CN115045105B - Preparation method of bionic fiber - Google Patents
Preparation method of bionic fiber Download PDFInfo
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- CN115045105B CN115045105B CN202210740246.7A CN202210740246A CN115045105B CN 115045105 B CN115045105 B CN 115045105B CN 202210740246 A CN202210740246 A CN 202210740246A CN 115045105 B CN115045105 B CN 115045105B
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- 239000000835 fiber Substances 0.000 title claims abstract description 112
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 194
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 102
- 239000000839 emulsion Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 210000001595 mastoid Anatomy 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- 230000003592 biomimetic effect Effects 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- -1 silicate ester Chemical class 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 230000033444 hydroxylation Effects 0.000 claims description 7
- 238000005805 hydroxylation reaction Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 240000002853 Nelumbo nucifera Species 0.000 description 14
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 14
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- 239000002073 nanorod Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 239000002657 fibrous material Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000003075 superhydrophobic effect Effects 0.000 description 6
- 150000007529 inorganic bases Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000010892 electric spark Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000004001 molecular interaction Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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Images
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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
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- 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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Silicon Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a preparation method of a bionic silicon oxide fiber, which comprises the steps of hydroxylating the surface of a high-silica fiber, adsorbing an emulsion drop on the surface of the high-silica fiber through hydroxyl on the surface of the high-silica fiber, hydrolyzing silicate in a water phase of the emulsion drop, and further carrying out polycondensation reaction on a hydrolysate of the silicate and the hydroxyl on the surface of the high-silica fiber to grow a mastoid structure in situ on the surface of the high-silica fiber; the emulsion droplets are water-in-oil emulsion droplets.
Description
Technical Field
The invention relates to the field of bionics, in particular to a preparation method of a bionic fiber material with a mastoid structure on the surface.
Background
The lotus leaf effect refers to the super-hydrophobic and self-cleaning properties of the lotus leaf surface. Research shows that a large number of mastoid structures on the lotus leaf surface can form an air layer on the lotus leaf surface, the air layer can reduce the contact area between water and the lotus leaf, the shape of the water on the rough surface is almost spherical under the influence of surface tension, and the contact angle exceeds 150 degrees, so that the super-hydrophobic state is achieved. In addition, water droplets can roll very freely on the surface, giving the lotus leaf self-cleaning ability. Inspired by the leaf effect of the load, the material with a structure similar to mastoid is widely applied in the fields of antifouling, anticorrosion, self-cleaning and the like.
Methods such as in situ self-assembly, wet chemical synthesis, templating, sol-gel, and photolithography have been used to successfully synthesize materials with papillary structures. For example: the patent with publication number CN 106938359A discloses a controllable preparation method of a metal bionic micro-nano structure, which adopts a laser three-dimensional scanning technology to collect a micro-nano structure on the surface of a living being (such as lotus leaves, rose petals, shark skin and the like) and generate a three-dimensional model, and then duplicates the micro-nano structure on the surface of the living being on the metal surface through a micro-nano electric spark processing technology. The patent with publication number CN 104802488A discloses a super-hydrophobic material with a hierarchical coarse structure coating, which is prepared by carrying out in-situ self-assembly on layers of static electricity, namely, solid spherical SiO with the grain diameters of 10-50 nm and 70-500 nm 2 NanoparticlesCoating on a porous substrate such as stainless steel to prepare the super-hydrophobic material with the surface topological structure similar to that of lotus leaves. The patent with publication number CN 106835079A discloses a copper-based super-hydrophobic surface of an anti-fog micro-nano composite structure, which comprises the steps of firstly polishing a metal copper substrate by using sand paper to construct a regular micron-sized coarse structure, and then preparing a ZnO nanorod cone array structure on the surface of the micron-sized coarse structure by using a wet chemical synthesis method, thereby realizing the construction of the micro-nano hierarchical composite structure on the surface of the copper substrate.
However, the method has the problems of complex process, large energy consumption, low bonding strength, poor controllability and the like. In view of the above, a new technical solution is needed to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a hydroxyl-positioned liquid drop template method which is simple in process, low in cost, flexible and controllable in structure and used for preparing a bionic fiber material which is similar to a lotus leaf surface mastoid structure and flexible and controllable in structure.
