CN110273189B - Continuous silicon steel long fiber electrical magnetic material and preparation method thereof - Google Patents
Continuous silicon steel long fiber electrical magnetic material and preparation method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 73
- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 58
- 239000000696 magnetic material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002505 iron Chemical class 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 239000012046 mixed solvent Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims abstract description 9
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 8
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 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 10
- 239000001913 cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000008901 benefit Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001125 extrusion Methods 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
- 239000002657 fibrous material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Soft Magnetic Materials (AREA)
Abstract
In order to solve the defects of the prior art, the invention provides a preparation method of a continuous silicon steel long fiber electrical magnetic material, which comprises the following steps: s1, mixing an organic solvent, manganese hydroxide and deionized water, wherein the molar ratio of the organic solvent to the manganese oxide is 1:0.5-20, and the pH value is kept at 5.6-8.5; s2, adding a metal iron salt into the mixed solvent, wherein the mass ratio of the metal iron salt to the mixed solvent is as follows: 1: 5-20; s3, dehydrating the mixed solution at the temperature of 60-80 ℃ in vacuum to a gel state to obtain iron gel; s4, adding silicon tetrachloride at the temperature of 15-20 ℃ of the iron gel, and stirring until a preset ratio of silicon element to iron element is achieved; s5, spinning the mixed gel by adopting a high-voltage electrostatic spinning method; s6, obtaining the continuous silicon steel magnetic long fiber after heat treatment operation. The invention finally spins the continuous silicon steel long fiber with the length-diameter ratio of more than 4000:1, but not short fiber.
Description
Technical Field
The invention belongs to the technical field of magnetic materials, and particularly relates to a continuous silicon steel long fiber electrical magnetic material.
Background
Soft magnetic materials used in low-frequency magnetic fields are required to have high magnetic permeability, low coercive force, and other properties. The magnetic conductivity is high, and when the number of turns of the coil is fixed, high magnetic induction intensity can be generated by passing small excitation current, so that high output voltage is obtained. The coercive force of the material is low, the area of a magnetic hysteresis loop is small, and the iron loss is also small. Therefore, the iron core made of the material with high magnetic permeability and low coercive force is beneficial to reducing the size of a product and improving the sensitivity.
The low-frequency soft magnetic material is mainly silicon steel sheets. Adding 0.8-4.5% of silicon into iron containing a small amount of carbon to obtain the silicon steel. Compared with pure iron for electricians, the silicon steel has higher resistivity and low iron loss, and the magnetic aging is basically eliminated. At present, silicon steel sheets are widely used for iron cores of products such as motors, transformers, relays, mutual inductors, switches and the like. Although the saturation magnetic induction of the silicon steel sheet is high, the silicon steel sheet contains silicon element, so that the heat conductivity of the silicon steel sheet is reduced, the hardness is improved, and the brittleness is increased. For this reason, the magnetic properties of the high-performance cold-rolled silicon steel sheet are sensitive to the influence of stress, and stress is generated during punching, stacking, or winding of the iron core, thereby deteriorating the magnetic properties. This drawback greatly limits the application of silicon steel sheets to equipment of various specific configurations and dimensions.
Focusing on the fact that the production and application of magnetic fiber materials are mature day by day, the production of continuous silicon steel long fiber electrical materials for low-frequency magnetic fields becomes possible. The continuous silicon steel long fiber can be regarded as one-dimensional embodiment of a silicon steel sheet, and is required to be in a filiform shape, the width is in a nanometer or micrometer level, and the length-diameter ratio is higher. The continuous silicon steel long fiber electrical material changes a silicon steel sheet from a three-dimensional structure to a one-dimensional structure of silicon steel fibers, and can further improve the magnetic conductivity and greatly reduce the coercive force under the nanometer and micrometer scales.
