CN113774655B - Full-water-based super-hydrophobic coating with reversible wettability as well as preparation method and application thereof - Google Patents
Full-water-based super-hydrophobic coating with reversible wettability as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN113774655B CN113774655B CN202111088266.2A CN202111088266A CN113774655B CN 113774655 B CN113774655 B CN 113774655B CN 202111088266 A CN202111088266 A CN 202111088266A CN 113774655 B CN113774655 B CN 113774655B
- Authority
- CN
- China
- Prior art keywords
- water
- coating
- suspension
- preparing
- super
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000000576 coating method Methods 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 65
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000002441 reversible effect Effects 0.000 title claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 19
- 229920002678 cellulose Polymers 0.000 claims abstract description 19
- 239000001913 cellulose Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920000742 Cotton Polymers 0.000 claims description 112
- 239000004744 fabric Substances 0.000 claims description 100
- 238000000926 separation method Methods 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 10
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract description 25
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 47
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 37
- 229960000907 methylthioninium chloride Drugs 0.000 description 37
- 238000006731 degradation reaction Methods 0.000 description 32
- 239000000839 emulsion Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 29
- 230000015556 catabolic process Effects 0.000 description 28
- 239000011521 glass Substances 0.000 description 28
- 239000003921 oil Substances 0.000 description 24
- 230000008859 change Effects 0.000 description 21
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000002296 dynamic light scattering Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 229950005499 carbon tetrachloride Drugs 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 9
- 229940012189 methyl orange Drugs 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 8
- 239000000295 fuel oil Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 235000019476 oil-water mixture Nutrition 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000007764 o/w emulsion Substances 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229940099373 sudan iii Drugs 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000007281 self degradation Effects 0.000 description 4
- 239000007762 w/o emulsion Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- FHNINJWBTRXEBC-HXEHWPEMSA-N sudan iii Chemical compound OC1=CC=C2C=CC=CC2=C1\N=N\C(C=C1)=CC=C1\N=N/C1=CC=CC=C1 FHNINJWBTRXEBC-HXEHWPEMSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000003913 Coccoloba uvifera Nutrition 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000008976 Pterocarpus marsupium Species 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 238000002272 high-resolution X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000346 nonvolatile oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- 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
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0414—Surface modifiers, e.g. comprising ion exchange groups
- B01D2239/0428—Rendering the filter material hydrophobic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a full water-based super-hydrophobic coating with reversible wettability as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing FS-3100 aqueous solution and nano TiO 2 Mixing and stirring the mixture and cellulose in proportion to form a suspension; adding AS and KH-570 into the suspension drop by drop, and stirring uniformly; finally, adding FAS into the mixture, and continuously stirring to prepare the coating; coating the coating on the surface of a substrate to obtain the fully water-based super-hydrophobic coating with reversible wettability. The surface with full water-based reversible wettability prepared by the invention has photocatalytic performance, the original wettability is super-hydrophobic/super-oleophilic, the wettability is converted into super-hydrophilic/underwater super-oleophobic after UV irradiation, and the wettability can be recovered after heating.
Description
Technical Field
The invention belongs to the technical field of paint preparation, and particularly relates to a full water-based super-hydrophobic coating with reversible wettability, and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The development of industry has led to an increasing pollution of water resources by various pollutants. Research has shown that materials with extreme wettability have great potential in oil-water separation. Therefore, super-hydrophobic/super-oleophilic, super-hydrophilic/underwater super-oleophobic and responsive wettability materials are produced. As is well known, a superhydrophobic surface consists of a micro-nano structure and a low surface energy substance. In recent years, production techniques such as photolithography, sol-gel method, chemical vapor deposition method, electrostatic spinning method, and the like have been improved. The most common wet chemical method in these technologies is to use organic solvent to disperse micro-nano particles or dissolve low-surface-energy substances when preparing super-hydrophobic materials, but the organic solvent is usually toxic or volatile. The use of organic solvents not only increases the production cost and the environmental risk but also is not conducive to large-scale production. The use of toxic and volatile organic solvents should be reduced.
In fact, water is a desirable solvent. However, the development of all-water-based superhydrophobic coatings has been slow, since the low surface energy materials required to prepare superhydrophobic surfaces are essentially insoluble in water, and organic binders for improving the mechanical strength of superhydrophobic surfaces are not suitable for use in aqueous systems. The existing preparation method of the full water-based super-hydrophobic comprises the following steps: "paint + glue" and "one-piece". The 'paint + glue' method separately uses water and adhesive, and solves the problem that organic adhesive is insoluble in water. But the operation is complex compared with the integral type, and the method is not suitable for large-scale production. Some preparation methods utilize a water-soluble inorganic Adhesive (AP) to replace a traditional organic adhesive (epoxy resin and the like) to prepare the super-hydrophobic material, so that the mechanical strength of a super-hydrophobic system is enhanced. Although the above-described preparation method is "monolithic", coatings prepared using inorganic binders often require very high temperatures during curing, and are clearly unsuitable for substrates that are not resistant to high temperatures.
In addition, the wettability of the existing all-water-based super-hydrophobic coating is single, and most of the coating used in the preparation process is non-renewable resources.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a full water-based super-hydrophobic coating with reversible wettability, and a preparation method and application thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a full water-based super-hydrophobic coating with reversible wettability, which comprises the following steps:
FS-3100 aqueous solution and nano TiO 2 Mixing and stirring the mixture and cellulose in proportion to form suspension;
adding AS and KH-570 into the suspension, and then stirring uniformly;
finally, adding FAS into the mixture, and continuously stirring to obtain a coating;
coating the coating on the surface of a substrate to obtain the fully water-based super-hydrophobic coating with reversible wettability.
In some embodiments, AS and KH-570 are added dropwise to the suspension. The reaction can be more complete when the solution is gradually added dropwise.
In some embodiments, the concentration of the aqueous FS-3100 solution is 0.1-0.5. Mu.l/ml, preferably 0.2. Mu.l/ml.
Further, nano TiO 2 And cellulose in a mass ratio of 2 to 5, preferably 3 to 5, and more preferably 4.
