WO2019102459A1 - Sonochemical coating of surfaces with superhydrophobic particles - Google Patents
Sonochemical coating of surfaces with superhydrophobic particles Download PDFInfo
- Publication number
- WO2019102459A1 WO2019102459A1 PCT/IL2018/051249 IL2018051249W WO2019102459A1 WO 2019102459 A1 WO2019102459 A1 WO 2019102459A1 IL 2018051249 W IL2018051249 W IL 2018051249W WO 2019102459 A1 WO2019102459 A1 WO 2019102459A1
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- WIPO (PCT)
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title abstract description 33
- 239000011248 coating agent Substances 0.000 title abstract description 28
- 239000002245 particle Substances 0.000 title description 9
- 229920009638 Tetrafluoroethylene-Hexafluoropropylene-Vinylidenefluoride Copolymer Polymers 0.000 claims abstract description 110
- 239000002105 nanoparticle Substances 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000004753 textile Substances 0.000 claims abstract description 40
- 239000011521 glass Substances 0.000 claims abstract description 16
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 238000005580 one pot reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 62
- 239000004698 Polyethylene Substances 0.000 claims description 61
- 229920000573 polyethylene Polymers 0.000 claims description 61
- 230000008569 process Effects 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims description 26
- 150000004706 metal oxides Chemical class 0.000 claims description 26
- -1 polyethylene Polymers 0.000 claims description 17
- 238000000527 sonication Methods 0.000 claims description 16
- 229920002334 Spandex Polymers 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000004759 spandex Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 240000008042 Zea mays Species 0.000 claims description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 9
- 235000005822 corn Nutrition 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000012154 double-distilled water Substances 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 229920001410 Microfiber Polymers 0.000 claims description 7
- 239000004677 Nylon Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920000297 Rayon Polymers 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000010985 leather Substances 0.000 claims description 7
- 239000003658 microfiber Substances 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000123 paper Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000002964 rayon Substances 0.000 claims description 7
- 210000002268 wool Anatomy 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001222 biopolymer Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 38
- 239000010410 layer Substances 0.000 description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 8
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004630 atomic force microscopy Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229920003020 cross-linked polyethylene Polymers 0.000 description 3
- 239000004703 cross-linked polyethylene Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 239000004706 High-density cross-linked polyethylene Substances 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- 239000004704 Ultra-low-molecular-weight polyethylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920004932 high density cross-linked polyethylene Polymers 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002032 lab-on-a-chip Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012990 sonochemical synthesis Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
- B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
- B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
- B06B1/20—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of a vibrating fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
-
- 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
- C09D7/65—Additives macromolecular
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
-
- 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
- D06M11/42—Oxides or hydroxides of copper, silver or gold
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- 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
-
- 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
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
-
- 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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
-
- 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
Definitions
- the present invention relates to the sonochemical coating of substrates. More particularly, the present invention relates to imparting superhydrophobic functionality to substrates by a sonochemical method.
- a superhydrophobic surface requires the combination of microscale and nanoscale hierarchical structures with low- surface-energy materials (see, R. N. Wenzel, Ind. Eng. Chem. (1936), 28, 988-994 and A. B. D. Cassie et al., Trans. Faraday Soc. (1944), 40, 546-551).
- NPs nanoparticles
- microjets are formed upon the collapse of the acoustic bubbles.
- the microjets are directed toward the solid surface and move at a sufficiently high speed (>500 m/s) to embed the newly-formed particles into the substrate (I. Perelshtein et al., Cellulose, (2013), 20, 1215-1221).
- TSV Tetrafluoroethylene-Hexafluoropropylene- Vinylidene Fluoride copolymer
- Dyneon LLC U.S.A.
- T M 165°C for THV 220G
- the as-obtained PE surface exhibits a WCA of 160° and excellent durability under outdoor conditions for two months, which is crucial for practical applications.
- This novel bilayer coating exhibits even wider high-contact angles (up to 169°).
- a sonochemical one-pot process for in-situ generation of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) nanoparticles (NPs) and their deposition on a substrate comprising:
- Another embodiment of the invention provides a process as described above, wherein the resulting surface which exhibits superhydrophobic properties, wherein: - the THV solvent is acetone and the concentration of the THV therein is 4 mg/ml;
- the THV solution is sonicated for about 1 h at a temperature of about 30°C;
- the solution is irradiated for about 30 min with an ultrasonic corn in the presence of a polymer sheet;
- Yet another embodiment of the invention provides a process as described above, wherein the substrate is kept at a constant distance of about 2 cm from the sonicator tip during the entire reaction.
- One embodiment of the invention provides a sonochemical process for a layer-by- layer (SLBL) generation of a surface exhibiting improved superhydrophobic properties on a polymer sheet, comprising, prior to performing the process above- described process:
- Another embodiment of the invention provides a layer-by-layer process as described above, wherein the concentration of metal-acetate in double-distilled water (DDW) is 0.1 - 2 mg/ml
- Yet another embodiment of the invention provides a layer-by-layer process as described above, wherein the metal-acetate is selected from zinc acetate [Zn(0Ac) 2 -2H 2 0] or copper acetate [Cu(0Ac) 2 -H 2 0].
- the substrate for coating comprises or is made of a polymer, glass, paper, textile, wood, ceramic, fur, metal, carbon, a biopolymer and/or silicon.
- the textile may be any one of cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene and spandex.
- a further embodiment of the invention provides a process as described above, wherein the polymer is a polyethylene sheet.
- One embodiment of the invention provides an article, manufactured according to the process as described above, having superhydrophobic functionality.
- Another embodiment of the invention provides an article as described above for use in a device selected from touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
- Fig. 1 shows the HR-SEM images of (A) pristine PE, (B) PE coated with THV NPs, (C) PE coated with ZnO NPs and (D) PE coated with CuO NPs.
- Fig. 2 shows the FTIR spectra of the pristine PE (purple line) and the THV-coated PE (red line).
- Fig. B shows the atomic force microscopy (AFM) images of PE sheet: (A) pristine, (B) coated with THV NPs, (C) coated with ZnO@THV nanoparticles and (D) coated with CuO@THV NPs.
- AFM atomic force microscopy
- Fig. 4 shows the X-ray diffraction (XRD) pattern of (A) CuO NPs and (B) ZnO NPs.
- Fig. 5 shows the water contact angle (WCA) measurements of (A) a pristine PE sheet, (B) a PE sheet coated with THV NPs, (C) a PE sheet coated with ZnO@THV NPs and (D) a PE sheet coated with CuO@THV NPs.
- WCA water contact angle
- Fig. 6 demonstrates the transmittance in the visible region of uncoated PE bag (red line) and coated (grey line).
- Fig. 7 shows the water contact angle (WCA) measurement of cotton coated with THV NPs.
- Fig. 8 Selected time sequence images of water droplet falling on (a) untreated textile, and (b) textile coated with THV NPs. Arrows point to water droplet. Time (seconds) from shooting first image is indicated below images.
