution, adding a high molecular polymer into absolute ethyl alcohol, uniformly stirring to obtain a high molecular polymer solution, adding the metal salt mixed solution into the high molecular polymer solution, and continuously stirring to obtain a precursor solution;
2) Drawing the precursor solution in the step 1) by adopting a glass flat plate under certain humidity to obtain organic gel fibers, simultaneously drying by adopting hot air to remove part of the solvent, and then collecting the organic gel fibers and putting the organic gel fibers into an oven for drying;
3) Putting the organic gel fiber dried in the step 2) into a tubular furnace to carry out sectional heat treatment process sintering to obtain the spinel ferrite hollow fiber.
The second metal salt may be two or more of chloride, sulfate, nitrate, perchlorate, carbonate and acetylacetonate of nickel, cobalt, zinc, manganese, iron, calcium, titanium, aluminum, lithium, copper, vanadium and chromium, and the metal of the second metal salt is preferably nickel and zinc.
The metal iron salt can be one of ferric chloride, ferric nitrate, ferric sulfate, ferric perchlorate, ferric carbonate and ferric acetylacetonate.
The organic solvent is N, N-Dimethylformamide (DMF), tetrahydrofuran (THF) or dimethyl carbonate (DMC); the high molecular polymer is polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN), polyethylene oxide (PEO) or polyvinylidene fluoride (PVDF).
The molar ratio of ferric ions to total second metal ions of the metallic iron salt is 2.
In the metal salt mixed solution, the total mass fraction of the metal iron salt and the second metal salt is 20-30 wt.%.
In the high molecular polymer solution, the mass fraction of the high molecular polymer is 20-25 wt.%.
In step 2), the humidity is lower than 70%.
The segmented heat treatment process in the step 3) comprises the following steps: preoxidation and heat preservation are carried out on the organic gel fiber at 195-220 ℃ for 120min in the air atmosphere, then the temperature is raised to 450-750 ℃ for 120min, and the organic gel fiber is cooled to room temperature along with a furnace and then taken out; the temperature rise speed is 2-4 ℃/min, and the flow rate is 60-120 mL/min.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The spinel ferrite hollow fiber prepared by the invention has good magnetic hysteresis loss and wave-absorbing performance, and is expected to be widely applied to wave-absorbing coating materials; due to the characteristics of the hollow fiber structure, the requirements of light and thin wave-absorbing coating materials can be improved, and the internal multiple attenuation reflection is increased to improve the electromagnetic wave absorption effect;
(2) The spinel ferrite hollow fiber prepared by the invention has good formability, the diameters of the spinel ferrite hollow fiber are all between 0.5 and 2 mu m, the volume density is low, and the microstructure is uniform and compact;
(3) The method has simple and economic process, the shape and the structure of the fiber can be regulated and controlled by adjusting the technical parameters such as the proportion of metal salt, the mass concentration of PVP, the sintering temperature and the like, the popularization is convenient to realize the industrial production, and particularly, the adding proportion of the metal salt directly influences the integrity and the magnetic property of the hollow shell layer formed by the spinel ferrite hollow fiber; the mass concentration of PVP is adjusted in such a way that the viscosity of the precursor can be controlled, and the viscosity influences the diameter of the fiber; the sintering temperature is adjusted in such a way that the low-temperature calcination part is selected to be slightly higher than the glass transition temperature (Tg =180 ℃) of PVP, PVP macromolecules can move more freely, a precursor forms a shell layer through polymer chain diffusion, PVP is completely decomposed at a high-temperature stage, and finally a spinel ferrite hollow fiber structure is formed.
Drawings
FIG. 1 is an infrared (FT-IR) spectrum of the spinel ferrite hollow fiber prepared in examples 1-4.
FIG. 2 is an X-ray diffraction (XRD) pattern of the spinel ferrite hollow fibers prepared in examples 1 to 4.