In some embodiments, FS-3100 aqueous solution, nano TiO 2 Mixing with cellulose, and stirring at 50-70 deg.C for a set time to form suspension.
Further, FS-3100 aqueous solution and nano TiO 2 Mixing with cellulose, and stirring at 55-65 deg.C for 1-2 hr to obtain suspension. Further preferably, the suspension is formed by stirring at 60 ℃ for 1.5h.
In some embodiments, the volume ratio of suspension, AS and KH-570 is 15-25:2-3:1.
Further, AS and KH-570 are added dropwise to the suspension, followed by stirring at 55-65 deg.C for 0.5-1.5h, preferably at 60 deg.C for 1h. Too high temperature AS, KH-570 and too fast FAS reaction accelerate the agglomeration between particles, resulting in cross-linking of particles; the temperature is too low, the reaction is insufficient, and the modification of the silane coupling agent on the particles is influenced.
In some embodiments, the concentration of FAS added to the suspension is from 0.01 to 0.03g/ml, preferably 0.0232g/ml.
Further, after FAS is added to the suspension, stirring is continued for 2-4h, preferably 3h.
In some embodiments, the coating is prepared by a dipping method for the flexible substrate; for the hard substrate, the spraying mode is adopted for preparation.
In a second aspect, the invention provides a full water-based super-hydrophobic coating with reversible wettability, which is prepared by the preparation method.
In a third aspect, the invention provides an application of the all-water-based super-hydrophobic coating with reversible wettability in oil-water separation and photocatalytic degradation of soluble pollutants in water.
In a fourth aspect, the invention provides a preparation method of filter cloth for oil-water separation and wastewater purification, which comprises the steps of preparing a coating and preparing the filter cloth by soaking cotton cloth; wherein, the first and the second end of the pipe are connected with each other,
the preparation of the coating comprises the following steps: mixing FS-3100 aqueous solution and nano TiO 2 Mixing and stirring the mixture and cellulose to form a suspension;
dropwise adding AS and KH-570 into the suspension, uniformly mixing, adding FAS into the suspension, and stirring for a set time to obtain a coating;
and soaking the cotton fabric into the coating for a set time, and taking out and drying to obtain the coating.
In a fifth aspect, the invention provides a filter cloth for oil-water separation and wastewater purification, which is prepared by the preparation method.
The above one or more embodiments of the present invention have the following beneficial effects:
the surface with full water-based reversible wettability prepared by the invention has photocatalytic performance, the original wettability is super-hydrophobic/super-oleophilic, the wettability is converted into super-hydrophilic/underwater super-oleophobic after UV irradiation, and the wettability can be recovered after heating.
The coating utilizes TiO 2 The (25 nm) and cellulose (25 μm) structure micro-nano roughness, and silane coupling agent AS and KH-570 which can react with water are used for connecting the particles, so that the adhesive force between the particles can be enhanced. FAS is used to reduce the surface tension of the system, thereby obtaining a superhydrophobic surface.
The surface has good super-hydrophobicity, and also has good mechanical stability and chemical stability. The cotton cloth modified by the coating can separate insoluble oil (light oil and heavy oil) in water, can separate stable emulsion, and can even degrade water-soluble organic pollutants (MB, MO and the like). This can satisfy the need for providing an idea for the purification of more complex water pollution systems.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a mechanism and flow diagram for the preparation of coatings according to one or more embodiments of the present invention;
fig. 2 is SEM images of original cotton fabric (a) and modified cotton fabric (b). The modified cotton fabric is mapped to elements of C (C), F (d), N (e), ti (F), si (g) and O (h). TGA curves (i) for original and modified superhydrophobic cotton fabrics. Change (j) of the same position of the water drop on the modified glass with time WCA;
fig. 3 shows the change of the image of the water drop on the surface of the coated glass under UV irradiation and heating (a), and the wettability conversion cycle (b). Underwater oil contact angles (c) of the UV treated modified cotton to different organic liquids. HR-XPS spectra of F1s (e), O1s (F) and C1s (g) on the surface of the modified cotton cloth before (upper) UV irradiation, after (middle) UV irradiation and after (lower) heating. A modified cotton wettability transformation mechanism diagram (h);
figure 4 is the change in WCA after 480 rubs of the modified superhydrophobic cotton (inset is picture of water drop after rubbing cotton) (a). Abrasion test the abrasion test is carried out on a sandpaper coated glass weighing 100g, and the inset is the picture (b) of the experimental set-up. WCA change after soaking the modified glass in different organic solvents (c). The WCA of the modified glass changed within 10min in acid-base solutions of different pH (d). Maintaining the modified glass in different acid-base solutions for super-hydrophobic soaking time and WCA (e);
FIG. 5 is a diagram showing the separation of an oil-water mixture by using a modified cotton cloth;
FIG. 6 is a digital image of the separation of water (a) in diesel, water (b) in octane, water (c) in tetrachloromethane and water (d) in dichloromethane with a modified superhydrophobic cotton fabric, respectively. DLS results of droplet sizes before and after filtration of four water-in-oil emulsions (insets) are (e-h), respectively; flux and separation efficiency (i) of different water-in-oil emulsions;
FIG. 7 is a digital image of an emulsion of diesel oil (a), octane (b), tetrachloromethane (c) and dichloromethane (d) in water separated from each other by a super hydrophilic cotton cloth. The DLS results for droplet sizes before and after filtration of the four oil-in-water emulsions (insets) are (e-h), respectively. Flux and separation efficiency of different oil-in-water emulsions (i);
FIG. 8 is a mechanism diagram (a) of the modified cotton cloth degrading the dye in water. Degradation of 10. Mu.g/mL, 30. Mu.g/mL, 50. Mu.g/mL MB solution, the UV-visible absorption spectrum of MB solution (b-d) with increasing UV irradiation time. Change in degradation rate the same cotton cloth 6 was multiplied by the 10 μ g/mL MB degradation (f) solution. The solution for the sixth degradation of the UV-visible absorption spectrum of the modified cotton cloth by 10 μ g/mL MB (g). Comparison of degradation rates with or without modification of cotton (h). Comparison of kinetically-explained degradation rates with or without modified cotton (i);
fig. 9 is a diagram showing in situ separation and degradation of a mixture of MB contaminated water and dichloromethane;
FIG. 10 is the change in WCA after oleic acid staining, UV irradiation and heating of the coated cotton fabric (a). Degradation digital photographs of sudan iii (b) and MB (c) stained cotton fabrics. Digital photograph (d) of hexagonal glass mask dyed in air with MB solution after uv irradiation. Photograph of glass in water with hexagonal superhydrophobic regions (e).