In order to achieve the purpose, the invention adopts the following technical means:
a preparation method of bionic silicon oxide fiber comprises the steps of hydroxylating the surface of high-silica fiber, enabling emulsion liquid drops to be adsorbed on the surface of the high-silica fiber through hydroxyl on the surface of the high-silica fiber, and enabling silicate ester to be hydrolyzed in a water phase of the emulsion liquid drops, so that a hydrolysis product of the silicate ester and the hydroxyl on the surface of the high-silica fiber are subjected to condensation polymerization reaction to grow a mastoid structure on the surface of the high-silica fiber in situ;
the emulsion droplets are water-in-oil emulsion droplets.
The high silica fiber has a silica content of 96-98wt.%;
the average diameter of the high silica fiber is 10-15 μm.
The method comprises the steps of hydroxylating the surface of the high silica fiber by adopting an inorganic alkali solution;
the inorganic base comprises sodium hydroxide or potassium hydroxide;
the temperature of the hydroxylation is 75-85 ℃;
the hydroxylation time is 6-10h;
the concentration of the solution of the inorganic base is 3-5M.
Comprises the steps of hydroxylating the surface of the high silica fiber, dispersing the hydroxylated high silica fiber in emulsion, and adsorbing emulsion droplets in the emulsion on the surface of the high silica fiber through hydroxyl on the surface of the high silica fiber.
The emulsion comprises an emulsifier;
the emulsifier comprises CTAB.
The oil phase of the emulsion comprises a sparingly water-soluble alcohol;
the slightly water-soluble alcohol includes butanol or pentanol.
The water phase of the emulsifier comprises an emulsion drop stabilizer;
the emulsion droplet stabilizer comprises sodium citrate.
The silicate comprises tetraethyl orthosilicate.
The water phase of the emulsifier comprises a silicate ester hydrolysis catalyst;
the silicate hydrolysis catalyst comprises ammonia.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the bionic fiber provided by the invention has the advantages that the reaction condition is mild, the reaction can be carried out at normal temperature and normal pressure, the reaction using instrument is simple, and the synthesis cost is low;
2. the preparation method of the bionic fiber provided by the invention has the advantages that the reaction conditions are easy to control, the operation is simple, and the mastoid structure can be accurately controlled by regulating and controlling the types of reactants, the concentrations of the reactants, the reaction conditions and other factors;
3. the mastoid structure of the bionic fiber material prepared by the preparation method of the bionic fiber provided by the invention is beneficial to playing an important role in the field of super-wettability materials.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below.
FIG. 1 shows a scanning electron micrograph of hydroxylated high-silica fibers prepared in example 1;
FIG. 2 shows the FT-IR spectrum of the hydroxylated high silica fiber prepared in example 1;
FIG. 3 shows a scanning electron micrograph of the high silica fibers prepared in example 1;
FIG. 4 is a length statistic chart showing the mastoid structure of the surface of the biomimetic silica fiber prepared in example 1;
FIG. 5 shows a diameter statistical chart of the mastoid structure of the surface of the biomimetic silica fiber prepared in example 1;
FIG. 6 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 2;
FIG. 7 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 3;
FIG. 8 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 4;
FIG. 9 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 5;
FIG. 10 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 6;
FIG. 11 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 7;
FIG. 12 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 8;
FIG. 13 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 9;
FIG. 14 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 10;
FIG. 15 shows a scanning electron micrograph of a biomimetic silica fiber prepared in example 11;
FIG. 16a shows the wettability of the high silica fibers prepared in example 1 by water;
FIG. 16b shows the wettability of the high silica fibers prepared in example 8 to water;
FIG. 16c shows the wettability of the high silica fibers prepared in example 10 to water.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
The invention provides a preparation method of a bionic silicon oxide fiber, which simulates a super-hydrophobic mastoid structure of lotus leaves. The invention thus provides a method of growing papilla structures on the surface of silica fibers. Specifically, the method firstly hydroxylates the surface of the high silica fiber, so that the surface of the high silica fiber is fully distributed with hydroxyl groups to become more hydrophilic. Then, the emulsion droplets in the water-in-oil emulsion are adsorbed on the surface of the high silica fibers through the hydroxyl groups on the surface of the high silica fibers, because the aqueous phase in the emulsion droplets has high compatibility with the hydroxyl groups and is driven by the surface tension, and the emulsion droplets are spontaneously adsorbed on the surface of the high silica fibers. At this time, the silicate is hydrolyzed in the aqueous phase of the emulsion droplets, and the hydrolysis product of the silicate undergoes a polycondensation reaction with the hydroxyl groups on the surface of the high-silica fibers to grow papillary structures in situ on the surface of the high-silica fibers. These emulsion droplets adsorbed on the surface of the high silica fibers form templates that guide the in situ growth of papillary structures on the surface of the high silica fibers.