- One embodiment of the present invention provides a sonochemical process for the in-situ generation of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) nanoparticles (NPs) and their subsequent deposition on a substrate in a one-pot reaction, comprising:
- THV dissolving THV in acetone at a concentration of between 0.1 to 10 mg/ml; - sonicating the solution for 1 h at low temperature, in the range of 10° - 40°C; - adding an amount of ethanol to the solution, to bring the THV a final concentration of between 1 - 10 mg/ml; the volume ratio of acetone to ethanol is varied between 1:1 and 1:4.
- Another embodiment of the present invention provides a sonochemical process for a layer-by-layer (SLBL) generation of a superhydrophobic surface on a substrate, comprising:
- reaction beaker placed in a cooling bath, while maintaining a constant temperature of between 10° - 30 °C during the reaction;
- a further embodiment of the invention relates to a layer-by-layer (SLBL) generation of a superhydrophobic surface as described above, wherein the metal-acetate is selected from zinc acetate [Zn(0Ac) 2 -2H 2 0] or copper acetate [Cu(0Ac) 2 -H 2 0].
- SLBL layer-by-layer
- the substrate may be a polymer, glass, paper, textile, wood, ceramic, fur, metal, carbon, a biopolymer and/or silicon, and the likes.
- the substrate in any one of above- mentioned methods is a polymer, in some of these embodiments, the polymer is a polyethylene sheet.
- the substrate may be a textile selected from: cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene and spandex.
- Yet another embodiment of the present invention provides a process according to any one of above-mentioned methods for use in imparting a superhydrophobic functionality to a substrate.
- any one of the above-mentioned processes is used in imparting a superhydrophobic functionality to touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
- the coated substrate is or forms a part of an article.
- an article e.g., an article- of-manufacture
- a THV NPs coated substrate as prepared by the processes described herein.
- Some embodiments of the invention provide an article, generated according to the process as described above, having a superhydrophobic functionality.
- the invention provides an article, generated according to the process described above, having a superhydrophobic functionality, for use in touch screens, medical devices, surgical swabs, textiles, polymeric surfaces, car interior and glasses.
- the present invention provides a sonochemical method for imparting superhydrophobicity to a substrate, such as a polyethylene (PE) sheet or any other suitable polymeric substrate.
- a substrate such as a polyethylene (PE) sheet or any other suitable polymeric substrate.
- This is achieved by sonochemically depositing nanoparticles (NPs) of a THV hydrophobic polymer on the PE sheets.
- the NPs of THV are generated and deposited on the surface of the PE using ultrasound irradiation. Optimizing the process results in a homogeneous distribution of 110-200 nm THV NPs on the PE surface.
- the coated surface displays a water-contact angle of 140-160°, indicating an excellent superhydrophobicity.
- This superhydrophobic surface shows high stability under outdoor conditions for two months, which is essential for various applications.
- metal-oxide nanoparticles can be integrated into the THV coating to increase the surface roughness and, as a result, further improve the superhydrophobicity
- the process of the present invention involves inexpensive precursors and is fast.
- the as-obtained functional PE with high superhydrophobicity can be used in a range of applications, such as electronic devices, medical equipment, hospital surfaces and more. Furthermore, this approach can be adapted to other surfaces, allowing sonochemical deposition of THV on other substrates and thus expanding the utilization of this methodology to additional applications.
- THV refers to a tetrafluoroethylene-hexafluoropropylene- vinylidene fluoride copolymer.
- These polymers are hydrophobic, flexible, transparent, partially-fluorinated thermoplastic polymers, characterized by very low surface energy, good chemical resistance and a low processing temperature.
- Non limiting examples of THV polymers used in the present invention are THV 220G (Dyneon 3M Co.), or other fluorine rich polymers.
- polyethylene refers to any polymer having the chemical formula (C 2 H 4 ) n , or a mixture of similar polymers of ethylene with various values of n.
- Said term may refer to, but not limited to, ultra-high-molecular-weight polyethylene (UHMWPE), ultra-low-molecular-weight polyethylene (ULMWPE or PE- WAX), high-molecular-weight polyethylene (HMWPE), high-density polyethylene (HDPE), high-density cross-linked polyethylene (HDXLPE), cross-linked polyethylene (PEX or XLPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and very-low-density polyethylene (VLDPE).
- UHMWPE ultra-high-molecular-weight polyethylene
- ULMWPE or PE- WAX ultra-low-molecular-weight polyethylene
- HMWPE high-molecular-weight polyethylene
- metal oxide refers to a substance comprising one or more metal atoms and one or more oxygen atoms, wherein one or more of the metal atom(s) is in association with one or more oxygen atom(s).
- the metal oxides include, without limitation, oxides of alkali metals, alkaline earth metals, lanthanides, actinides, transition metals, metalloids, or any other metals.
- Non limiting examples of metal oxides of the present invention may include Ti0 2 , MgO, ZrO, ZnO, CuO and Si0 2 . In some embodiments of the invention, the metal oxide is ZnO or CuO.
- the term “sonochemistry” refers to a chemical reaction which is driven by an ultrasound irradiation in the 20-100 kHz range.
- superhydrophobic refers to surfaces which are highly hydrophobic, i.e., extremely difficult to wet.
- the term refers to surfaces having a contact angle of a water droplet exceed 150°.
- the term "textile” encompasses both natural and synthetic textiles, and refers to fabrics such as: cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene, spandex, and many more.
- THV 220G The THV which was used in the examples below is THV 220G, purchased from Dyneon 3M Co. Unless otherwise specified, all chemical reagents of chemical grade were purchased from Sigma-Aldrich, without further purification. All the experiments were conducted in the presence of a PE sheet.
- the particle morphology and size were characterized using high-resolution scanning electron microscopy (HR-SEM) with a Magellan, FEI microscope, at an accelerating voltage, over the range of 5-15 kV.
- HR-SEM high-resolution scanning electron microscopy
- the coated and uncoated PE sheets were further characterized by Fourier-transform infrared (FTIR) spectroscopy using Nicolet iSlO, performing 100 scans for each spectrum.
- FTIR Fourier-transform infrared
- the roughness of the coated and uncoated surfaces was determined by atomic force microscopy (AFM), using a Digital Instruments Nanoscope.
- the determination of the roughness factor (r) is based on the ratio of the calculated area, comprised of 3 points (X, Y, Z), versus the scanned area.
- the surface wettability of the superhydrophobic PE sheets was characterized using WCA measurements, with a Dataphysics OCA20 contact-angle system at ambient temperature.
- the ZnO and CuO content on the PE sheets was determined by inductively coupled plasma (ICP) using ULTIMA JY2501, after treating the sample with 0.5 M of HN0 3 .
- the X-ray diffraction (XRD) patterns of the product were measured using a Bruker D8 diffractometer (Karlsruhe, Germany) with Cu Ka radiation.
- the THV (0.1 - 0.9 g, Dyneon) was dissolved in 50 - 100 ml acetone THV polymer and the solution was sonicated in a sonication bath for 1 h at 30 °C.
- 50 ml acetone were used to dissolve the THV
- 50 ml of ethanol were added to the solution after completing the sonication bath.