In fig. 11, SEM image (a) of cotton surface coating, elemental analysis image (b) of cotton surface coating, water contact angle (d) in air of cotton, wood, glass after coating modification, and rolling angle image (e) of water drop on modified glass surface;
FIG. 12 is EDS and XPS plots of modified cotton cloth surfaces;
FIG. 13 shows the WCA variation of the modified glass treated at high temperature 150 ℃ to 300 ℃ (a) and low temperature-10 ℃ to-50 ℃ (b) for 2 h.
Fig. 14 comparison of the first and sixth degradation rates of MB in the same piece of cotton cloth (a). Color change of different concentrations of MB solutions with UV irradiation (b). Absorption spectrum (c) of MO. Congo red photographs, color comparison before and after degradation of MB + MO mixed solution with Sudan B (d).
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Experimental part
1) Material
Titanium dioxide (TiO) 2 ) (anatase, hydrophilic, particle size 10-25 nm), alpha-cellulose (25 μm) gamma-methacryloxypropyl (KH-570, C 10 H 20 O 5 Si), N-aminoethyl-gamma-aminopropyltrimethoxysilane (AS, C) 8 H 22 N 2 O 3 Si), n-octane, oleic acid, sudan III, congo red are provided by alatin;
FS-3100 is supplied by DuPont;
1H, 2H-perfluorodecyl trimethoxysilane (FAS) was supplied by JINANTONG TUITAI FU CHEMICAL CO., LTD;
methylene chloride, carbon tetrachloride, diesel oil, gasoline, ethanol, N-dimethylformamide, sodium chloride (NaCl), sodium hydroxide (NaOH), hydrochloric acid (HCl), petroleum ether, 1, 2-dichloroethane, toluene, ammonia water, acetic acid, tween-80, and span-80, and Sudan Ming B are provided by national pharmaceutical Agents Co., ltd;
methylene Blue (MB) and Methyl Orange (MO) were provided by tianjinda mao chemicals, ltd.
All reagents were analytically pure and no special handling. The cotton fabric was a commercial cotton cloth, washed ultrasonically with distilled water and ethanol for 30min, and then completely dried in an oven at 60 ℃.
2) The preparation method of the all-water-based super-hydrophobic coating with reversible wettability comprises the following steps:
FS-3100 (4. Mu.l) was added to 20ml of deionized water and sonicated for 20min to form a homogeneous solution. Adding appropriate amount of TiO into the aqueous solution 2 And cellulose (mass ratio =4 = 1),stirring at 60 deg.C for 1.5h to form a suspension, adding 2.5ml AS and 1ml KH-570 dropwise into the suspension, and stirring at 60 deg.C for 1h. Finally, 0.5g of FAS was added thereto and stirring was continued for 3 hours. The washed cotton cloth was then dipped in the emulsion for approximately 30min and placed in an oven at 100 ℃ to dry. For the preparation of substrates of hard material (glass, wood, aluminium sheets), the suspension is sprayed onto the surface by means of a spray gun (ET 4000, STAT, germany) at a distance of 10cm from the surface. And curing for 8 hours in a forced air drying oven at 100 ℃ to obtain the super-hydrophobic coating.
3) Testing of Superhydrophobic coating Properties
1. Coating to substrate adhesion test
In order to test the adhesion of the coatings to different substrates, the coatings adhered to the different substrates were adhered to spindles with AB glue, the spindles were loaded with 200g weights, and then dried at room temperature for 3 days. The adhesion between the coating and the substrate was tested by means of pulling with an adhesion tester.
2. Wettability conversion
The modified cotton cloth and glass sheets are super-hydrophobic/super-oleophilic in air environment and pass through a UV-LED lamp (0.45W/cm) -2 λ =365 nm) was irradiated vertically for 90min, the wettability was changed to super-hydrophilic/underwater super-oleophobic. Soaking the irradiated cotton cloth and glass sheets in water, drying in a 150 deg.C forced air drying oven for 12 hr, and recovering to super-hydrophobic/super-oleophylic state. The frequency of the modified cotton cloth wettability conversion was continuously studied according to the above procedure.
3. Preparation of surfactant-containing emulsion
Water-in-oil emulsion: 0.35g of span 80 is weighed and added into a single-mouth round-bottom flask, then 57ml of dichloromethane, n-octane, diesel oil and carbon tetrachloride are respectively added, the mixture is stirred at room temperature until the dichloromethane, the n-octane, the diesel oil and the carbon tetrachloride are completely dissolved, 1ml of deionized water is added, and the stirring at room temperature is continued for 2 hours, so that 4 surfactant-stabilized water-in-oil emulsions are formed.
Oil-in-water emulsion: weighing 0.3g of Tween 80, adding into a single-neck round-bottom flask, adding 60ml of deionized water, stirring at room temperature until the Tween is completely dissolved, adding 2ml of dichloromethane, n-octane, diesel oil and carbon tetrachloride, and continuously stirring at room temperature for 2 hours to form 4 surfactant-stabilized oil-in-water emulsions.