At present, most of the related patents of the magnetic fibers relate to the preparation method of the short magnetic fibers, and the related aspects of the silicon steel fibers are rarely related. The patent "Mn-Zn ferrite fiber and its preparation method" (see patent publication No. CN 101104556A) specifically describes the specific preparation method of Mn-Zn ferrite fiber. The patent mainly discloses that the prepared ferrite fiber is mainly used in the field of high-frequency magnetic fields. Meanwhile, the fiber is obtained by filament picking, filament drawing or filament throwing, and the diameter of the obtained fiber is 0.2-100 mu m and does not reach the nanometer size. The patent of a shell-core structure magnetic fibrous silicon dioxide nanoparticle and a preparation method and application thereof (see patent publication No. CN 107362775A) concretely describes a shell-core structure magnetic fibrous silicon dioxide nanoparticle and a preparation method thereof. The outer layer is fibrous silicon dioxide, and the inner core is hollow ferroferric oxide. The patent results in short fibers or nanoparticles with short aspect ratios. And meanwhile, the nano particles are finally obtained only by alternately cleaning distilled water and absolute ethyl alcohol and then drying, and the efficiency is low. The invention relates to a far infrared flat ECDP magnetic fiber and a preparation method thereof (see patent publication No. CN 102011210A), and discloses a flat magnetic fiber with antibacterial, anti-ultraviolet and far infrared health care functions. The patent adopts a melt spinning method, a non-sol-gel method and a high-voltage electrostatic spinning method are combined, and the whole process is more complex. In the patent of a magnetic fiber and a manufacturing method thereof (see patent publication No. CN 101649503A), a double-screw extruder is adopted for extrusion and granulation to obtain a magnetic fiber core layer material. And spinning the skin layer material and the core layer material in proportion by using a skin-core spinning machine to form a wound filament. Different from the above patents, the invention mainly provides a preparation method of silicon steel fibers, which combines a sol-gel method and a high-voltage electrostatic spinning method, and adopts special process flow and proportion to finally obtain the continuous magnetic long fibers.
Disclosure of Invention
The invention provides a preparation method of a continuous silicon steel long fiber electrical magnetic material aiming at the problems in the prior art, which comprises the following steps:
s1, mixing an organic solvent, manganese hydroxide and deionized water, wherein the molar ratio of the organic solvent to the manganese oxide is 1:0.5-20, adding the deionized water to keep the pH value of the solution at 5.6-8.5, and uniformly stirring to obtain a mixed solvent;
s2, adding a metal iron salt into the mixed solvent, wherein the mass ratio of the metal iron salt to the mixed solvent is as follows: 1:5-20, and uniformly stirring to obtain a mixed solution;
s3, dehydrating the mixed solution at the temperature of 60-80 ℃ in vacuum to a gel state to obtain iron gel;
s4, dropwise adding silicon tetrachloride at the temperature of 15-20 ℃ of the iron gel, and stirring until a preset ratio of silicon element to iron element is achieved to obtain mixed gel;
s5, spinning the mixed gel by adopting a high-voltage electrostatic spinning method, and collecting the obtained long fibrous cellulose filaments;
s6, placing the long fibrous long fiber obtained in the step S5 in a heating device, and performing heat treatment operation to obtain the continuous silicon steel magnetic long fiber.
Further, in step S1, the organic solvent is: one or both of polyvinyl alcohol and citric acid.
Further, in step S2, the metallic iron salt is: one or both of ferric nitrate and ferric chloride.
Further, the molar mass of the silicon element is A, and the molar mass of the iron element is B; step S4, the predetermined ratio of si to fe is: a: b is 1-10: 90-99.
Further, the molar mass A of the silicon element satisfies the following condition: a/(a + B) ═ C; the value range of C is as follows: 0.01-0.1.
Further, in step S5, the control parameters of the high voltage electrostatic spinning are as follows: the flow rate is 0.5-1.2ml/h, the voltage is 15-25kV, and the distance between the two electrodes is 12-16 cm.
Further, the heat treatment operation of step S6 includes:
(1) filling nitrogen-hydrogen mixed gas into a heating device with long fibrous cellulose filaments, gradually raising the temperature of the heating device, and finally stabilizing at the temperature of 730-;
(2) controlling the temperature of the heating device to be 380-420 ℃, and calcining for 4-5 hours in an air environment;
(3) filling hydrogen, gradually raising the temperature of the heating device, and finally stabilizing at the temperature of 730-.