- the solution was irradiated for 30 min with an ultrasonic corn (Ti horn, with booster 30% efficiency 750 W) in the presence of a PE sheet (2.5x3.5 cm 2 ). Using a wire, the PE sheet was kept at a constant distance of 2 cm from the sonicator tip during the entire reaction.
- the sonication beaker was placed in a cooling bath, maintaining a constant temperature of 30 °C during the reaction.
- the PE sheet was removed from the solution, washed with water and dried at room temperature for 0.5 h.
- One of the goals of this embodiment of the invention is to provide a homogeneous, uniform coating of THV NPs on the surface of PE that exhibits a large WCA.
- the amount of THV and the type of solvent were found to be critical parameters in obtaining a coating with good superhydrophobic properties. According to the manufacturer (3M) of the THV polymer, it does not dissolve in most of the common solvents, but does dissolve in acetone.
- the first coating was prepared from an acetone solution of THV (Ex. 1). Almost no coating was observed across the sample, resulting in a low contact angle of 110°. The contact angle of the bare surface was 100°.
- Table 1 indicates that a maximal contact angle is obtained when 0.2 g of THV is dissolved in 100 ml of the mixed solvent.
- THV polymer Ex. 2 and 3
- homogeneous coating is obtained; however, lower WCA values are measured.
- a smaller WCA is also obtained upon increasing the concentration of THV in the solution, as in Ex. 5. This is attributed to the non-homogeneous layer, exposing less fluorine atoms to water.
- the beaker was placed in a cooling bath, while maintaining a constant temperature of 30 °C during the reaction.
- the PE sheet was removed from the solution, washed with water and dried at room temperature for 0.5 h.
- the THV NPs were deposited as a second layer on top of the metal-oxide layer, applying the same procedure as described in Ex. 4.
- one object of the present invention is to impart superhydrophobicity in a one-pot sonochemical coating process.
- the THV and metal oxide were deposited in one-pot reaction, the amount of THV attached to the surface was too low and the recorded WCA was only 112°.
- SLBL Sonochemical Layer-by-Layer
- the first layer is composed of metal-oxide NPs and the second layer of THV NPs.
- the layer composed of metal-oxide nanoparticles increased the surface roughness, and the THV-NP layer decreased the surface free energy, consequently increasing the WCA.
- the as-obtained SLBL coating exhibits a WCA of 169° and generates a homogeneous coating covering the PE surface.
- the content of CuO and ZnO deposited on the PE sheets was evaluated by inductively coupled plasma (ICP) analysis and found to be 0.036 and 0.042 wt%, respectively. To prepare the sample for ICP, the metal oxide was dissolved in 0.5 M HN0 3 and the ion content was probed.
- ICP inductively coupled plasma
- the uncoated and coated sheets were characterized by HR-SEM.
- the uncoated PE surface is plain and smooth (Fig. 1A).
- Fig. IB shows a rough coating of THV-polymer NPs.
- the PE surface is homogeneously covered by the THV polymer with nanoscale grains.
- the particle size of the THV NPs is between 100 and 200 nm.
- the pre-layer coating is composed of metal-oxide NPs, which were also examined by HR-SEM (Figs. 1C and ID). It is clear that the surface is coated with ZnO and CuO NPs, which are further covered by a layer of THV NPs.
- the particle size of the ZnO is in the range of 110-170 nm, while the size of the CuO NPs is ⁇ 50 nm.
- the hierarchical structure of the metal-oxide NPs increases the surface roughness dramatically, which can explain the observed improvement in the WCA.
- the crystallinity of the sonochemically-prepared CuO and ZnO was examined by XRD (Fig. 4).
- the XRD pattern of the sonochemically-prepared ZnO NPs is shown in Fig. 4A and it is indeed crystalline.
- the diffraction peaks match the hexagonal phase of ZnO (PDF: 89-7102) very well.
- the 2 ⁇ peaks appear at 31.77, 34.42, 36.25, 47.54, 56.6, 62.85 and 67.95° and are assigned to the (100), (002), (101), (102), (110), (103) and (112) reflection planes of the hexagonal ZnO particles, respectively. No peaks characteristic of any impurities were detected.
- the XRD patterns of the sonochemically-prepared CuO NPs are shown in Fig. 4B.
- the copper oxide is crystalline, and the diffraction peaks match the PDF file 80-1916.
- the wettability of the PE-coated sheets was evaluated by measuring the WCA. Water droplets (5.0 pL) were dripped carefully onto the coating films. The contact angle value was obtained by measuring five different positions of the same sample (Fig. 5).
- the pristine PE surface exhibits a WCA of 100° (Fig. 5A).
- the WCA increases to 160° (Fig. 5B), demonstrating the superhydrophobicity of the coated PE.
- the integration of a pre-layer of either ZnO or CuO NPs increases the roughness of the PE surface, resulting in a higher WCA of 169° (Figs. 5C and 5D).
- the superhydrophobic surface must be durable under outdoor conditions such as scorching sun and heavy rain.
- the following experiment was carried out. The samples were placed on the roof of a building, exposed to harsh conditions (rain, low temperature, sun, wind, dust, etc.). The experiments were conducted during December and January with an average temperature of 18 °C and an average relative humidity of 50%. The average amount of precipitation during the experiment period was IBB mm. After two months, no visual change was observed, and there was almost no change in the WCA.
- PE coated with THV, ZnO@THV, and CuO@THV NPs revealed WCAs of 160°, 169°, and 167°, respectively. After a dust storm, the samples were contaminated and lost their superhydrophobicity, and the WCA decreased to 110°.
- Textile was coated by dissolving THV (0.3-0.9 g, Dyneon) in 50 - 100 ml acetone THV polymer and the solution was sonicated in a sonication bath for 1 h at 30 °C.
- 50 ml acetone were used to dissolve the THV
- 50 ml of ethanol were added to the solution after completing the sonication bath.
- the solution was irradiated for 30 min with an ultrasonic corn (Ti horn, with booster 30% efficiency 750 W) in the presence of a piece of textile (cotton, nonwoven, polyester , a mixture of polyester/cotton).
- the sonication beaker was placed in a cooling bath, maintaining a constant temperature of 30 °C during the reaction.
- the textile was removed from the solution, washed with water and dried at room temperature for 0.5 h.
- a Layer-by-layer coating with metal oxides is applicable.
- the wettability of the textile coated with THV NPs sheets was evaluated by measuring the WCA. Water droplets (5 pL) were dripped carefully onto a piece of textile. The WCA was at least 140° (Fig. 7), demonstrating the superhydrophobicity of the coated textile.
- Fig. 8 shows selected time sequence images of water droplet (5 pL) falling on (A) untreated textile, and (B) textile coated with THV NPs, which was disposed in a sloping position.
- the water droplet rolls off the THV NP coated textile, while on the untreated textile the water gets absorbed in the fabric, again demonstrating superhydrophobicity of the coated textile.
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Abstract
The present invention relates to the sonochemical coating of various substrates such as polymers, textiles, glass etc. Specifically, the present invention relates to imparting superhydrophobic functionality to substrates by a sonochemical one-pot process for generation of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) nanoparticles (NPs) and their deposition on the substrate.