4. Separation of immiscible oil-water mixture and emulsion
Separation of immiscible oil-water mixtures
Separating heavy oil and water with super-hydrophobic/super-oleophilic cotton cloth, irradiating with UV, and converting into super-hydrophilic/underwater super-oleophilic cotton cloth to separate light oil and water. Methylene chloride, 1, 2-dichloroethane, and carbon tetrachloride were used as heavy oils and petroleum ether, toluene, n-octane, and gasoline were used as light oils. The oil (stained with sudan iii) and water (stained with methylene blue) were poured into a separation apparatus in a volume ratio of 1. Note that the cotton cloth was wetted before separating the light oil and water from the ultra hydrophilic/underwater ultra oleophobic cotton cloth. Calculating the flux in the separation process:
wherein V (L) is the volume of the mobile phase before separation, S (m) 2 ) The effective area of cotton cloth separation, and t (h) the time of oil-water separation.
5. Separation of oil-in-water and water-in-oil emulsions
And separating the water-in-oil emulsion and the oil-in-water emulsion by using a separation device. 30ml of the emulsion was poured into a separate device and the throughput was calculated by recording the time 20ml of emulsion was collected.
6. UV degradation Properties
First, 30ml of prepared 10. Mu.g/ml, 30. Mu.g/ml, 50. Mu.g/ml Methylene Blue (MB) aqueous solution and prepared superhydrophobic cotton cloth (3 m. Times.3 cm) were put together in a 50ml centrifuge tube. The centrifuge tube was placed at a distance of about 10cm from the UV-LED lamp and irradiated for a certain time until the solution became colorless. During the degradation, 3ml of the solution was taken out every 30min and the absorbance of MB was measured with an ultraviolet spectrophotometer. After each degradation, heating the cotton cloth in the air at 120 ℃ for 1h, and performing next degradation after the cotton cloth is dried. The degradation rate (η,%) is given by the formula:
wherein A is 0 And A t The absorbance at 665nm of the original solution and the solution after t-time irradiation, respectively. (Note: 665nm is a characteristic peak of the MB solution in visible light.)
7. Testing and characterization
The surface morphology of the coatings was measured using a German supra atm55 thermal field emission scanning electron microscope (SEM, germany) at 5 kV. Energy dispersive x-ray (EDX) spectroscopy was observed with a scanning electron microscope (SEM, germany). Thermogravimetric analysis (TGA) was performed using a thermogravimetric analyzer (mettle-toledo). The static contact angle and sliding angle of the surface were measured by a contact angle meter (SL 250 USA KINO Industry co., ltd). The underwater contact angle is measured using the KR ü SS DSA25S (Germany) contact angle system. The composition of the cotton surface was tested using x-ray photoelectron spectroscopy (XPS, thermo, america, ESCALABXi +). 365nm ultraviolet lamp (SJMAEA-SJUV 4M, shanghai, china) is used for the light irradiation treatment of cotton fabric. The absorbance of the colored solution was measured with an ultraviolet-visible spectrophotometer (UV-2600, japan). The droplet size was characterized by Dynamic Light Scattering (DLS), zetasizer Nano ZS 90. The adhesion of the prepared coatings to different substrates was tested using a pull-off adhesion tester (XH-M, beijing, china).
4) Results and discussion
1. Surface topography and chemical characterization
As described above, the superhydrophobic/superoleophilic all-water-based paint was prepared using a simple method, as shown in FIG. 1. Adding TiO into the mixture 2 Dispersing the nano particles and cellulose into an aqueous solution containing a fluorine-containing surfactant (DuPont, FS-3100), adding three silanes of AS, KH-570 and FAS, simply blending, and modifying different substrates by spraying or dip coating. Two silane coupling agents, AS and KH-570, on the one hand aggregate the nanoparticles, building up the roughness required for superhydrophobic coatings, and on the other hand can link the particles to the substrate. FAS can reduce the surface energy of the coating and complete the hydrophobic modification of the particles. It is known that water has a surface tension of 72.8N/m, and that fluorosurfactants can reduce the surface tension of solvent water and enhance the water solubility of the modified hydrophobic particles.
The surface topography and the chemical composition of the surface of the modified cotton cloth were studied, as shown in fig. 2. In fig. 2a, it can be observed that the cotton surface before modification is smooth and flat. In FIG. 2b, the cotton cloth after modification is rough in surface and TiO 2 The nano particles are aggregated into clusters with different sizes under the action of the coupling agent, and the clusters and the micron-sized cellulose particles jointly form the micro-nano roughness required by the super-hydrophobicity. In FIG. 11a, clustered TiO can be seen 2 And the cellulose is tightly combined with the flaky cellulose, and the compact structure is more favorable for stabilizing the super-hydrophobicity of the surface.
FIGS. 2C-h, FIG. 12 are EDS and XPS graphs of the modified cotton cloth surface, which shows that C, O, N, F, si, ti are uniformly distributed on the cotton cloth surface, and this also shows that the cotton cloth can be successfully modified by a simple dip coating method. The specific content of these elements on the surface of the cotton is presented in FIG. s1 b. In addition, the TGA test showed that the mass ratio of the modified cotton cloth was 27.86%. The above data indicate that water-based superhydrophobic/superoleophilic coatings have been successfully prepared and cotton cloth has been successfully modified.
2. Original wettability
The water contact angle of cotton cloth, wood and glass modified by the coating in the air can reach 160.2 degrees (+ -2 degrees), 156.3 degrees (+ -2 degrees and 163 degrees (+ -2 degrees) (FIG. 11 c), the rolling angles are respectively 9.7 degrees, 5.6 degrees and 3.0 degrees (FIG. 11 d), and FIG. 11e is a picture of the rolling angle of water drops on the surface of the modified glass. In FIG. 11c, naCl, naOH (1M), HCl (1M) and strongly oxidizing potassium permanganate were dripped on the modified wood, cotton, glass, all spherical. In addition, the coating also has super-hydrophobic properties under oil, and it can be seen from fig. 11e that water (stained by MB) is spherical on the modified glass surface in n-octane. Fig. 2j shows the change in water contact angle for a drop of water over 9min, and it can be seen that the contact angle ranges from 164 ° (± 2 °) to 158 ° (± 2 °).