Further, in the nitrogen-hydrogen mixed gas in the step (1), the ratio of nitrogen: hydrogen is 1: 5-20;
further, the temperature of the heating device is gradually increased in the step (1) and the step (3), and the temperature rising speed is 5-30 ℃/min.
Further, magnesium oxide or chromium oxide coating materials are adopted to perform spray coating on the continuous silicon steel magnetic long fibers obtained in the step S6.
In addition, the invention also provides a continuous silicon steel long fiber electrical magnetic material which is prepared by the preparation method of the continuous silicon steel long fiber electrical magnetic material.
The invention has at least one of the following advantages:
the invention provides a preparation method of a continuous silicon steel long fiber electrical material. It has at least the following advantages.
1. The invention combines two technologies of a sol-gel method and a high-voltage electrostatic spinning method to obtain a proper spinnable precursor according to different proportions. By controlling the parameters of a proper high-voltage electrostatic spinning machine and combining a drum type collector, continuous silicon steel long fibers with the length-diameter ratio of more than 4000:1 are finally spun instead of short fibers. The manufacturing process of the silicon steel long magnetic fiber provided by the invention is completely different from the cold rolling or hot rolling process of the existing silicon steel sheet.
2. From the aspect of magnetization characteristics, the one-dimensional continuous silicon steel long fiber under the nanoscale obtained by the invention is closer to the scale level of the iron simple substance, so that the obtained magnetic permeability is higher, and the coercive force is reduced. The electrical magnetic material of continuous silicon steel long fiber utilizes the advantages of nanotechnology, greatly improves the magnetic property of the material from the source, and leads the equipment to obtain larger magnetic field intensity under the same volume. Therefore, the size of the electrical and electronic equipment can be reduced by one step, and the consumption of resources is saved.
3. The continuous silicon steel long fiber obtained by the invention has the advantage of one-dimensional structure, and is beneficial to constructing advanced product equipment structure, so that the continuous silicon steel long fiber is really developed towards flattening and microminiaturization. Through a special process, the fibers with one-dimensional structures can be woven into a two-dimensional planar membrane. This advantage is particularly advantageous for the development of a flat device. Through the process transformation, the magnetic core can be even directly constructed in the electrical chip, the new chip manufacturing process is promoted, and new industry and business opportunities are inoculated. Through the 3D printing technology, a three-dimensional structure can be directly obtained, the processes of riveting, welding and the like in the traditional process manufacturing are omitted, and the production and delivery speed of the product is greatly improved. And 4.0 industry of flexible manufacturing and personalized customization, and basic technical innovation support is provided.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A continuous silicon steel long fiber electrical magnetic material is prepared by the following method:
s1, mixing an organic solvent, manganese hydroxide and deionized water, wherein the molar ratio of the organic solvent to the manganese oxide is 1:10, adding the deionized water to keep the pH value of the solution at 7.2, and uniformly stirring to obtain a mixed solvent; step S1 the organic solvent is: polyvinyl alcohol.
S2, adding a metal iron salt into the mixed solvent, wherein the mass ratio of the metal iron salt to the mixed solvent is as follows: 1:10, and uniformly stirring to obtain a mixed solution; the metallic iron salt in the step S2 is: ferric nitrate.
S3, dehydrating the mixed solution at 70 ℃ in vacuum to a gel state to obtain iron gel;
s4, adding silicon tetrachloride dropwise at the iron gel temperature of 18 ℃, and stirring until a preset ratio of silicon element to iron element is achieved to obtain mixed gel; the molar mass of the silicon element is A, and the molar mass of the iron element is B; step S4, the predetermined ratio of si to fe is: a: and B is 2: 98.
S5, spinning the mixed gel by adopting a high-voltage electrostatic spinning method, and collecting the obtained long fibrous cellulose filaments;
the control parameters of the high-voltage electrostatic spinning in the step S5 are as follows: the flow rate was 0.8ml/h, the voltage was 20kV, and the distance between the electrodes was 14 cm.