Description
Sonochemical Coating of Surfaces with Superhydrophobic Particles
Field of the Invention
The present invention relates to the sonochemical coating of substrates. More particularly, the present invention relates to imparting superhydrophobic functionality to substrates by a sonochemical method.
Background of the Invention
Superhydrophobic surfaces inspired by the lotus leaf exhibit a water contact angle (WCA) larger than 150° and excellent water repellence (W. Barthlott et al., Planta (1997), 202, 1-8). Generally, a water droplet on such surfaces tends to bounce and roll off without wetting or contaminating them. A superhydrophobic surface requires the combination of microscale and nanoscale hierarchical structures with low- surface-energy materials (see, R. N. Wenzel, Ind. Eng. Chem. (1936), 28, 988-994 and A. B. D. Cassie et al., Trans. Faraday Soc. (1944), 40, 546-551).
During the past decade, superhydrophobic surfaces have attracted much attention, due to their potential use in various applications, such as microfluidics, textile, oil- water separation, anti-corrosion coatings and more. Various strategies have been used to functionalize surfaces with hydrophobic properties, including lithographic processes, electrospinning, electrodeposition, sol-gel processes and layer-by-layer deposition. However, most of these techniques are costly, complicated and require several steps. In contrast, a sonochemical method is a low-cost, quick and simple technique for synthesizing nanometals, metal oxide, and organic and organo-metalic nanomaterials. During the sonochemical synthesis process, stable nanoparticles (NPs) are formed by the high energy released in the collapse of cavitation bubbles. This collapse creates a very high temperature and pressure that lead to the rupture of chemical bonds. According to the explanation proposed in the literature for the sonochemical coating process, microjets are formed upon the collapse of the acoustic bubbles. The microjets are directed toward the solid surface and move at a
sufficiently high speed (>500 m/s) to embed the newly-formed particles into the substrate (I. Perelshtein et al., Cellulose, (2013), 20, 1215-1221).
Fluorine-containing polymers are widely used to fabricate superhydrophobic surfaces as low-surface-energy materials. Tetrafluoroethylene-Hexafluoropropylene- Vinylidene Fluoride copolymer (THV), such as the commercial THV 220G sold by Dyneon LLC, U.S.A., is a partially-fluorinated thermoplastic polymer characterized by very low surface energy, a high hydrophobicity, good chemical resistance and a low processing temperature (for example, TM =165°C for THV 220G).
There are several reports on utilizing the THV polymer in microfluidics. For example, Begolo et al. (Lab on a Chip, (2001), 11, 508-512) assembled monolithic chips by hot embossing from THV plates. They demonstrated the transport of water droplets in fluorinated oil, and fluorescence detection of DNA within the droplets, without any measurable interaction between the droplets and the channel walls. In addition, these chips can resist harsh organic solvents. Perreard et al. (RSC Advances, (2015), 5, 11128-11131) produced surface modification of a microchannel of Dyneon THV by subjecting it to local electrochemical carbonization followed by the absorption of specific functions or bio-molecules. Rothmaier et al. (Sensors, (2008), 8, 4318-4329) developed pressure-sensitive textile prototypes, based on flexible optical-fiber technology, that were dip-coated using THV polymer material to prevent sticky behavior.
Therefore, it is an object of the present invention to provide a novel and simple process that involves the in-situ generation of THV nanoparticles under ultrasound irradiation and their subsequent deposition on various substrates, for example, polyethylene (PE) sheets, in a one-pot reaction. The as-obtained PE surface exhibits a WCA of 160° and excellent durability under outdoor conditions for two months, which is crucial for practical applications.
It is another object of the invention to provide a process in which an additional layer is deposited, consisting of either ZnO or CuO NPs, before the addition of THV NPs, in order to increase the surface roughness and further increase the hydrophobicity. This novel bilayer coating exhibits even wider high-contact angles (up to 169°).
It is a further object of the invention to apply such superhydrophobic surface nanofabrication to various surfaces, such as various polymers, textiles, paper, glass, ceramic bodies, and metal surfaces for creating a protective layer in a wide range of applications, such as touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
Other objects and advantages of the invention will become apparent as the description proceeds.
Summary of the Invention
In one embodiment of the invention, a sonochemical one-pot process for in-situ generation of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) nanoparticles (NPs) and their deposition on a substrate is provided. The process comprising:
- dissolving THV in a solvent;
- sonicating the solution;
- irradiating the solution with an ultrasonic corn in the presence of a polymer sheet, wherein the substrate is kept at a suitable distance from the sonicator tip during the entire reaction;
- placing the sonication beaker in a cooling bath, maintaining a constant temperature thereof during the reaction;
- removing the substrate from the solution, washing with water and drying.
Another embodiment of the invention provides a process as described above, wherein the resulting surface which exhibits superhydrophobic properties, wherein:
- the THV solvent is acetone and the concentration of the THV therein is 4 mg/ml;
- the THV solution is sonicated for about 1 h at a temperature of about 30°C;
- an equal amount of ethanol is added to the solution, to bring the THV to a final concentration to 2 mg/ml;
- the solution is irradiated for about 30 min with an ultrasonic corn in the presence of a polymer sheet;
- placing the sonication beaker in a cooling bath, maintaining a constant temperature of about 30 °C during the reaction;
- removing the substrate from the solution, washing with water and drying at room temperature.
Yet another embodiment of the invention provides a process as described above, wherein the substrate is kept at a constant distance of about 2 cm from the sonicator tip during the entire reaction.
One embodiment of the invention provides a sonochemical process for a layer-by- layer (SLBL) generation of a surface exhibiting improved superhydrophobic properties on a polymer sheet, comprising, prior to performing the process above- described process:
- dissolving a metal-acetate in double-distilled water (DDW);
- adding ethanol to the aqueous solution to a final volume ration of waterethanol of between 1:1 and 1:12;
- irradiating the solution with an ultrasonic horn in the presence of a polymer sheet, wherein the substrate is kept at a constant distance from the sonicator tip during the entire reaction;
- heating the solution to a temperature of between 30° - 60 °C, and adding ammonia drop-wise until a pH of about 8 is reached;
- placing the reaction beaker in a cooling bath, while maintaining a constant temperature of between 10° - 60 °C during the reaction;
- removing the substrate from the solution, washing with water and drying at room temperature to obtain a substrate coated with a metal-oxide layer; and
- depositing the THV NPs as a second layer on top of the metal-oxide layer.
Another embodiment of the invention provides a layer-by-layer process as described above, wherein the concentration of metal-acetate in double-distilled water (DDW) is 0.1 - 2 mg/ml
Yet another embodiment of the invention provides a layer-by-layer process as described above, wherein the metal-acetate is selected from zinc acetate [Zn(0Ac)2-2H20] or copper acetate [Cu(0Ac)2-H20].
According to some embodiments of the invention, the substrate for coating comprises or is made of a polymer, glass, paper, textile, wood, ceramic, fur, metal, carbon, a biopolymer and/or silicon. In some of these embodiments, the textile may be any one of cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene and spandex.
A further embodiment of the invention provides a process as described above, wherein the polymer is a polyethylene sheet.