3. Wettability transformation and transformation mechanism
The wettability of the original modified cotton cloth is super-hydrophobic/super-oleophilic in air, after UV irradiation for 90min, the wettability is changed into super-hydrophilic/super-oleophobic under water, the wettability can be restored to a super-hydrophobic/super-oleophilic state by heating for 12h at 120 ℃, and the contact angle change in the process is shown as figure 3a. In fig. 3b it is shown that the modified cotton cloth can be repeatedly switched 3 times between superhydrophobic/superoleophilic and superhydrophilic/underwater superoleophobic. To test the underwater superoleophobicity of cotton cloth after UV irradiation, the contact angles of various light and heavy oils in water were tested. In fig. 3c it is shown that the underwater contact angles for the different oils are all over 150 deg., demonstrating that the cotton fabric has a very good oil repellency.
To investigate the mechanism of the wettability transition, XPS of cotton before and after UV irradiation was analyzed. In FIG. 3d, the XPS survey shows a large change in the F, O, and C elements before and after UV irradiation. FIG. 3f shows the high resolution spectrum of O1 s. The modified cotton cloth has 4 obvious fitting values of 532.7eV, 532.5eV, 531.1eV and 529.6eV, which respectively represent Si-O-Si, ti-O-H, si-O-Ti and Ti-O-Ti. By comparing the O1s of the different treated cotton cloths, it was found that the peak area fraction of Ti-O-H increases significantly after illumination, whereas the peak area fraction of Ti-O-H decreases after heating. Similarly, in FIG. 3g, the high resolution spectra of C1s are shown with-CF at 293.8eV and 291.7eV 3 、-CF 2 The peak area also decreased after the UV irradiation treatment, but recovered after the heating treatment. With respect to-CF 3 and-CF 2 The change in F1s before and after UV irradiation is also demonstrated in FIG. 3 e.
From the results of XPS analysis, the mechanism of the modified cotton wettability transition was presumed as shown in fig. 3h. In the presence of TiO 2 Has O on the surface 2 And H 2 Adsorption equilibrium of O. After UV irradiation, tiO on the one hand 2 The surface generates a large number of hydrophilic hydroxyl groups. Table S1 shows that the Ti-O-H peak area fraction increased from 34.02% to 51.19% after UV irradiation. On the other hand, tiO 2 There is a partial degradation of the low surface energy substances (FAS) on the surface. The two reasons are that the wettability of the modified cotton cloth is changed. But after heating, the TiO 2 Oxygen vacancies on the surface will adsorb air O 2 Thereby replacing the hydrophilic hydroxyl groupAnd the cotton cloth is enabled to recover super-hydrophobicity. In addition, FAS has a property of migrating to the surface at high temperature, which also helps the cotton cloth to recover superhydrophobicity.
4. Stability of the preparation of coatings
To test the durability of the coatings, the WCA was tested under different environments, as shown in fig. 4.
Cotton cloth rubbing test:
the modified cotton cloth was repeatedly rubbed with hands for 3s for 480 cycles. The change in contact angle during rubbing is shown in fig. 4 a. After the kneading is finished, the water contact angle of the cotton cloth can still reach 152.8 degrees.
Abrasive paper abrasion test:
the coated glass sheet was placed upside down on sandpaper (1000 mesh), and then loaded with a 100g weight, and the cycle was repeated at 20cm, and 10 cycles were allowed. The change in water contact angle during this process is shown in figure 4 b. The results show that the superhydrophobicity remains after abrasion. And the adhesive strength was measured with an adhesion tester. The adhesion strength of the coating on different substrates can reach megapascals levels (e.g., 6.5MPa on ceramic).
Organic liquid and salt solution soaking resistance test:
the modified glass sheet still can keep super-hydrophobicity after being soaked in absolute ethyl alcohol, n-octane, dichloromethane, DMF, tetrahydrofuran, water and sodium chloride (0.1M) solution for 7 days. The WCA after soaking is shown in fig. 4 c.
Acid and alkali resistance test:
soaking the modified glass sheet in NaOH (0.1M), NH 3 H 2 O(25％)，CH 3 COOH, HCl (0.1M, 1.0M), aqua regia, and tested the WCA of the glass over 10min. In fig. 4d it can be seen that the WCA of the treated glass sheets did not change much, but the WCA of the glass sheets soaked with aqua regia became 145.9 ° at 10min, still maintaining superhydrophobicity. In fig. 4e, the longest soaking time to maintain superhydrophobicity in the above-described environment is explored and the coating is found to be more suitable in an acidic environment relative to a strongly alkaline environment. Wherein the soak time in HCl (0.1M) was up to 103h and the WCA was 150.1 deg..
And (3) temperature testing: the modified glasses were placed at different temperatures (-50 ℃ C. -300 ℃ C.) for 2h and tested for WCA. The variation in WCA is shown in fig. 13, demonstrating that coatings treated at different temperatures can still remain superhydrophobic.
5. Purified water
Oil/water mixture separation
Cotton cloth is the most commonly used 2D material for oil-water separation. The modified cotton cloth is clamped between two glass containers to form an oil-water mixture separating device. Because the modified cotton cloth can be subjected to wettability conversion, different types of oil-water mixture separation can be performed according to requirements. For mixtures of heavy oil (dichloromethane, 1, 2-dichloroethane, carbon trichloride) and water, modified cotton cloth was used directly. The modified cotton cloth has super-hydrophobicity/super-lipophilicity, heavy oil flows down rapidly under the action of gravity, and water is isolated above the cotton cloth, so that the heavy oil and the water are separated. In fig. 5a, methylene chloride and water were separated by modified cotton. For the mixture of light oil and water, we only need to irradiate the modified cotton cloth with UV to be hydrophilic. In fig. 5b, the superhydrophilic cotton cloth was first wetted with water, and then a mixture of light oil (petroleum ether) and water was poured into the apparatus, and it was found that water passed through the cotton cloth, while petroleum ether was blocked above the cotton cloth by the underwater superoleophobic properties of the cotton cloth. In fig. 5c, several other model oil and water separation efficiencies and throughputs were also tested, with separation efficiencies >90%. In addition, methylene chloride and petroleum ether were selected as representatives of heavy oil and light oil, respectively, and the separation efficiency of cotton cloth separation was tested 20 times. As can be seen in fig. 5d, the separation efficiency after 20 times and the initial separation efficiency did not change much. This also proves that the oil-water separation efficiency of the cotton cloth is stable.