When the bionic silicon oxide fiber material with the mastoid structure similar to the lotus leaf surface is prepared, hydroxyl groups are formed on the surface of the high-silica fiber as much as possible, the surface of the high-silica fiber can attract more emulsion drops to adhere to form templates, and the templates can provide more nucleation sites for the in-situ composite growth of the silicon dioxide nanometer mastoid structure on the surface of the silicon oxide fiber. Preferably, in certain embodiments of the present invention, the surface of the high silica fibers is treated with an inorganic base at elevated temperatures to hydroxylate the surface. By adopting the method, when the high silica fiber is hydroxylated, hydroxyl ions can destroy siloxane bonds of silicon dioxide, and a silicon dioxide network is dissolved. Reactions (1) and (2) show the chemical reactions that occur during hydroxylation of the surface of the high silica fibers. As shown in reaction (1), the siloxane bonds on the surface of high-silica fibers form nonbridging oxygens (. Ident.Si-O-) with hydroxide ions. As shown in reaction (2), the non-bridging oxygen formed in reaction (1) interacts with another water molecule to produce a hydroxyl ion (OH-). The hydroxyl ions provided by the reaction (2) can freely participate in the reaction (1) repeatedly. The cyclic reaction can increase the number of active silanol groups (≡ Si-OH) on the fiber surface, can also improve the attachment point and the bonding strength of emulsion droplets, and further helps the in-situ growth of the silica nanorods. The specific reaction equation is as follows:
≡Si-O-Si≡+OH - →≡Si-OH+≡Si-O- (1)
in certain embodiments of the invention, the oil phase employed in the water-in-oil emulsion is a sparingly water-soluble alcohol. Preferably, the slightly water-soluble alcohol may be butanol or pentanol. Of course, it will be appreciated by those skilled in the art that the invention may be practiced with other organic materials that form water-in-oil emulsions, such as ethyl acetate.
Specifically, taking ethyl orthosilicate as an example, the mastoid structure grows because ethyl orthosilicate undergoes a hydrolysis reaction in the aqueous phase (i.e., polar phase) inside the emulsified droplets, a polycondensation reaction occurs between partial hydrolysate and silicon hydroxyl groups to form silicon dioxide, and rod-like silicon dioxide is obtained under the control of the droplet template. By adopting the method of growing the silicon dioxide nanorods (namely mastoid structures) on the fiber surface in situ, not only can uniform and ordered protruding structures be obtained, but also the silicon dioxide nanorods prepared by the method are combined with the high silica fiber by chemical bonds, so that the bonding strength is high, and the protruding structures are not easy to fall off or collapse. The following is a schematic diagram of a specific chemical reaction:
when the mastoid structure grows on the surface of the hydroxylated high-silica fiber, the size of the template can be controlled by controlling the size of emulsion drops, and then the density of the mastoid structure growing on the surface of the high-silica fiber is controlled. Specifically, in order to form a stable water-in-oil emulsion, an emulsifier having amphiphilicity is used, and CTAB can be used as the emulsifier. CTAB is selected as an emulsifier because CTAB contains hydrophilic amino groups and hydrophobic hexadecyl moieties in the molecule, which can act as a surfactant. It will be appreciated by those skilled in the art that the invention may be practiced with other emulsifiers. In order to make the emulsion thermodynamically more stable, a droplet stabilizer may be added to the emulsion to control the size of the emulsion droplets. Preferably, sodium citrate can be used as a droplet stabilizer. The interaction between the citrate ions and the CTAB molecule improves the stability of the emulsion droplets.
The length and content of papilla structures can be controlled by adding to the emulsifier a weak base which catalyzes the hydrolysis of the silicate. The addition of a weak base as a polar phase affects, on the one hand, the size of the emulsion droplets and thus the size of the mastoid structure and, on the other hand, the shape of the mastoid structure by controlling the hydrolysis rate of the silicate. Preferably, the weak base is ammonia. It will be appreciated by those skilled in the art that the invention may be practiced with other weak bases capable of promoting hydrolysis of silicates, such as ammonium bicarbonate.