One embodiment of the invention provides an article, manufactured according to the process as described above, having superhydrophobic functionality.
Another embodiment of the invention provides an article as described above for use in a device selected from touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
Brief Description of the Figures
Fig. 1 shows the HR-SEM images of (A) pristine PE, (B) PE coated with THV NPs, (C) PE coated with ZnO NPs and (D) PE coated with CuO NPs.
Fig. 2 shows the FTIR spectra of the pristine PE (purple line) and the THV-coated PE (red line).
Fig. B shows the atomic force microscopy (AFM) images of PE sheet: (A) pristine, (B) coated with THV NPs, (C) coated with ZnO@THV nanoparticles and (D) coated with CuO@THV NPs.
Fig. 4 shows the X-ray diffraction (XRD) pattern of (A) CuO NPs and (B) ZnO NPs.
Fig. 5 shows the water contact angle (WCA) measurements of (A) a pristine PE sheet, (B) a PE sheet coated with THV NPs, (C) a PE sheet coated with ZnO@THV NPs and (D) a PE sheet coated with CuO@THV NPs.
Fig. 6 demonstrates the transmittance in the visible region of uncoated PE bag (red line) and coated (grey line).
Fig. 7 shows the water contact angle (WCA) measurement of cotton coated with THV NPs.
Fig. 8 Selected time sequence images of water droplet falling on (a) untreated textile, and (b) textile coated with THV NPs. Arrows point to water droplet. Time (seconds) from shooting first image is indicated below images.
Detailed Description of the Invention
One embodiment of the present invention provides a sonochemical process for the in-situ generation of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) nanoparticles (NPs) and their subsequent deposition on a substrate in a one-pot reaction, comprising:
- dissolving THV in acetone at a concentration of between 0.1 to 10 mg/ml; - sonicating the solution for 1 h at low temperature, in the range of 10° - 40°C;
- adding an amount of ethanol to the solution, to bring the THV a final concentration of between 1 - 10 mg/ml; the volume ratio of acetone to ethanol is varied between 1:1 and 1:4.
- irradiating the solution for 3 to 60 min with an ultrasonic corn in the presence of a substrate, wherein the substrate is kept at a constant distance of between 0.8 and 4 cm from the sonicator tip during the entire reaction;
- after a period of time in the range 3 to 10 min, placing the sonication beaker in a cooling bath, maintaining a constant temperature of between 10° - 40 °C during the reaction;
- removing the substrate from the solution, washing with water and drying at room temperature.
Another embodiment of the present invention provides a sonochemical process for a layer-by-layer (SLBL) generation of a superhydrophobic surface on a substrate, comprising:
- dissolving a metal-acetate in double-distilled water (DDW) to a concentration of 1 - 10 mg/ml;
- adding ethanol to the aqueous solution to a final volume ration of waterethanol of between 1:1 and 1:12;
- irradiating the solution for a period of time between 3 and 60 min with an ultrasonic horn in the presence of a substrate, wherein the substrate is kept at a constant distance of between 0.8 and 4 cm from the sonicator tip during the entire reaction;
- heating the solution to a temperature between 30° - 60 °C, and adding ammonia drop-wise until a pH of about 8 is reached;
- placing the reaction beaker in a cooling bath, while maintaining a constant temperature of between 10° - 30 °C during the reaction;
- removing the substrate from the solution, washing with water and drying at about room temperature to obtain a substrate coated with a metal-oxide layer;
- depositing the THV NPs as a second layer on top of the metal-oxide layer, applying the same procedure as described above.
A further embodiment of the invention relates to a layer-by-layer (SLBL) generation of a superhydrophobic surface as described above, wherein the metal-acetate is selected from zinc acetate [Zn(0Ac)2-2H20] or copper acetate [Cu(0Ac)2-H20].
According to some embodiments of the present invention, the substrate may be a polymer, glass, paper, textile, wood, ceramic, fur, metal, carbon, a biopolymer and/or silicon, and the likes.
Thus, according to some embodiments, the substrate in any one of above- mentioned methods is a polymer, in some of these embodiments, the polymer is a polyethylene sheet.
In some other embodiments, the substrate may be a textile selected from: cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene and spandex.
Yet another embodiment of the present invention provides a process according to any one of above-mentioned methods for use in imparting a superhydrophobic functionality to a substrate.
In certain embodiments, any one of the above-mentioned processes is used in imparting a superhydrophobic functionality to touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
In some embodiments, the coated substrate is or forms a part of an article. Hence, according to an aspect of the invention, there is provided an article (e.g., an article-
of-manufacture) comprising a THV NPs coated substrate, as prepared by the processes described herein.
Some embodiments of the invention provide an article, generated according to the process as described above, having a superhydrophobic functionality.
In other embodiments the invention provides an article, generated according to the process described above, having a superhydrophobic functionality, for use in touch screens, medical devices, surgical swabs, textiles, polymeric surfaces, car interior and glasses.
Generally speaking, the present invention provides a sonochemical method for imparting superhydrophobicity to a substrate, such as a polyethylene (PE) sheet or any other suitable polymeric substrate. This is achieved by sonochemically depositing nanoparticles (NPs) of a THV hydrophobic polymer on the PE sheets. The NPs of THV are generated and deposited on the surface of the PE using ultrasound irradiation. Optimizing the process results in a homogeneous distribution of 110-200 nm THV NPs on the PE surface. The coated surface displays a water-contact angle of 140-160°, indicating an excellent superhydrophobicity. This superhydrophobic surface shows high stability under outdoor conditions for two months, which is essential for various applications. In addition, metal-oxide nanoparticles can be integrated into the THV coating to increase the surface roughness and, as a result, further improve the superhydrophobicity properties of the surface. The metal oxides are also deposited sonochemically.
The process of the present invention involves inexpensive precursors and is fast. The as-obtained functional PE with high superhydrophobicity can be used in a range of applications, such as electronic devices, medical equipment, hospital surfaces and more. Furthermore, this approach can be adapted to other surfaces, allowing sonochemical deposition of THV on other substrates and thus expanding the utilization of this methodology to additional applications.
As used herein, the term "THV" refers to a tetrafluoroethylene-hexafluoropropylene- vinylidene fluoride copolymer. These polymers are hydrophobic, flexible, transparent, partially-fluorinated thermoplastic polymers, characterized by very low surface energy, good chemical resistance and a low processing temperature. Non limiting examples of THV polymers used in the present invention are THV 220G (Dyneon 3M Co.), or other fluorine rich polymers.
As used herein, the term "polyethylene", or "PE" refers to any polymer having the chemical formula (C2H4)n, or a mixture of similar polymers of ethylene with various values of n. Said term may refer to, but not limited to, ultra-high-molecular-weight polyethylene (UHMWPE), ultra-low-molecular-weight polyethylene (ULMWPE or PE- WAX), high-molecular-weight polyethylene (HMWPE), high-density polyethylene (HDPE), high-density cross-linked polyethylene (HDXLPE), cross-linked polyethylene (PEX or XLPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and very-low-density polyethylene (VLDPE).