Water-in-oil and oil-in-water emulsion separation
Water-in-oil or oil-in-water emulsions are the most common oil-water mixtures. Compared with the heterogeneous mixture of oil and water, the emulsion is more stable and is more difficult to separate. The separation of different water-in-oil and oil-in-water emulsions was successfully carried out with modified cotton cloth.
Separation of water-in-oil emulsion: in FIGS. 6a-d, four emulsions were prepared, a-d corresponding to water-in-diesel, water-in-n-octane, water-in-carbon tetrachloride, and water-in-methylene chloride, respectively. Before separation, the emulsion was milk-like in color, turbid. The emulsion after separation became clear and transparent. To further demonstrate the ability of cotton to separate the above emulsion. Dynamic light scattering (DLC) experiments were performed on the emulsions before and after separation, and DLS results of droplet sizes before and after filtration of the four oil-in-water emulsions (insets) are shown in FIGS. 6e-h, respectively (FIG. 6e is a DLS result chart for water-in-diesel, FIG. 6f is a DLS result chart for water-in-n-octane, FIG. 6g is a DLS result chart for water-in-carbon tetrachloride, and FIG. 6h is a DLS result chart for water-in-methylene chloride). The particle size of the emulsion before separation is 100nm-1000nm, and the particle size after separation is below 100 nm. The separation efficiency and flow of the cotton cloth to the four emulsions were also calculated. Figure 6i shows the flux and separation efficiency of different oil-in-water emulsions, from which it can be seen that the separation efficiency of all four emulsions is >95%.
The wettability can be converted to superhydrophilicity by UV irradiation, and therefore, the separation of oil-in-water emulsions is also possible: separating diesel oil in water, n-octane in water, carbon tetrachloride in water and dichloromethane in water by using the modified cotton cloth. In FIGS. 7a-b, a photographic comparison of four oil-in-water emulsions before and after separation is shown. The oil-in-water emulsion was milky white before separation. The emulsion after separation is colorless and transparent. FIGS. 7e-h are graphs of the particle size change before and after separation of the four emulsions. Before and after separation, the particle size is changed from 1000-2000nm to 6-15nm. In fig. 7i, the separation efficiency and throughput of the hydrophilic cotton cloth separation oil-in-water emulsion is shown, it can be seen that the separation efficiency is >99%.
Photocatalytic degradation of soluble pollutants in water
Actual contaminated water contains not only insoluble oils but also soluble organic chemicals. The modified cotton cloth can degrade soluble pollutants in water through photocatalysis. The mechanism for photocatalytic degradation of soluble contaminants in water is shown in fig. 8 a. TiO 2 2 The (anatase) nano particles have strong photoresponse, and can generate high-activity photo-generated electron-hole pairs under the irradiation of ultraviolet rays. A portion of the photogenerated electrons and holes migrate to the TiO 2 Surface and H with surface 2 O and O 2 Reaction to generate high-activity O 2 · - And OH radicals, which are capable of undergoing redox reactions in the presence of water-soluble contaminants to decompose organic species into H 2 O and CO 2 Etc. to clean water. In order to test the degradation capability of the modified cotton cloth, three methylene blue aqueous solutions of 10. Mu.g/mL, 30. Mu.g/mL and 50. Mu.g/mL are prepared. The degradation of the solutions with the above three concentrations takes 150min,180min and 210min respectively under the conditions of the same volume (35 mL), the same cotton cloth size (3 cm multiplied by 3 cm), the same illumination intensity and the same illumination distance (10 cm).
In the process, the solution becomes lighter and lighter until transparent, as shown in fig. 14 b. In order to accurately measure the concentration change of MB, the absorbance of the solution was measured every 30min. In FIGS. 8b-d, it can be seen that the characteristic MB peak (665 nm) decreases with increasing irradiation time, indicating that methylene blue is gradually degraded. In addition, in order to test the cycle performance of the cotton cloth for degrading the methylene blue solution, the 10 microgram/mL methylene blue solution is degraded by the same piece of modified cotton cloth for multiple times, and the cotton cloth needs to be dried in an oven at 90 ℃ for 30min between the two degradations. The results show that the cotton cloth can continuously degrade 6 times of the methylene blue solution, and the degradation efficiency of 6 times is stable, as shown in fig. 8 f. In FIG. 8g, the absorbance change over time was measured for the 6 th time, and it can be seen that the absorbance change for the sixth time was slightly faster than the absorbance change for the first time in FIG. 8 c. Presumably, the reason is that TiO increased with the UV irradiation time 2 At the same time as MB in the water is degraded, some of the compounds grafted on the cotton cloth are also degraded. This results in TiO 2 The exposed sites increase and the degradation rate becomes greater. A graph comparing the first and sixth degradation rates is shown in fig. 14 a. The methylene blue solution is subject to self-degradation under UV irradiation. To explore the effect of self-degradation of MB solutions, the degradation rates of MB solutions with and without modified cotton were compared at three concentrations, as shown in fig. 8 h. The results show that the modified cotton cloth is degraded at a much faster rate than the rate of self-degradation during the overall degradation process. FIG. 8i shows the first order reaction rate constant (k) of the degradation process. By comparisonThe degradation rate of the modified cotton cloth is 21-71 times of the self-degradation rate. In addition to using the modified cotton cloth to degrade the MB solution, other common pollutant dyes such as Congo red, methyl Orange (MO), rhodamine B and mixed solution of MB and MO are explored and degraded by the modified cotton cloth to finally become transparent, as shown in FIG. 14 d. And FIG. 14c shows the change in absorbance of MO during degradation.