FIG. 3 is a VSM spectrum of the spinel ferrite hollow fiber prepared in examples 1-4.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the surface of the spinel ferrite hollow fiber ceramic prepared in examples 1 to 4. In FIG. 4, (a) the spinel ferrite hollow fiber prepared in example 1 was sintered at 450 ℃; (b) The spinel ferrite hollow fiber prepared by corresponding to the embodiment 2 is sintered at 550 ℃; (c) The spinel ferrite hollow fiber prepared in the corresponding example 3 is sintered at 650 ℃; (d) The spinel ferrite hollow fiber prepared corresponding to example 4 was sintered at 750 ℃.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
1. 0.578g of NiCl 2 ·6H 2 O,0.220g ZnCl 2 And 3.268g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 10mL of DMF in sequence, wherein the mass fraction of the metal salt is 30%, and ultrasonically dispersing the mixed solution for 20min;
2. 20mL of absolute ethyl alcohol is placed in a magnetic stirrer to be stirred at the rotating speed of 30rpm under the normal temperature state, 4.50g of PVP is uniformly and slowly added into the absolute ethyl alcohol, wherein the mass fraction of polyvinylpyrrolidone is 22%, and the stirring is continuously carried out for 2h to obtain viscous solution;
3. adding the mixed solution of DMF and metal salt into PVP/absolute ethyl alcohol solution, adjusting the rotating speed of a magnetic stirrer to 60rpm, and continuously stirring for 3 hours to obtain uniform and transparent yellowish-brown precursor solution;
4. in a room temperature environment with the air humidity lower than 70%, drawing by adopting a parallel glass plate to obtain organic gel fibers, performing auxiliary drying by adopting hot air at 60 ℃ to remove part of the solvent, collecting the organic gel fibers in a culture dish, and heating and drying in an oven at 80 ℃ for 5 hours to sufficiently remove the organic solvent;
5. putting the organic gel fiber obtained by drying into a tube furnace, carrying out low-temperature preoxidation and heat preservation for 120min at 200 ℃, then raising the temperature to 450 ℃, preserving the heat for 120min, finally cooling to room temperature along with the furnace, and taking out to obtain the spinel ferrite hollow fiber; the sintering atmosphere is air, the heating rate is 3 ℃/min, and the flow rate is preferably 60mL/min.
Example 2
1. 0.578g of NiCl 2 ·6H 2 O,0.220g ZnCl 2 And 3.268g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 10mL of DMF in sequence, wherein the mass fraction of the metal salt is 30%, and ultrasonically dispersing the mixed solution for 20min;
2. placing 20mL of absolute ethyl alcohol into a magnetic stirrer, stirring at the rotating speed of 30rpm under the normal temperature state, uniformly and slowly adding 4.50g of PVP into the absolute ethyl alcohol, wherein the mass fraction of polyvinylpyrrolidone is 22%, and continuously stirring for 2 hours to obtain a viscous solution;
3. adding the mixed solution of the DMF and the metal salt into a PVP/absolute ethyl alcohol solution, adjusting the rotating speed of a magnetic stirrer to 60rpm, and continuously stirring for 3 hours to obtain a uniform and transparent yellowish-brown precursor solution;
4. in a room temperature environment with the air humidity below 70%, drawing by adopting a parallel glass plate to obtain organic gel fibers, carrying out auxiliary drying by adopting hot air at 60 ℃ to remove part of the solvent, collecting the organic gel fibers in a culture dish, and heating and drying in an oven at the temperature of 80 ℃ for 5 hours to sufficiently remove the organic solvent;
5. putting the organic gel fiber obtained by drying into a tube furnace, carrying out low-temperature pre-oxidation at 200 ℃ for heat preservation for 120min, then raising the temperature to 550 ℃ for heat preservation for 120min, finally cooling to room temperature along with the furnace, and taking out to obtain the spinel ferrite hollow fiber; the sintering atmosphere is air, the heating rate is 3 ℃/min, and the flow rate is preferably 60mL/min.