The length and content of the mastoid structure can also be controlled by controlling the water content of the emulsion and the conditions such as reaction temperature, reaction time and the like. The change in water content results in a change in emulsion droplet size, thereby affecting the diameter and length of the mastoid structure; the influence of temperature on the structure of the silica nanorods is mainly achieved through two aspects. On the one hand, the temperature increase increases the solubility of water in pentanol, while at the same time the molecular interaction between CTAB, citrate and water is reduced, leading to the expulsion of CTAB molecules and thus to the contraction of the emulsion droplets. In addition, elevated temperatures lead to enhanced silicate diffusion within the emulsion droplets, accelerating axial growth of the mastoid structure, enhanced brownian motion of the mastoid structure and terminal water droplets at higher temperatures, and increased likelihood of collision and agglomeration of adjacent droplets leading to the formation of curved structures; the adhesion of the emulsion droplets to the fiber surface and the growth of the mastoid structure occur simultaneously at the initial stage of the reaction, and the adhesion is saturated within a certain reaction time, after which the length of the mastoid structure is further increased.
In certain embodiments of the present invention, the length and diameter of the mastoid structure on the surface of the biomimetic silica fiber can be controlled in the range of 180-368nm and 194-1489nm, respectively, and the mastoid structure also changes from a straight rod shape to a curved rod shape.
In certain embodiments of the present invention, the high silica fibers have a silica content of 96-98wt.%; the silicon oxide contains a large amount of silicon hydroxyl and is the key for synthesizing the mastoid structure on the surface of the bionic silicon oxide fiber. The average diameter of the high silica fiber is 10-15 μm.
Comprises the step of hydroxylating the surface of the high silica fiber by adopting a solution of inorganic base;
in certain embodiments of the invention, the inorganic base comprises sodium hydroxide or potassium hydroxide; the temperature of hydroxylation is 75-85 ℃; the hydroxylation time is 6-10h;
comprises the steps of hydroxylating the surface of the high silica fiber, dispersing the hydroxylated high silica fiber in emulsion, and adsorbing emulsion droplets in the emulsion on the surface of the high silica fiber through hydroxyl on the surface of the high silica fiber.
The present invention is further illustrated by the following specific examples.
High silica fibers were purchased from Nanjing, capital, telex glass fibers, inc.
Example 1
(1) Preparation of surface hydroxylated high silica fiber
(1) 3 parts of sodium hydroxide particles and 25 parts of deionized water are weighed in a beaker and stirred to obtain a sodium hydroxide aqueous solution.
(2) Dispersing high silica fiber in the alkali solution prepared in the step (1), and stirring in a water bath at 80 ℃ for 8h.
(3) And after stirring, repeatedly washing and drying by using deionized water to prepare the high silica fiber with the hydroxylated surface.
(2) Preparation of bionic fiber material with mastoid structure similar to lotus leaf surface
(1) 12.5 parts of CTAB and 100 parts of n-pentanol are weighed into an erlenmeyer flask and dissolved after stirring.
(2) 7.5 parts of high silica fiber are weighed and dispersed in the solution prepared in step 1 by ultrasound.
(3) 2.8 parts of deionized water, 1 part of 0.28M sodium citrate aqueous solution, 9.5 parts of absolute ethyl alcohol and 2 parts of ammonia water are weighed, added in sequence, stirred and mixed uniformly.
(4) Weighing 1 part of TEOS, stirring and mixing uniformly, and reacting for 6h under the condition of 50 ℃ water bath.
(5) And (3) centrifugally cleaning the reaction product with ethanol for several times, and drying to obtain the bionic high silica fiber with the structure similar to the papilla on the lotus leaf surface.
FIG. 1 shows the hydroxylated high silica fibers of example 1, as shown in FIG. 1, the fibers were smooth and free of protruding structures. FIG. 2 is an infrared spectrum of a hydroxylated high silica fiber, 950cm -1 The presence of Si-OH is evidenced by nearby absorption peaks. Fig. 3 shows the bionic fiber material based on the papillary structure on the lotus leaf surface prepared in embodiment 1, and the silicon dioxide nanorods uniformly grow on the fiber surface. Statistically (specifically shown in FIG. 4 and FIG. 5), the average length and the average diameter of the silica nanorods on the surfaces of the bionic fibers are 1.6 μm and 256nm respectively. Fig. 16a shows the wettability of the bionic fiber prepared in embodiment 1 on water drops, and the contact angle of the water drops on the fiber surface is obviously larger than 90 degrees, and the bionic fiber is in a hydrophobic state.