S6, placing the long fibrous long fiber obtained in the step S5 in a heating device, and performing heat treatment operation to obtain the continuous silicon steel magnetic long fiber.
Example 2
A continuous silicon steel long fiber electrical magnetic material is prepared by the following method:
s1, mixing an organic solvent, manganese hydroxide and deionized water, wherein the molar ratio of the organic solvent to the manganese oxide is 1:20, adding the deionized water to keep the pH value of the solution at 5.6, and uniformly stirring to obtain a mixed solvent; step S1 the organic solvent is: and (4) citric acid.
S2, adding a metal iron salt into the mixed solvent, wherein the mass ratio of the metal iron salt to the mixed solvent is as follows: 1:20, and uniformly stirring to obtain a mixed solution; the metallic iron salt in the step S2 is: ferric chloride.
S3, dehydrating the mixed solution at the temperature of 80 ℃ in vacuum to a gel state to obtain iron gel;
s4, adding silicon tetrachloride dropwise at the temperature of 20 ℃ of the iron gel, and stirring until a preset ratio of silicon element to iron element is achieved to obtain mixed gel; the molar mass of the silicon element is A, and the molar mass of the iron element is B; step S4, the predetermined ratio of si to fe is: a: and B is 10: 99.
S5, spinning the mixed gel by adopting a high-voltage electrostatic spinning method, and collecting the obtained long fibrous cellulose filaments;
the control parameters of the high-voltage electrostatic spinning in the step S5 are as follows: the flow rate was 1.2ml/h, the voltage was 25kV, and the distance between the electrodes was 16 cm.
S6, placing the long fibrous long fiber obtained in the step S5 in a heating device, and performing heat treatment operation to obtain the continuous silicon steel magnetic long fiber.
Example 3
A continuous silicon steel long fiber electrical magnetic material is prepared by the following method:
s1, mixing an organic solvent, manganese hydroxide and deionized water, wherein the molar ratio of the organic solvent to the manganese oxide is 1:0.5, adding the deionized water to keep the pH value of the solution at 8.5, and uniformly stirring to obtain a mixed solvent; step S1 the organic solvent is: polyvinyl alcohol and citric acid are mixed in equal proportion.
S2, adding a metal iron salt into the mixed solvent, wherein the mass ratio of the metal iron salt to the mixed solvent is as follows: 1:5, and uniformly stirring to obtain a mixed solution; the metallic iron salt in the step S2 is: mixing ferric nitrate and ferric chloride in equal proportion.
S3, dehydrating the mixed solution at the temperature of 60 ℃ in vacuum to a gel state to obtain iron gel;
s4, adding silicon tetrachloride dropwise at the temperature of 15 ℃ of the iron gel, and stirring until a preset ratio of silicon element to iron element is achieved to obtain mixed gel; the molar mass of the silicon element is A, and the molar mass of the iron element is B; step S4, the predetermined ratio of si to fe is: a: and B is 1: 90.
S5, spinning the mixed gel by adopting a high-voltage electrostatic spinning method, and collecting the obtained long fibrous cellulose filaments;
the control parameters of the high-voltage electrostatic spinning in the step S5 are as follows: the flow rate was 0.5ml/h, the voltage was 15kV, and the distance between the two electrodes was 12 cm.
S6, placing the long fibrous long fiber obtained in the step S5 in a heating device, and performing heat treatment operation to obtain the continuous silicon steel magnetic long fiber.
Example 4
A continuous silicon steel long fiber electrical magnetic material is prepared by the following method:
s1, mixing an organic solvent, manganese hydroxide and deionized water, wherein the molar ratio of the organic solvent to the manganese oxide is 1:3, adding the deionized water to keep the pH value of the solution at 6.8, and uniformly stirring to obtain a mixed solvent; step S1 the organic solvent is: polyvinyl alcohol and citric acid are mixed in equal proportion.
S2, adding a metal iron salt into the mixed solvent, wherein the mass ratio of the metal iron salt to the mixed solvent is as follows: 1:12, and uniformly stirring to obtain a mixed solution; the metallic iron salt in the step S2 is: mixing ferric nitrate and ferric chloride in equal proportion.
S3, dehydrating the mixed solution at 70 ℃ in vacuum to a gel state to obtain iron gel;
s4, adding silicon tetrachloride dropwise at the iron gel temperature of 18 ℃, and stirring until a preset ratio of silicon element to iron element is achieved to obtain mixed gel; the molar mass of the silicon element is A, and the molar mass of the iron element is B; step S4, the predetermined ratio of si to fe is: a: and B is 5: 98.
S5, spinning the mixed gel by adopting a high-voltage electrostatic spinning method, and collecting the obtained long fibrous cellulose filaments;
the control parameters of the high-voltage electrostatic spinning in the step S5 are as follows: the flow rate was 0.8ml/h, the voltage was 18kV, and the distance between the electrodes was 13 cm.
S6, placing the long fibrous long fiber obtained in the step S5 in a heating device, and performing heat treatment operation to obtain the continuous silicon steel magnetic long fiber.
Example 5
Based on any one of embodiments 1 to 4, the molar mass A of the silicon element satisfies the following condition: a/(a + B) ═ C; the value range of C is as follows: 0.01-0.1. Compared with the fiber length of the final product under the condition of the rest silicon element proportion, the fiber length of the final product can be obviously improved by controlling the molar mass of the silicon element within the range, and the fiber length is increased by 15-20 percent compared with the fiber length of the final product.
Example 6
In any of embodiments 1-4, the heat treatment of step S6 includes:
(1) filling nitrogen-hydrogen mixed gas into a heating device with long fibrous cellulose filaments, gradually raising the temperature of the heating device, and finally stabilizing at 770 ℃ of 730 and preferably 750 ℃, and heating for 3-4 hours, preferably 3.5 hours;
(2) controlling the temperature of the heating device to be 380-420 ℃, preferably 400 ℃, and calcining for 4-5 hours, preferably 4.5 hours in an air environment;
(3) filling hydrogen and gradually raising the temperature of the heating device, and finally stabilizing at 770 ℃ of 730 and preferably 750 ℃, and heating for 4-6 hours, preferably 5 hours.
In the nitrogen-hydrogen mixed gas in the step (1), the ratio of nitrogen: hydrogen is 1:5-20, preferably 1: 10; and (3) gradually raising the temperature of the heating device in the steps (1) and (3), wherein the temperature raising speed is 5-30 ℃/min, and preferably 15 ℃/min. The operation can remove the redundant oxygen element in the silicon steel long fiber.
Based on 1 embodiment of the invention, magnesium oxide or chromium oxide coating materials are adopted to perform spray coating on the continuous silicon steel magnetic long fiber obtained in the step S6, so that a good anti-corrosion effect can be achieved.
The invention has at least one of the following advantages:
the invention provides a preparation method of a continuous silicon steel long fiber electrical material. It has at least the following advantages.
1. The invention combines two technologies of a sol-gel method and a high-voltage electrostatic spinning method to obtain a proper spinnable precursor according to different proportions. By controlling the parameters of a proper high-voltage electrostatic spinning machine and combining a drum type collector, continuous silicon steel long fibers with the length-diameter ratio of more than 4000:1 are finally spun instead of short fibers. The manufacturing process of the silicon steel long magnetic fiber provided by the invention is completely different from the cold rolling or hot rolling process of the existing silicon steel sheet.
2. From the aspect of magnetization characteristics, the one-dimensional continuous silicon steel long fiber under the nanoscale obtained by the invention is closer to the scale level of the iron simple substance, so that the obtained magnetic permeability is higher, and the coercive force is reduced. The electrical magnetic material of continuous silicon steel long fiber utilizes the advantages of nanotechnology, greatly improves the magnetic property of the material from the source, and leads the equipment to obtain larger magnetic field intensity under the same volume. Therefore, the size of the electrical and electronic equipment can be reduced by one step, and the consumption of resources is saved.