Example 3
1. 0.578g of NiCl 2 ·6H 2 O,0.220g ZnCl 2 And 3.268g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 10mL of DMF in sequence, wherein the mass fraction of the metal salt is 30%, and ultrasonically dispersing the mixed solution for 20min;
2. 20mL of absolute ethyl alcohol is placed in a magnetic stirrer to be stirred at the rotating speed of 30rpm under the normal temperature state, 4.50g of PVP is uniformly and slowly added into the absolute ethyl alcohol, wherein the mass fraction of polyvinylpyrrolidone is 22%, and the stirring is continuously carried out for 2h to obtain viscous solution;
3. adding the mixed solution of the DMF and the metal salt into a PVP/absolute ethyl alcohol solution, adjusting the rotating speed of a magnetic stirrer to 60rpm, and continuously stirring for 3 hours to obtain a uniform and transparent yellowish-brown precursor solution;
4. in a room temperature environment with the air humidity lower than 70%, drawing by adopting a parallel glass plate to obtain organic gel fibers, performing auxiliary drying by adopting hot air at 60 ℃ to remove part of the solvent, collecting the organic gel fibers in a culture dish, and heating and drying in an oven at 80 ℃ for 5 hours to sufficiently remove the organic solvent;
5. putting the organic gel fiber obtained by drying into a tube furnace, carrying out low-temperature preoxidation and heat preservation at 200 ℃ for 120min, then raising the temperature to 650 ℃ and preserving the heat for 120min, finally cooling to room temperature along with the furnace and taking out to obtain the spinel ferrite hollow fiber; the sintering atmosphere is air, the heating rate is 3 ℃/min, and the flow rate is preferably 60mL/min.
Example 4
1. 0.578g of NiCl 2 ·6H 2 O,0.220g ZnCl 2 And 3.268g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 10mL of DMF in sequence, wherein the mass fraction of the metal salt is 30%, and ultrasonically dispersing the mixed solution for 20min;
2. 20mL of absolute ethyl alcohol is placed in a magnetic stirrer to be stirred at the rotating speed of 30rpm under the normal temperature state, 4.50g of PVP is uniformly and slowly added into the absolute ethyl alcohol, wherein the mass fraction of polyvinylpyrrolidone is 22%, and the stirring is continuously carried out for 2h to obtain viscous solution;
3. adding the mixed solution of DMF and metal salt into PVP/absolute ethyl alcohol solution, adjusting the rotating speed of a magnetic stirrer to 60rpm, and continuously stirring for 3 hours to obtain uniform and transparent yellowish-brown precursor solution;
4. in a room temperature environment with the air humidity lower than 70%, drawing by adopting a parallel glass plate to obtain organic gel fibers, performing auxiliary drying by adopting hot air at 60 ℃ to remove part of the solvent, collecting the organic gel fibers in a culture dish, and heating and drying in an oven at 80 ℃ for 5 hours to sufficiently remove the organic solvent;
5. putting the organic gel fiber obtained by drying into a tube furnace, carrying out low-temperature pre-oxidation at 200 ℃ for heat preservation for 120min, then raising the temperature to 750 ℃ for heat preservation for 120min, finally cooling to room temperature along with the furnace, and taking out to obtain the spinel ferrite hollow fiber; the sintering atmosphere is air, the heating rate is 3 ℃/min, and the flow rate is preferably 60mL/min.
The infrared (FT-IR) spectrum (FIG. 1) of the spinel ferrite hollow fiber of the present invention shows that 570cm are present in all samples -1 The nearby absorption band, which is caused by the vibration between the metal ion and the oxygen ion at the A site of the tetrahedron, demonstrates that the spinel ferrite phase is formed by this method at a low temperature stage (450 ℃ C.). The spinel ferrite hollow fiber of the present invention has a plurality of characteristic peaks of spinel ferrite in an X-ray diffraction (XRD) pattern (fig. 2), wherein 2 θ =29.5 °/35.1 °/42.8 °/56.9 °/62.4 ° correspond to (220)/(311)/(400)/(511)/(440) crystal planes of spinel ferrite, respectively, and the intensity of the diffraction peaks is gradually increased as the temperature is increased. The VSM spectrogram of the spinel ferrite hollow fiber is shown in figure 3, a magnetic hysteresis loop of a sample is in a saturated state, and the magnetic saturation intensity of the sample is gradually increased along with the temperature. The Scanning Electron Microscope (SEM) picture of the spinel ferrite hollow fiber is shown in figure 4, the ferrite hollow fiber is good in integrity, smooth and compact in surface, and the diameter range of the fiber is 0.5-2 mu m.
The invention adopts a sol-gel method, simultaneously utilizes a flat-plate spinning drawing technology to prepare and obtain the continuous spinel ferrite hollow fiber, improves the manufacturing cost and the spinning safety, simultaneously does not generate the change of the valence state of metal ions in the reaction process, ensures that the purity of the product is high, utilizes polyvinylpyrrolidone/absolute ethyl alcohol solution as a precursor, and takes Fe in a liquid phase state 3+ ，Ni 2+ ，Zn 2+ Uniformly mixing, in a low-temperature pre-oxidation stage, generating ferrite on the surface layer by taking polyvinylpyrrolidone as a framework, and removing the polyvinylpyrrolidone at a high temperature to obtain hollow ferrite fibers; the hollow ferrite fiber is used as a wave absorbing material, the overall wave absorbing performance is improved, the overall quality can be reduced, or the fiber is spread on the outer layer of the material in a coating mode, the electromagnetic wave attenuation capability of the material can be improved through multiple attenuation reflection, and the hollow ferrite fiber has great application value in the aspects of radars, stealth materials, electromagnetic shielding and the like.
Claims (10)
1. A preparation method of a spinel ferrite hollow fiber is characterized by comprising the following steps:
1) Dissolving a metal iron salt and two or more than two second metal salts in an organic solvent to obtain a metal salt mixed solution, adding a high molecular polymer into absolute ethyl alcohol, uniformly stirring to obtain a high molecular polymer solution, adding the metal salt mixed solution into the high molecular polymer solution, and continuously stirring to obtain a precursor solution;
2) Drawing the precursor solution in the step 1) by using a glass flat plate under a certain humidity to obtain organogel fibers, simultaneously drying by using hot air to remove part of the solvent, and then collecting the organogel fibers and putting the organogel fibers into an oven for drying;
3) And putting the dried organogel fiber into a tubular furnace for sintering by a segmented heat treatment process to obtain the spinel ferrite hollow fiber.
2. The method for preparing a spinel ferrite hollow fiber according to claim 1, wherein the method comprises the following steps: the second metal salt can be two or more of chloride, sulfate, nitrate, perchlorate, carbonate and acetylacetone salt of nickel, cobalt, zinc, manganese, iron, calcium, titanium, aluminum, lithium, copper, vanadium and chromium, and the metal of the second metal salt is preferably nickel and zinc.
3. The method for preparing a spinel ferrite hollow fiber according to claim 1, wherein the method comprises the following steps: the metal iron salt can be one of ferric chloride, ferric nitrate, ferric sulfate, ferric perchlorate, ferric carbonate and ferric acetylacetonate.
4. The method for preparing a spinel ferrite hollow fiber according to claim 1, wherein the method comprises the following steps: the organic solvent is N, N-Dimethylformamide (DMF), tetrahydrofuran (THF) or dimethyl carbonate (DMC); the high molecular polymer is polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN), polyethylene oxide (PEO) or polyvinylidene fluoride (PVDF).
5. The method for preparing a spinel ferrite hollow fiber according to claim 1, wherein the method comprises the following steps: the molar ratio of ferric ions of the metallic iron salt to total secondary metal ions is 2.
6. The method for preparing a spinel ferrite hollow fiber according to claim 1, wherein the method comprises the following steps: in the metal salt mixed solution, the total mass fraction of the metal iron salt and the second metal salt is 20-30 wt%, and the total mass fraction of the organic solvent is 70-80 wt%.
7. The method for preparing a spinel ferrite hollow fiber according to claim 1, characterized by comprising the following steps: in the high molecular polymer solution, the mass fraction of the high molecular polymer is 20-25 wt.%.
8. The method for preparing a spinel ferrite hollow fiber according to claim 1, wherein the method comprises the following steps: in step 2), the humidity is lower than 70%.
9. The method for preparing the spinel ferrite hollow fiber according to claim 1, wherein the step 3) comprises the following steps: preoxidation and heat preservation are carried out on the organic gel fiber at 195-220 ℃ for 120min in the air atmosphere, then the temperature is raised to 450-750 ℃ for 120min, and the organic gel fiber is cooled to room temperature along with a furnace and then taken out; the temperature rise speed is 2-4 ℃/min, and the air flow rate is 60-120 mL/min.
10. A spinel ferrite hollow fiber produced by the production method according to any one of claims 1 to 9.
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