As used herein, the term "metal oxide" refers to a substance comprising one or more metal atoms and one or more oxygen atoms, wherein one or more of the metal atom(s) is in association with one or more oxygen atom(s). The metal oxides include, without limitation, oxides of alkali metals, alkaline earth metals, lanthanides, actinides, transition metals, metalloids, or any other metals. Non limiting examples of metal oxides of the present invention may include Ti02, MgO, ZrO, ZnO, CuO and Si02. In some embodiments of the invention, the metal oxide is ZnO or CuO.
As used herein, the term "sonochemistry" refers to a chemical reaction which is driven by an ultrasound irradiation in the 20-100 kHz range.
The term "superhydrophobic", as used herein, refers to surfaces which are highly hydrophobic, i.e., extremely difficult to wet. The term refers to surfaces having a contact angle of a water droplet exceed 150°.
As used herein, the term "textile" encompasses both natural and synthetic textiles, and refers to fabrics such as: cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene, spandex, and many more.
Examples
Chemicals and Materials
The THV which was used in the examples below is THV 220G, purchased from Dyneon 3M Co. Unless otherwise specified, all chemical reagents of chemical grade were purchased from Sigma-Aldrich, without further purification. All the experiments were conducted in the presence of a PE sheet.
Analytical Characterization
The particle morphology and size were characterized using high-resolution scanning electron microscopy (HR-SEM) with a Magellan, FEI microscope, at an accelerating voltage, over the range of 5-15 kV. The coated and uncoated PE sheets were further characterized by Fourier-transform infrared (FTIR) spectroscopy using Nicolet iSlO, performing 100 scans for each spectrum. The roughness of the coated and uncoated surfaces was determined by atomic force microscopy (AFM), using a Digital Instruments Nanoscope. The determination of the roughness factor (r) is based on the ratio of the calculated area, comprised of 3 points (X, Y, Z), versus the scanned area. The surface wettability of the superhydrophobic PE sheets was characterized using WCA measurements, with a Dataphysics OCA20 contact-angle system at ambient temperature. The ZnO and CuO content on the PE sheets was determined by inductively coupled plasma (ICP) using ULTIMA JY2501, after treating the sample
with 0.5 M of HN03. The X-ray diffraction (XRD) patterns of the product were measured using a Bruker D8 diffractometer (Karlsruhe, Germany) with Cu Ka radiation.
All the examples were prepared sonochemically in the presence of a substrate. In the first stage, the THV reaction parameters were varied to obtain the best conditions for coating. In the next step, improved superhydrophobicity functionality was imparted to the substrate by SLBL deposition, where the first layer is composed of metal-oxide NPs and the second is the THV polymer.
Examples 1 - 5: THV Polymer Coating
The THV (0.1 - 0.9 g, Dyneon) was dissolved in 50 - 100 ml acetone THV polymer and the solution was sonicated in a sonication bath for 1 h at 30 °C. In the case wherein 50 ml acetone were used to dissolve the THV, 50 ml of ethanol were added to the solution after completing the sonication bath. In the next stage, the solution was irradiated for 30 min with an ultrasonic corn (Ti horn, with booster 30% efficiency 750 W) in the presence of a PE sheet (2.5x3.5 cm2). Using a wire, the PE sheet was kept at a constant distance of 2 cm from the sonicator tip during the entire reaction. After 10 min, the sonication beaker was placed in a cooling bath, maintaining a constant temperature of 30 °C during the reaction. At the end of the sonication, the PE sheet was removed from the solution, washed with water and dried at room temperature for 0.5 h.
One of the goals of this embodiment of the invention is to provide a homogeneous, uniform coating of THV NPs on the surface of PE that exhibits a large WCA. The amount of THV and the type of solvent were found to be critical parameters in obtaining a coating with good superhydrophobic properties. According to the manufacturer (3M) of the THV polymer, it does not dissolve in most of the common solvents, but does dissolve in acetone. The first coating was prepared from an acetone solution of THV (Ex. 1). Almost no coating was observed across the sample, resulting in a low contact angle of 110°. The contact angle of the bare surface was
100°. Then, an anti-solvent (ethanol) was mixed with the acetone (1:1 ratio) and the deposition of the THV was carried out using this mixture, in an attempt to increase the amount deposited on the PE (Ex. 2-5). The different compositions used for the coating and the measured WCA are presented in Table 1.
Table 1: Optimization of the THV coating process
Ex. Amount of THV (g/100 ml) Solvent (100 ml) Contact angle
T 0.2 100 acetone 110
2 0.1 50:50 acetone:ethanol 135°
3 0.15 50:50 acetone:ethanol 145°
4 0.2 50:50 acetone:ethanol 160°
5 0.3 50:50 acetone:ethanol 147
The results indicate that the contact angle of the product depends on the amount of THV polymer in the starting solution. Table 1 indicates that a maximal contact angle is obtained when 0.2 g of THV is dissolved in 100 ml of the mixed solvent. For solutions with smaller amounts of THV polymer (Ex. 2 and 3), homogeneous coating is obtained; however, lower WCA values are measured. A smaller WCA is also obtained upon increasing the concentration of THV in the solution, as in Ex. 5. This is attributed to the non-homogeneous layer, exposing less fluorine atoms to water.
The results also indicate that 0.2 g of THV polymer in 50ml:50ml acetone:ethanol mixture (Ex. 4) is the optimal amount for achieving a homogeneous uniform coating and a high WCA. However, excellent results, particularly when combined with a first metal-oxide layer, can be achieved using different concentrations and solvent and they are therefore also one of the important objects of the invention. Therefore, further analysis and characterization were performed for this sample. As mentioned above, superhydrophobicity is governed by both the chemical composition and geometrical structure of the solid surface. Here, the combination of a rough spherical surface of THV NPs and the hydrophobic nature of the polymer resulted in high superhydrophobicity of the surface.
These results clearly demonstrate the unpredicted crucial role of ethanol in this process as a non-solvent (i.e., the precipitator). Ethanol decreases the solubility of the THV polymer in the mixture, resulting in the precipitation of the particles, which are thrown onto the PE surface by the microjets formed after the collapse of the acoustic bubble.
Example 6: Sonochemical Layer-by-Layer THV@ZnO and THV@CuO Coating
A sample of 0.02 g of either zinc acetate [Zn(0Ac)2-2H20] or copper acetate [Cu(OAc) 2-H20] was dissolved in 10 ml of double-distilled water (DDW), and 90 ml of ethanol were added to the aqueous solution. In the next stage, the solution was irradiated for 30 min with an ultrasonic horn (Ti horn, with booster 30% efficiency, 750 W) in the presence of a PE sheet, at the same position described above. The solution was heated to 60 °C, and 0.5 ml of ammonia (28% wt) was added drop-wise until a pH of 8 was reached. The beaker was placed in a cooling bath, while maintaining a constant temperature of 30 °C during the reaction. At the end of the sonication, the PE sheet was removed from the solution, washed with water and dried at room temperature for 0.5 h. The THV NPs were deposited as a second layer on top of the metal-oxide layer, applying the same procedure as described in Ex. 4.
As explained above, one object of the present invention is to impart superhydrophobicity in a one-pot sonochemical coating process. However, when the THV and metal oxide were deposited in one-pot reaction, the amount of THV attached to the surface was too low and the recorded WCA was only 112°.
Therefore, a Sonochemical Layer-by-Layer (SLBL) coating was used, where the first layer is composed of metal-oxide NPs and the second layer of THV NPs. The layer composed of metal-oxide nanoparticles increased the surface roughness, and the THV-NP layer decreased the surface free energy, consequently increasing the WCA. The as-obtained SLBL coating exhibits a WCA of 169° and generates a homogeneous coating covering the PE surface. The content of CuO and ZnO deposited on the PE
sheets was evaluated by inductively coupled plasma (ICP) analysis and found to be 0.036 and 0.042 wt%, respectively. To prepare the sample for ICP, the metal oxide was dissolved in 0.5 M HN03 and the ion content was probed.
Structure and Morphology
To show the shape and size of the THV NPs on the PE surface, the uncoated and coated sheets were characterized by HR-SEM. The uncoated PE surface is plain and smooth (Fig. 1A). Fig. IB shows a rough coating of THV-polymer NPs. The PE surface is homogeneously covered by the THV polymer with nanoscale grains. The particle size of the THV NPs is between 100 and 200 nm. As mentioned above, the pre-layer coating is composed of metal-oxide NPs, which were also examined by HR-SEM (Figs. 1C and ID). It is clear that the surface is coated with ZnO and CuO NPs, which are further covered by a layer of THV NPs. The particle size of the ZnO is in the range of 110-170 nm, while the size of the CuO NPs is ~50 nm.
To further verify that the PE sheet was covered with THV-polymer NPs, the FTIR spectra of pristine PE and THV-coated PE were recorded (Fig. 2). Both spectra show the characteristic bands of PE. In Fig. 2, following the coating process (red line), a new peak at 1,189 cm 1 is observed, which is attributed to C-F stretching vibrations.
One of the parameters that influence the superhydrophobicity of the surface is its roughness. Therefore, AFM measurements were carried out in order to study the surface roughness (Fig. 3). The root-mean-square roughness (Rq) of the uncoated PE surface is 8.95 nm (Fig. 3A), while that of the THV-coated PE sheet is 15.8 nm (Fig. 3B), indicating that the surface roughness increases after coating with THV NPs. When the metal-oxide layer was deposited before the THV layer, the Rq value increased significantly, reaching 110 and 116 nm for ZnO@THV and CuO@THV, respectively (Figs. 3C and 3D). The hierarchical structure of the metal-oxide NPs increases the surface roughness dramatically, which can explain the observed improvement in the WCA.
The crystallinity of the sonochemically-prepared CuO and ZnO was examined by XRD (Fig. 4). The XRD pattern of the sonochemically-prepared ZnO NPs is shown in Fig. 4A and it is indeed crystalline. The diffraction peaks match the hexagonal phase of ZnO (PDF: 89-7102) very well. The 2ϋ peaks appear at 31.77, 34.42, 36.25, 47.54, 56.6, 62.85 and 67.95° and are assigned to the (100), (002), (101), (102), (110), (103) and (112) reflection planes of the hexagonal ZnO particles, respectively. No peaks characteristic of any impurities were detected.
The XRD patterns of the sonochemically-prepared CuO NPs are shown in Fig. 4B. Similarly to ZnO, the copper oxide is crystalline, and the diffraction peaks match the PDF file 80-1916. The peaks appear at 2ϋ = 32.47, 35.49, 38.68, 48.65, 58.25 and 61.45, and are assigned to the (110), (-111), (111), (-202), (202) and (-113) reflection planes of the monoclinic CuO particles, respectively. No characteristic peaks of any impurities were detected.
Contact-Angle Measurements, Durability
The wettability of the PE-coated sheets was evaluated by measuring the WCA. Water droplets (5.0 pL) were dripped carefully onto the coating films. The contact angle value was obtained by measuring five different positions of the same sample (Fig. 5). The pristine PE surface exhibits a WCA of 100° (Fig. 5A). After coating with THV NPs, the WCA increases to 160° (Fig. 5B), demonstrating the superhydrophobicity of the coated PE. The integration of a pre-layer of either ZnO or CuO NPs increases the roughness of the PE surface, resulting in a higher WCA of 169° (Figs. 5C and 5D).
For practical applications, the superhydrophobic surface must be durable under outdoor conditions such as scorching sun and heavy rain. In order to examine the durability of the THV-, ZnO@THV- and CuO@THV-NP-coated PE sheets under outdoor conditions in a realistic environment, the following experiment was carried out. The samples were placed on the roof of a building, exposed to harsh conditions (rain, low temperature, sun, wind, dust, etc.). The experiments were conducted during December and January with an average temperature of 18 °C and an average
relative humidity of 50%. The average amount of precipitation during the experiment period was IBB mm. After two months, no visual change was observed, and there was almost no change in the WCA. PE coated with THV, ZnO@THV, and CuO@THV NPs revealed WCAs of 160°, 169°, and 167°, respectively. After a dust storm, the samples were contaminated and lost their superhydrophobicity, and the WCA decreased to 110°.
Transparency
Another important factor in the implementation of superhydrophobic coating is its ability to restore the transparency of the bare surface. To verify this, a transparency test was carried out. The test was performed with a coated PE bag, since the PE sheets that were used in the experiment were not transparent. Compared to the unmodified PE bag (red line), the THV NP-coated bag (grey line) showed 97% transmittance in the visible region (Fig. 6).
Example 7: THV Textile Coating
Textile was coated by dissolving THV (0.3-0.9 g, Dyneon) in 50 - 100 ml acetone THV polymer and the solution was sonicated in a sonication bath for 1 h at 30 °C. In the case wherein 50 ml acetone were used to dissolve the THV, 50 ml of ethanol were added to the solution after completing the sonication bath. In the next stage, the solution was irradiated for 30 min with an ultrasonic corn (Ti horn, with booster 30% efficiency 750 W) in the presence of a piece of textile (cotton, nonwoven, polyester , a mixture of polyester/cotton). After 10 min, the sonication beaker was placed in a cooling bath, maintaining a constant temperature of 30 °C during the reaction. At the end of the sonication, the textile was removed from the solution, washed with water and dried at room temperature for 0.5 h.
In textiles, as well as in polymers, a Layer-by-layer coating with metal oxides is applicable.
The wettability of the textile coated with THV NPs sheets was evaluated by measuring the WCA. Water droplets (5 pL) were dripped carefully onto a piece of textile. The WCA was at least 140° (Fig. 7), demonstrating the superhydrophobicity of the coated textile.
Fig. 8 shows selected time sequence images of water droplet (5 pL) falling on (A) untreated textile, and (B) textile coated with THV NPs, which was disposed in a sloping position. The water droplet rolls off the THV NP coated textile, while on the untreated textile the water gets absorbed in the fabric, again demonstrating superhydrophobicity of the coated textile.
Although embodiments of the invention have been described by way of illustration, it will be understood that the invention may be carried out with many variations, modifications, and adaptations, without exceeding the scope of the claims.
Claims
1. A sonochemical one-pot process for in-situ generation of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) nanoparticles (NPs) and their deposition on a substrate, comprising:
- dissolving THV in a solvent;
- sonicating the solution;
- irradiating the solution with an ultrasonic corn in the presence of a substrate, wherein the substrate is kept at a suitable distance from the sonicator tip during the entire reaction;
- placing the sonication beaker in a cooling bath, maintaining a constant temperature thereof during the reaction;
- removing the substrate from the solution, washing with water and drying.
2. A process according to claim 1, wherein the resulting surface which exhibits superhydrophobic properties, wherein:
- the THV solvent is acetone and the concentration of the THV therein is 4 mg/ml;
- the THV solution is sonicated for about 1 h at a temperature of about 30°C;
- an equal amount of ethanol is added to the solution, to bring the THV to a final concentration to 2 mg/ml;
- the solution is irradiated for about 30 min with an ultrasonic corn in the presence of a substrate;
- placing the sonication beaker in a cooling bath, maintaining a constant temperature of about 30 °C during the reaction;
- removing the substrate from the solution, washing with water and drying at room temperature.
3. A process according to claim 2, wherein the substrate is kept at a constant distance of about 2 cm from the sonicator tip during the entire reaction.
4. A process according to claim 1, wherein said substrate comprises or is made of a polymer, glass, paper, textile, wood, ceramic, fur, metal, carbon, a biopolymer and/or silicon.
5. A process according to claim 4, wherein the polymer is a polyethylene sheet.
6. A process according to claim 4, wherein the textile is selected from cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene and spandex.
7. An article, manufactured according to the process of claim 1, having superhydrophobic functionality.
8. An article according to claim 7, for use in touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
9. A sonochemical process for a layer-by-layer (SLBL) generation of a surface exhibiting improved superhydrophobic properties on a substrate, comprising, prior to performing the process of claim 1:
- dissolving a metal-acetate in double-distilled water (DDW);
- adding ethanol to the aqueous solution to a final volume ration of waterethanol of between 1:1 and 1:12;
- irradiating the solution with an ultrasonic horn in the presence of a polymer sheet, wherein the substrate is kept at a constant distance from the sonicator tip during the entire reaction;
- heating the solution to a temperature of between 30° - 60 °C, and adding ammonia drop-wise until a pH of about 8 is reached;
- placing the reaction beaker in a cooling bath, while maintaining a constant temperature of between 10° - 60 °C during the reaction;
- removing the substrate from the solution, washing with water and drying at room temperature to obtain a substrate coated with a metal-oxide layer; and
- depositing the THV NPs as a second layer on top of the metal-oxide layer.
10. A process according to claim 9, wherein the concentration of metal-acetate in double-distilled water (DDW) is 0.1 - 2 mg/ml.
11. A process according to claim 9, wherein the metal-acetate is selected from zinc acetate [Zn(0Ac)2-2H20] or copper acetate [Cu(0Ac)2-H20].
12. A process according to claim 9, wherein said substrate comprises or is made of a polymer, glass, paper, textile, wood, ceramic, fur, metal, carbon, a biopolymer and/or silicon.
IB. A process according to claim 12, wherein the polymer is a polyethylene sheet.
14. A process according to claim 12, wherein the textile is selected from cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene and spandex.
15. An article, manufactured according to the process of claim 9, having superhydrophobic functionality.
16. An article according to claim 15, for use in touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
-19-
1. A sonochemical one-pot process for in-situ generation of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) nanoparticles (NPs) and their deposition on a substrate, comprising:
- dissolving THV in a solvent;
- sonicating the solution;
- irradiating the solution with an ultrasonic corn in the presence of a substrate, wherein the substrate is kept at a suitable distance from the sonicator tip during the entire reaction;
- placing the sonication beaker in a cooling bath, maintaining a constant temperature thereof during the reaction;
- removing the substrate from the solution, washing with water and drying.
2. A process according to claim 1, wherein the resulting surface which exhibits superhydrophobic properties, wherein:
- the THV solvent is acetone and the concentration of the THV therein is 4 mg/ml;
- the THV solution is sonicated for about 1 h at a temperature of about 30°C;
- an equal amount of ethanol is added to the solution, to bring the THV to a final concentration to 2 mg/ml;
- the solution is irradiated for about 30 min with an ultrasonic corn in the presence of a substrate;
- placing the sonication beaker in a cooling bath, maintaining a constant temperature of about 30 °C during the reaction;
- removing the substrate from the solution, washing with water and drying at room temperature.
3. A process according to claim 2, wherein the substrate is kept at a constant distance of about 2 cm from the sonicator tip during the entire reaction.
20
4. A process according to claim 1, wherein said substrate comprises or is made of a polymer, glass, paper, textile, wood, ceramic, fur, metal, carbon, a biopolymer and/or silicon.
5. A process according to claim 4, wherein the polymer is a polyethylene sheet.
6. A process according to claim 4, wherein the textile is selected from cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene and spandex.
7. An article, manufactured according to the process of claim 1, having superhydrophobic functionality.
8. An article according to claim 7, for use in touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
9. A sonochemical process for a layer-by-layer (SLBL) generation of a surface exhibiting improved superhydrophobic properties on a substrate, comprising, prior to performing the process of claim 1:
- dissolving a metal-acetate in double-distilled water (DDW);
- adding ethanol to the aqueous solution to a final volume ration of waterethanol of between 1:1 and 1:12;
- irradiating the solution with an ultrasonic horn in the presence of a polymer sheet, wherein the substrate is kept at a constant distance from the sonicator tip during the entire reaction;
- heating the solution to a temperature of between 30° - 60 °C, and adding ammonia drop-wise until a pH of about 8 is reached;
- placing the reaction beaker in a cooling bath, while maintaining a constant temperature of between 10° - 60 °C during the reaction;
21
- removing the substrate from the solution, washing with water and drying at room temperature to obtain a substrate coated with a metal-oxide layer; and
- depositing the THV NPs as a second layer on top of the metal-oxide layer.
10. A process according to claim 9, wherein the concentration of metal-acetate in double-distilled water (DDW) is 0.1 - 2 mg/ml.
11. A process according to claim 9, wherein the metal-acetate is selected from zinc acetate [Zn(0Ac)2-2H20] or copper acetate [Cu(0Ac)2-H20].
12. A process according to claim 9, wherein said substrate comprises or is made of a polymer, glass, paper, textile, wood, ceramic, fur, metal, carbon, a biopolymer and/or silicon.
IB. A process according to claim 12, wherein the polymer is a polyethylene sheet.
14. A process according to claim 12, wherein the textile is selected from cotton, polyester, lycra, wool, silk, canvas, suede/leather, corduroy, flannel, poplin, sailcloth, sateen, terry cloth, linen, fleece, nylon, microfiber, acetate, acrylic, rayon, poly blends, olefin, polypropylene and spandex.
15. An article, manufactured according to the process of claim 9, having superhydrophobic functionality.
16. An article according to claim 15, for use in touch screens, medical devices, surgical swabs, clothing textiles, polymeric surfaces, car interior and glasses.
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