3. The continuous silicon steel long fiber obtained by the invention has the advantage of one-dimensional structure, and is beneficial to constructing advanced product equipment structure, so that the continuous silicon steel long fiber is really developed towards flattening and microminiaturization. Through a special process, the fibers with one-dimensional structures can be woven into a two-dimensional planar membrane. This advantage is particularly advantageous for the development of a flat device. Through the process transformation, the magnetic core can be even directly constructed in the electrical chip, the new chip manufacturing process is promoted, and new industry and business opportunities are inoculated. Through the 3D printing technology, a three-dimensional structure can be directly obtained, the processes of riveting, welding and the like in the traditional process manufacturing are omitted, and the production and delivery speed of the product is greatly improved. And 4.0 industry of flexible manufacturing and personalized customization, and basic technical innovation support is provided.
It is to be noted and understood that various modifications and improvements can be made to the invention described in detail above without departing from the spirit and scope of the invention as claimed. Accordingly, the scope of the claimed subject matter is not limited by any of the specific exemplary teachings provided.
Claims (2)
1. A method for preparing a continuous silicon steel long fiber electrical magnetic material is characterized by comprising the following steps:
s1, mixing an organic solvent, manganese hydroxide and deionized water, wherein the molar ratio of the organic solvent to the manganese hydroxide is 1:0.5-20, adding the deionized water to keep the pH value of the solution at 5.6-8.5, and uniformly stirring to obtain a mixed solvent;
s2, adding a metal iron salt into the mixed solvent, wherein the mass ratio of the metal iron salt to the mixed solvent is as follows: 1:5-20, and uniformly stirring to obtain a mixed solution;
s3, dehydrating the mixed solution at the temperature of 60-80 ℃ in vacuum to a gel state to obtain iron gel;
s4, dropwise adding silicon tetrachloride at the temperature of 15-20 ℃ of the iron gel, and stirring until a predetermined ratio of silicon element to iron element is achieved to obtain mixed gel;
s5, spinning the mixed gel by adopting a high-voltage electrostatic spinning method, and collecting the obtained long fibrous cellulose filaments;
s6, placing the long filamentous vegetarian fiber obtained in the step S5 into a heating device, and performing heat treatment to obtain continuous silicon steel magnetic long fibers;
step S1 the organic solvent is: one or two of polyvinyl alcohol or citric acid are mixed;
the metallic iron salt in the step S2 is: mixing one or both of ferric nitrate and ferric chloride;
the molar mass of the silicon element is A, and the molar mass of the iron element is B; step S4, the predetermined ratio of si to fe is: a: b is 1-10: 90-99;
the molar mass A of the silicon element meets the following conditions: a/(a + B) ═ C; the value range of C is as follows: 0.01-0.1;
the control parameters of the high-voltage electrostatic spinning in the step S5 are as follows: the flow rate is 0.5-1.2ml/h, the voltage is 15-25kV, and the distance between the two electrodes is 12-16 cm;
step S6 the heat treatment operation includes:
(1) filling nitrogen-hydrogen mixed gas into a heating device with long fibrous cellulose filaments, gradually raising the temperature of the heating device, and finally stabilizing at the temperature of 730-;
(2) controlling the temperature of the heating device to be 380-420 ℃, and calcining for 4-5 hours in an air environment;
(3) filling hydrogen, gradually raising the temperature of the heating device, and finally stabilizing at the temperature of 730-;
in the nitrogen-hydrogen mixed gas in the step (1), the ratio of nitrogen: hydrogen is 1: 5-20;
gradually raising the temperature of the heating device in the steps (1) and (3), wherein the temperature raising speed is 5-30 ℃/min;
and (4) adopting a magnesium oxide or chromium oxide coating material to perform spray coating on the continuous silicon steel magnetic long fiber obtained in the step S6.
2. A continuous long silicon steel fiber electrical magnetic material, which is prepared by the method of claim 1.
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CN103498285A (en) * | 2013-10-18 | 2014-01-08 | 苏州大学 | Method using electrospinning technique to prepare ordered nanometer magnetic composite material |
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