In situ separation and degradation of wastewater
Besides the coating cotton fabric can be degraded and separated independently, the coating cotton fabric is expected to realize the purification of wastewater through an in-situ separation-degradation process. As shown in FIG. 9, a mixture of dichloromethane (30 mL, sudan III staining) and MB contaminated water (30mL, 10. Mu.g/mL) was selected as the target wastewater. The coated cotton fabric was first able to immediately separate the dichloromethane from the aqueous MB solution before uv irradiation due to the superhydrophobicity of the coated cotton fabric. MB, which is soluble in water, is degraded by UV irradiation for 100 min. Meanwhile, under the irradiation of ultraviolet rays, the super-hydrophobicity of the coated cotton fabric is gradually changed into super-hydrophilicity. And finally, the purified water permeates into the cotton fabric for collection. The in-situ separation-degradation system can simultaneously separate oil and soluble pollutants, and meets higher purification requirements of the industry.
Photocatalytic extension applications
Superhydrophobic surfaces are susceptible to contamination by non-volatile oils. The coated cotton fabric was subjected to photocatalytic removal with a mixture of oleic acid and absolute ethanol (volume ratio 1). As shown in fig. 10a, the WCA dropped to around 40 ° after the coated cotton fabric was contaminated with oleic acid. After UV irradiation and heating, the fabric regains superhydrophobicity with a WCA greater than 150 °. This process can be reused several times without losing the superhydrophobicity of the coating. The photocatalytic performance of the cotton fabric under ultraviolet irradiation is proved through the degradation of oleic acid. Furthermore, contamination of cotton fabric with different dyes (e.g., sudan III and MB) can be cleaned by degradation of these dyes under uv irradiation (fig. 10b,10 c).
In addition, different shaped masks may be used to design the imprint in the water. As shown in fig. 10d, a hexagonal mask was used to cover the coated glass. After UV irradiation, the coated glass becomes superhydrophilic except for the hexagonal portion. The superhydrophilic portion was easily stained by MB solution, while the covered portion was not stained due to superhydrophobicity (fig. 10 d). When placed in water, the hexagonal superhydrophobic portions will reflect light due to the large number of bubbles, as shown in fig. 10 e.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. A preparation method of a full water-based super-hydrophobic coating with reversible wettability is characterized by comprising the following steps: the method comprises the following steps:
mixing FS-3100 aqueous solution and nano TiO 2 Mixing and stirring the cellulose particles and the micron-sized cellulose particles in proportion to form a suspension; the concentration of FS-3100 aqueous solution is 0.1-0.5 μ l/ml; nano TiO 2 2 And cellulose in a mass ratio of 2-5;
adding N-aminoethyl-gamma-aminopropyltrimethoxysilane and KH-570 into the suspension, and uniformly stirring;
finally, adding FAS into the mixture, and continuously stirring to obtain a coating; the concentration of FAS added to the suspension is 0.01-0.03g/ml;
coating the coating on the surface of a substrate to obtain the fully water-based super-hydrophobic coating with reversible wettability.
2. The method for preparing the all-water-based superhydrophobic coating with reversible wettability according to claim 1, characterized in that: n-aminoethyl-gamma-aminopropyltrimethoxysilane and KH-570 were added dropwise to the suspension.
3. The method for preparing the all-water-based superhydrophobic coating with reversible wettability according to claim 1, characterized in that: the concentration of FS-3100 aqueous solution was 0.2. Mu.l/ml.
4. The method for preparing the all-water-based superhydrophobic coating with reversible wettability according to claim 1, characterized in that: nano TiO 2 2 And cellulose in a mass ratio of 3-5.
5. The method for preparing the all water-based superhydrophobic coating having reversible wettability according to claim 1, wherein: nano TiO 2 2 And cellulose in a mass ratio of 4.
6. The method for preparing the all-water-based superhydrophobic coating with reversible wettability according to claim 1, characterized in that: the volume ratio of the suspension, the N-aminoethyl-gamma-aminopropyltrimethoxysilane and the KH-570 is 15-25:2-3:1.
7. The method for preparing the all-water-based superhydrophobic coating with reversible wettability according to claim 1, characterized in that: n-aminoethyl-gamma-aminopropyltrimethoxysilane and KH-570 are added into the suspension dropwise and stirred for 0.5 to 1.5 hours at the temperature of between 55 and 65 ℃.
8. The method for preparing the all-water-based superhydrophobic coating with reversible wettability according to claim 1, characterized in that: n-aminoethyl-gamma-aminopropyltrimethoxysilane and KH-570 were added dropwise to the suspension and stirred at 60 ℃ for 1h.
9. The method for preparing the all water-based superhydrophobic coating having reversible wettability according to claim 1, wherein: FAS was added to the suspension at a concentration of 0.0232g/ml.
10. The method for preparing the all-water-based superhydrophobic coating with reversible wettability according to claim 1, characterized in that: after the FAS is added to the suspension, stirring is continued for 2-4h.
11. The method for preparing the all-water-based superhydrophobic coating with reversible wettability according to claim 1, characterized in that: when the coating is prepared, the flexible substrate is prepared by adopting a dipping method; for the hard substrate, the spraying mode is adopted for preparation.
12. An all-water-based super-hydrophobic coating with reversible wettability, which is characterized in that: prepared by the preparation method of any one of claims 1 to 11.
13. The use of the all water-based superhydrophobic coating with reversible wettability according to claim 12 for oil-water separation and photocatalytic degradation of soluble contaminants in water.
14. A preparation method of filter cloth for oil-water separation and wastewater purification is characterized by comprising the following steps: the method comprises the steps of preparing a coating and preparing filter cloth by impregnating cotton cloth; wherein, the first and the second end of the pipe are connected with each other,
the preparation of the coating comprises the following steps: mixing FS-3100 aqueous solution and nano TiO 2 Mixing and stirring the mixture and micron-sized cellulose particles to form a suspension; the concentration of FS-3100 aqueous solution is 0.1-0.5 μ l/ml; nano TiO 2 2 And cellulose in a mass ratio of 2 to 5;
adding N-aminoethyl-gamma-aminopropyltrimethoxysilane and KH-570 into the suspension drop by drop, uniformly mixing, adding FAS into the suspension, and stirring for a set time to obtain a coating; the concentration of FAS added to the suspension is 0.01-0.03g/ml;
and soaking the cotton fabric into the coating for a set time, and taking out and drying to obtain the coating.