Examples 2 to 11
Examples 2 to 11 are based on the embodiment 1, and some process parameters are modified and adjusted, and the process parameters of each example are different from those of the embodiment 1 shown in table 1. In the following table
TABLE 1 Process parameters for examples 2-11
| Reaction time (h) | Reaction temperature (. Degree.C.) | Water content (parts) | Ammonia water content (parts) | |
| Example 2 | 0.5 | - | - | - |
| Example 3 | 1 | - | - | - |
| Example 4 | 3 | - | - | - |
| Example 5 | - | 30 | - | - |
| Example 6 | - | 40 | - | - |
| Example 7 | - | 60 | - | - |
| Example 8 | - | - | 2.4 | - |
| Example 9 | - | - | 3.2 | - |
| Embodiment 10 | - | - | - | 1.5 |
| Example 11 | - | - | - | 2.5 |
Fig. 6 to 15 are scanning electron micrographs of the biomimetic fiber materials prepared in examples 2 to 11, respectively, and by adjusting the reaction conditions and the reagent concentration, the structure of the nanorod protruding from the fiber surface is controllable, the length and diameter can be adjusted within the ranges of 180-368nm and 194-1489nm, respectively, and the morphology can also be changed from a straight rod shape to a curved rod shape. Fig. 16b and 16c show the wettability of the bionic fibers prepared in the embodiments 8 and 10 on water drops, and the contact angle of the water drops on the fiber surface is obviously larger than 90 degrees, and the bionic fibers are in a hydrophobic state.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A preparation method of bionic silicon oxide fiber is characterized by comprising the following steps:
hydroxylating the surface of high silica fiber, adding the hydroxylated high silica fiber into alcohol which is dissolved with emulsifier and is slightly soluble in water, stirring, then sequentially adding water, sodium citrate, absolute ethyl alcohol and weak base to form emulsion, dispersing the high silica fiber in the emulsion, and further adsorbing emulsion drops in the emulsion on the surface of the high silica fiber through hydroxyl on the surface of the high silica fiber; adding silicate ester into the emulsion, stirring and mixing uniformly, and reacting for 6h in a water bath at 50 ℃ to hydrolyze the silicate ester in the water phase of the emulsion droplets, and performing polycondensation reaction on the hydrolysis product and hydroxyl on the surface of the high silica fiber to grow a mastoid structure in situ on the surface of the high silica fiber;
the emulsion droplets are water-in-oil emulsion droplets;
the addition amount of the emulsifier is 100-200 mu L.
2. The method for preparing a biomimetic silica fiber according to claim 1, wherein:
the high silica fiber has a silica content of 96-98wt.%;
the average diameter of the high silica fiber is 10-15 μm.
3. The method for preparing a biomimetic silica fiber according to claim 1, wherein:
comprises the step of hydroxylating the surface of high silica fiber by adopting strong alkali solution;
the strong base comprises sodium hydroxide or potassium hydroxide;
the temperature of hydroxylation is 75-85 ℃;
the hydroxylation time is 6-10h;
the concentration of the strong alkali solution is 3-5M.
4. The method for preparing a biomimetic silica fiber according to claim 1, wherein:
the weak base comprises ammonia water;
the concentration of the ammonia water is 28-30%.
5. The method for preparing a biomimetic silica fiber according to claim 1, wherein:
the oil phase of the emulsion comprises a sparingly water-soluble alcohol;
the slightly water-soluble alcohol includes butanol or pentanol.
6. The method for preparing a biomimetic silica fiber according to claim 1, wherein:
the emulsifier comprises CTAB;
the CTAB is added in an amount of 0.25-0.75 g.
7. The method for preparing a biomimetic silica fiber according to claim 1, wherein:
the addition amount of the sodium citrate is 25-75 mu L.
8. The method for preparing a biomimetic silica fiber according to claim 1, wherein:
the silicate comprises tetraethyl orthosilicate;
the addition amount of the silicate ester is 25-75 mu L.
9. The method for preparing a biomimetic silica fiber according to claim 1, wherein:
in the emulsion, the weight ratio of the oil phase to the water phase is 20-40.
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