15. A filter cloth for oil-water separation and wastewater purification is characterized in that: the preparation method of claim 14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111088266.2A CN113774655B (en) | 2021-09-16 | 2021-09-16 | Full-water-based super-hydrophobic coating with reversible wettability as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111088266.2A CN113774655B (en) | 2021-09-16 | 2021-09-16 | Full-water-based super-hydrophobic coating with reversible wettability as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113774655A CN113774655A (en) | 2021-12-10 |
| CN113774655B true CN113774655B (en) | 2023-03-07 |
Family
ID=78851434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111088266.2A Active CN113774655B (en) | 2021-09-16 | 2021-09-16 | Full-water-based super-hydrophobic coating with reversible wettability as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113774655B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114134706B (en) * | 2021-12-14 | 2023-04-25 | 齐鲁工业大学 | Fluorine-free ultraviolet response superhydrophobic coating, preparation method and application |
| CN114457586B (en) * | 2022-02-14 | 2022-07-15 | 哈尔滨工业大学 | Preparation method of high-thermal-conductivity super-amphiphobic fabric with liquid drop one-way permeability |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10472769B2 (en) * | 2013-10-10 | 2019-11-12 | The Regents Of The University Of Michigan | Silane based surfaces with extreme wettabilities |
| CN104987520B (en) * | 2015-07-09 | 2018-04-17 | 北京航空航天大学 | A kind of super-hydrophobic nano clear coat and preparation method thereof |
| JP6818432B2 (en) * | 2016-05-11 | 2021-01-20 | 三菱電機株式会社 | Coating composition, luminaire, coating film laying method, and luminaire manufacturing method |
| US11242468B2 (en) * | 2017-10-17 | 2022-02-08 | Indian Institute Of Technology Madras (Itt Madras) | Aqueous composition and a method of producing durable and extremely efficient water repelling superhydrophobic materials at ambient condition thereof |
| US10377907B2 (en) * | 2017-11-08 | 2019-08-13 | King Fahd University Of Petroleum And Minerals | Substrate with a superhydrophobic coating and a method of fabricating thereof |
| CN108421421B (en) * | 2018-02-12 | 2021-07-06 | 上海大学 | Fabric mesh with underwater super-oleophobic composite coating and preparation method thereof |
| CN109364772B (en) * | 2018-11-05 | 2021-04-06 | 武汉工程大学 | PSMA (patterned silica)/nano-silica/fluorocarbon surfactant composite material for oil-water separation and preparation method thereof |
| CN111019473B (en) * | 2019-12-24 | 2021-05-28 | 齐鲁工业大学 | Preparation of coatings with excellent mechanical and chemical stability |
| CN111138917B (en) * | 2020-01-17 | 2021-04-20 | 中北大学 | Preparation method of super-hydrophobic coating based on micro/nano inorganic particle synergistic enhanced fluorocarbon resin |
-
2021
- 2021-09-16 CN CN202111088266.2A patent/CN113774655B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113774655A (en) | 2021-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113774655B (en) | Full-water-based super-hydrophobic coating with reversible wettability as well as preparation method and application thereof | |
| Wang et al. | Superhydrophobic and photocatalytic PDMS/TiO2 coatings with environmental stability and multifunctionality | |
| Cai et al. | Fluorine-free and hydrophobic hexadecyltrimethoxysilane-TiO2 coated mesh for gravity-driven oil/water separation | |
| Ge et al. | Fabrication of BiOBr-silicone aerogel photocatalyst in an aqueous system with degradation performance by sol-gel method | |
| Singh et al. | Fabrication of durable superhydrophobic coatings on cotton fabrics with photocatalytic activity by fluorine-free chemical modification for dual-functional water purification | |
| CN106422423B (en) | A kind of super-hydrophobic wire mesh and preparation method thereof | |
| Liu et al. | Photocatalytic superamphiphobic coatings and the effect of surface microstructures on superamphiphobicity | |
| US20070237943A1 (en) | Coating Material and Use Thereof | |
| Yang et al. | A less harmful system of preparing robust fabrics for integrated self-cleaning, oil-water separation and water purification | |
| CN111632581B (en) | Raspberry-like super-hydrophobic oleophylic cotton fiber oil-water adsorption/separation membrane and preparation method and application thereof | |
| CN110734655B (en) | PH-responsive super-hydrophobic coating material, and preparation method and application thereof | |
| CN108822603A (en) | A kind of preparation method of coating composition | |
| CN106178599B (en) | A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and its preparation and the application in water-oil separating | |
| CN111335038A (en) | Washable photocatalytic super-hydrophobic cotton fabric and preparation and application thereof | |
| Yu et al. | Biomimetic fabrication of superhydrophobic loofah sponge: robust for highly efficient oil–water separation in harsh environments | |
| CN107308928A (en) | The special titanium dioxide process of emulsion paint | |
| Cai et al. | Scalable Fabrication of Superhydrophobic Coating with Rough Coral Reef‐Like Structures for Efficient Self‐Cleaning and Oil‐Water Separation: An Experimental and Molecular Dynamics Simulation Study | |
| CN113683953A (en) | Preparation method of renewable double self-cleaning super-hydrophobic photocatalytic coating | |
| Zhao et al. | Stimuli-responsive wettability quartz sand filter material for efficient separation of oil/water mixture and controllable demulsification of oil/water emulsion | |
| CN114134706B (en) | Fluorine-free ultraviolet response superhydrophobic coating, preparation method and application | |
| Qi et al. | Cotton fabric loaded with self-dispersive and reactive biphasic TiO 2 for durable self-cleaning activity and ultraviolet protection | |
| CN115093673A (en) | Three-dimensional super-hydrophobic material prepared based on bismuth oxybromide and application thereof | |
| CN114262548A (en) | Coating with visible light catalysis function and preparation method thereof | |
| CN108485346A (en) | A kind of antifouling self-cleaning coating of asepsis environment-protecting and preparation method thereof | |
| CN109989273B (en) | Preparation method and application of photocatalytic coating fabric |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |