EP3551779A1 - Verfahren zur beschichtung eines basiselements für eine haushaltsgerätekomponente sowie haushaltsgerätekomponente - Google Patents
Verfahren zur beschichtung eines basiselements für eine haushaltsgerätekomponente sowie haushaltsgerätekomponenteInfo
- Publication number
- EP3551779A1 EP3551779A1 EP17821732.9A EP17821732A EP3551779A1 EP 3551779 A1 EP3551779 A1 EP 3551779A1 EP 17821732 A EP17821732 A EP 17821732A EP 3551779 A1 EP3551779 A1 EP 3551779A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- base element
- household appliance
- fluorosilane
- silicon dioxide
- coating
- 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.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 37
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 15
- 238000002485 combustion reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 230000003075 superhydrophobic effect Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 150000001282 organosilanes Chemical class 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 5
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 4
- PISDRBMXQBSCIP-UHFFFAOYSA-N trichloro(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC[Si](Cl)(Cl)Cl PISDRBMXQBSCIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 description 39
- 230000002209 hydrophobic effect Effects 0.000 description 15
- 238000011161 development Methods 0.000 description 14
- 230000018109 developmental process Effects 0.000 description 14
- 230000008021 deposition Effects 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 150000004819 silanols Chemical class 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910007157 Si(OH)3 Inorganic materials 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012761 high-performance material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- SXYHZEQKWNODPB-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane;1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F.COC(F)(F)C(F)(C(F)(F)F)C(F)(F)F SXYHZEQKWNODPB-UHFFFAOYSA-N 0.000 description 1
- 241001365789 Oenanthe crocata Species 0.000 description 1
- 208000007400 Relapsing-Remitting Multiple Sclerosis Diseases 0.000 description 1
- 229910007159 Si(CH3)4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
- B05D5/086—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers having an anchoring layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/453—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
- B05D2203/35—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/60—Adding a layer before coating
- B05D2350/63—Adding a layer before coating ceramic layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
- B05D3/044—Pretreatment
Definitions
- the invention relates to a method for coating a base element for a household appliance component.
- the invention further relates to a household appliance component comprising a coated base element, and to a household appliance comprising said household appliance component.
- Hydrophobic surfaces are a topic of increasing importance in household appliances and are required in many applications.
- a hydrophobic surface property is especially useful if water or other hydrophilic substances are required to be kept away from certain surface areas. Examples comprise water repellent surfaces on cooktops, easy to clean surfaces, anti-fingerprint properties, and the prevention of water from conductive or capacitive areas.
- currently known coatings either exhibit rather low degrees of hydrophobicity or require complex and expensive materials and coating methods to achieve sufficiently large contact angles.
- a further task of the invention consists in providing a household appliance component comprising a base element with an inexpensive hydrophobic coating. Still further, it is an object of the current invention to provide a household appliance comprising at least one household appliance component with an inexpensive hydrophobic coating.
- a first aspect of the invention relates to a method for coating a base element for a household appliance component, comprising at least the steps of depositing at least one silicon dioxide containing layer onto at least one surface of the base element by combustion chemical vapour deposition and coating at least a portion of the at least one silicon dioxide layer using at least one fluorosilane.
- the method according to the invention allows the manufacturing of hydrophobic and even superhydrophobic surfaces through the combination of one or more silicon dioxide containing layers, which are deposited onto at least one surface of the base element by combustion chemical vapour deposition, and the subsequent coating of the silicon dioxide containing layer(s) using at least one fluorosilane as coating agent.
- the deposition by combustion chemical vapour deposition comprises the flame-pyrolytic deposition of (usually amorphous) silicon dioxide onto the base material to create a type of silicate coating.
- the surface to be treated is fed through a gas flame which is doped with a silicon-containing material, the so called pyrosil.
- the pyrosil burns in the flame and deposits as nanoparticles of silica on the surface in a firmly adhering coating. Due to the short flame-substrate interaction the material's surface temperature remains low.
- the first deposition step is suitable not only for base materials made of glass, ceramics, or metal but also for base materials made of plastics, wood, or other materials, so that any kind of household appliance component may be provided with a hydrophobic coating.
- Freshly deposited silica layers are highly reactive and thus serve as adhesion promoting layers for the following coating with fluorosilane. Adhesion can be further improved by application of additional silane-based adhesion promoters. Alternatively it may be provided that the layer consists of silicon oxide.
- the present invention is based on the insight that the deposition of said one or more silicon dioxide containing layer(s) increases significantly the hydrophobicity, effectiveness, and controllability of the subsequent coating step with one or more fluorosilanes. It may be provided that the resulting layer consists of said one or more fluorosilanes. Alternatively, the resulting layer may comprise or consist of reaction products of the fluorosilane(s) and/or contain one or more further components. This allows for a fast and easy manufacturing of coatings with a higher degree of hydrophobicity than conventional coatings. Still further, the necessary base materials, i.e.
- the silicon-containing precursor material and the fluorosilane are commercially available so that no expensive high performance materials are needed to achieve hydrophobic or even superhydrophobic surface properties with water contact angles of at least 150° or more. Both steps, i.e. the deposition and the coating step, may independently of each other generally be carried out once or multiple times to adjust the respective layer properties.
- the silicon dioxide contained layer it might be also used a titanium contained based layer.
- the base element is at least in portions cleaned and/or pretreated before depositing the at least one silicon dioxide containing layer. This improves the adherence of the deposited silicon oxide layer(s).
- the base element is cleaned by applying a cleaning medium and/or by ultrasonic cleaning and/or that the base element is pretreated by drying and/or ozone treatment.
- the base material may be cleaned with water and a detergent or with an alcohol such as ethanol or isopropanol.
- the base material may be immersed in water and treated with ultrasounds for up to several minutes, e. g. 10 minutes. This may be repeated several times with optional intermediate rinsing steps.
- the base material may be dried by heating and/or by applying compressed air.
- an ozone treatment removes residuals from the surface and improves the adherence of the silicon dioxide containing layer(s) especially in the case of glass surfaces and other surfaces with free OH groups.
- an organosilane precursor in particular tetraethoxysilane and/or tetramethylsilane, is used for depositing the at ntaining layer.
- Tetraethoxysilane has the chemical formula (I)
- the base element at least two layers of silicon dioxide are deposited on the base element.
- the deposited silicon dioxide has an aggregated particle size of between 25 nm and 300 nm, for example 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, 1 10 nm, 1 15 nm, 120 nm, 125 nm, 130 nm, 135 nm, 140 nm, 145 nm, 150 nm, 155 nm, 160 nm, 165 nm, 170 nm, 175 nm, 180 nm, 185 nm, 190 nm, 195 nm,
- 1 H,1 H,2H,2H- perfluorooctyltriethoxysilane and/or trichloro(1 H,1 H,2H,2H-perfluorooctyl)silane is used as said fluorosilane.
- 1 H,1 H,2H,2H-perfluorooctyltriethoxysilane (PFOTESi) has the chemical formula (III)
- PFOTCSi perfluorooctyl)silane
- Both substances exhibit excellent hydrophobic properties in combination with the one or more silicon dioxide containing layer(s) due to their extreme low surface energy and the fast and easy reaction of their silane groups with hydroxyl groups of the silicon dioxide containing layer(s).
- the base element is coated with said at least one layer of fluorosilane by immersing at least a part of the base element one or multiple times for a predetermined time in a coating agent comprising said at least one fluorosilane.
- This so called dip coating step allows for a fast and easy coating of large base materials and of base materials with complex geometries. This step may of course be repeated once or multiple times with the same or different coating agents, allowing a series of thin layers to bulk up to a relatively thick final layer system.
- a concentration of the at least one fluorosilane in the coating agent is between 0.5 vol% and 50 vol%, for example 0,5 vol%, 0,6 vol%, 0,7 vol%, 0,8 vol%, 0,9 vol%, 1 ,0 vol%, 2 vol%, 3 vol%, 4 vol%, 5 vol%, 6 vol%, 7 vol%, 8 vol%, 9 vol%, 10 vol%, 1 1 vol%, 12 vol%, 13 vol%, 14 vol%, 15 vol%, 16 vol%, 17 vol%, 18 vol%, 19 vol%, 20 vol%, 21 vol%, 22 vol%, 23 vol%, 24 vol%, 25 vol%, 26 vol%, 27 vol%, 28 vol%, 29 vol%, 30 vol%, 31 vol%, 32 vol%, 33 vol%, 34 vol%, 35 vol%, 36 vol%, 37 vol%, 38 vol%, 39 vol%, 40 vol%, 41 vol%, 42 vol%, 43 vol%, 44 vol%, 45 vol%, 46 vol%
- the coating agent contains a solvent, in particular a fluorinated solvent, to dilute the fluorosilane as needed.
- the solvent may be or comprise for example methoxyperfluorobutane (HFE-7100).
- the predetermined time is between 10 seconds and 120 minutes, for example 10 s, 15 s, 20 s, 25 s, 30 s, 35 s, 40 s, 45 s, 50 s, 55 s, 60 s, 2 min, 4 min, 6 min, 8 min, 10 min, 12 min, 14 min, 16 min, 18 min, 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, 32 min, 34 min, 36 min, 38 min, 40 min, 42 min, 44 min, 46 min, 48 min, 50 min, 52 min, 54 min, 56 min, 58 min, 60 min, 62 min, 64 min, 66 min, 68 min, 70 min, 72 min, 74 min, 76 min, 78 min, 80 min, 82 min, 84 min, 86 min, 88 min, 90 min, 92 min, 94 min, 96 min, 98 min, 100 min, 102 min, 104 min, 106 min, 108 min, 1 10 min, 1 12 min,
- the base element is coated by chemical vapor deposition using said at least one fluorosilane.
- the base element which is already provided with the deposited silicon dioxide containing layer(s)
- the base element is exposed to one or more volatile fluorosilanes, which react and/or decompose on the substrate surface to produce the hydrophobic top layer.
- the fluorosilane may for example be hydrolyzed, which leads to the formation of silanols that are further condensated, thereby creating hydrogen bridges with the molecules of their same species and/or with OH groups of the silicon dioxide containing layer.
- the fluorosilane(s) decomposes and becomes covalently linked to the silicon dioxide containing base layer, thus providing the base material with durable hydrophobic surface characteristics.
- the at least one fluorosilane is exposed to water, in particular to humid air. This promotes the hydrolyzation of the fluorosilane and thus the condensation reactions with the silicon dioxide containing layer.
- the base element is post-treated after the coating step. This allows the removal of water, solvents, or unreacted compounds and/or the curing of unreacted compounds in the layers.
- the post-treatment comprises thermal treating of the coated base element at a predetermined temperature for a predetermined time and/or cleaning of the coated base element.
- the base material may for example be heated for up to 10 minutes to temperatures between 100 °C and 120 °C (1 10 °C) in order to evaporate water and to promote the condensation of unreacted silanol groups.
- the post-treatment may also comprise the cleaning of the coated base element, for example with acetone, to remove silanes or other impurities.
- a second aspect of the invention relates to a household appliance component comprising a base element, wherein at least one surface of the base element is at least partly coated with at least one combustion chemical vapor deposited silicon dioxide containing layer and at least one layer, which is manufactured by coating at least a portion of the at least one silicon dioxide layer using at least one fluorosilane.
- the household appliance component according to the invention thus comprises one or more hydrophobic or even superhydrophobic surfaces through the combination of one or more silicon dioxide containing layers, which are deposited onto at least one surface of the base element by combustion chemical vapour deposition, and the subsequent coating of the silicon dioxide containing layer(s) using at least one fluorosilane as coating agent.
- the deposition by combustion chemical vapour deposition comprises the flame-pyrolytic deposition of (usually amorphous) silicon dioxide onto the base material to create a type of silicate coating.
- the surface to be treated is fed through a gas flame which is doped with a silicon-containing material, the so called pyrosil.
- the pyrosil burns in the flame and deposits as nanoparticles of silica on the surface in a firmly adhering coating. Due to the short flame- substrate interaction the material's surface temperature remains low.
- any kind of base material for example base materials made of glass, ceramics, or metal but also base materials made of plastics, wood, or other materials, may be provided with a hydrophobic coating.
- Freshly deposited silica layers are highly reactive and thus serve as adhesion promoting layers for the following coating with fluorosilane. Adhesion can be further improved by application of additional silane-based adhesion promoters. Alternatively it may be provided that the layer consists of silicon oxide. Further, the present invention is based on the insight that the deposition of said one or more silicon dioxide containing layer(s) increases significantly the hydrophobicity, effectiveness, and controllability of the subsequent coating step with one or more fluorosilanes. It may be provided that the resulting layer(s) consists of said one or more fluorosilanes. Alternatively, the resulting layer(s) may comprise or consist of reaction products of the fluorosilane(s) and/or contain one or more further components.
- the necessary base materials i.e. the silicon-containing precursor material and the fluorosilane
- the base material may generally comprise one or more silicon dioxide containing layers and one or more layers made from fluorosilane(s) to adjust the respective layer properties.
- the at least one coated surface of the base element is superhydrophobic.
- the term "hydrophobic” relates to coatings having water contact angles of 90° to 149° while the term “superhydrophobic” relates to coatings having water contact angles of more than 149° and preferably of 160° or more, for example 150 °, 151 °, 152 °, 153 °, 154 °, 155 °, 156 °, 157 °, 158 °, 159 °, 160 °, 161 °, 162 °, 163 °, 164 °, 165 °, 166 °, 167 °, 168 °, 169 °, 170 ° or more. This ensures surfaces that are extremely difficult to wet.
- a third aspect of the invention relates to a household appliance comprising at least one household appliance component with at least one base element, which is manufactured by a method according to the first aspect of the invention and/or at least one household appliance component according to the second aspect of the invention.
- the household appliance may be configured as a dishwasher, a dryer, a washing machine, a microwave oven, and/or a steam oven.
- Fig. 1 a schematic sectional view of a base element for a household appliance component, onto which a silicon dioxide layer is deposited by combustion chemical vapour deposition; and Fig. 2 a schematic sectional view of the base element, which is further coated using a fluorosilane.
- Fig. 1 shows a schematic sectional view of a base element 1 made of glass for a household appliance component.
- the base element 1 is cleaned with water and soap, immersed in a water bath and charged with ultrasound for approximately 10 minutes. After rinsing the base material 1 , it is immersed once again in clean water and charged with ultrasound for further 10 minutes.
- the next cleaning step comprises immersing the base material 1 in ethanol and charging it with ultrasound for further 10 minutes.
- the base material 1 is dried with compressed air.
- the base material 1 is treated with ozone to remove any organic residuals and to expose the OH groups of the glass material.
- the pyrosil is an organosilane precursor, which is injected into a flame (air+propane) in an amount sufficient to saturate the flame with the vapour of the organosilane.
- the pyrosil may for example be tetraethoxysilane (Si(OC 2 H 5 ) 4 ) or tetramethylsilane (Si(CH 3 ) 4 ).
- Other organosilanes may be used as well as pyrosil/precursor.
- the presently used system for depositing the pyrosil comprises an evaporator to create the organosilane vapour.
- air passes through the evaporator and is saturated by the organosilane vapour and mixed with propane for combustion.
- the parameters of the system are: temperature of organosilane in chamber is approximately 26
- silanol melcules undergo condensation reactions with other silanol molecules and the OH groups of the glass surface of the base element 1 whereby the silanol molceules are covalently bonded to the surface of the base element 1. Consequently, a highly hydrophilic base layer 2 of siloxane (Si0 2 ) with a nanoporous structure is formed, which is firmly adhering to the base element 1. This step of depositing a silicon dioxide containing layer 2 may be repeated once or several times.
- the amount of deposited Si0 2 is directly related to the number of passes or repeats.
- the key factor is not necessarily the number of passes but the amount of deposited pyrosil/Si0 2 .
- the number of passes and therefore the number of layers 2 depends on the subsequent purpose of the base element 1 , the desired properties of the layer(s) 2, and the system and parameters used to create the layer(s) 2.
- FESEM field emission scanning electron microscopy
- Fig. 2 shows a schematic sectional view of the base element 1 , which is further coated using a fluorosilane.
- the fluorosilane or fluorinated silane
- Two different fluorosilanes were deposited by using two different methods. Generally, both methods may be used alternatively or additionally, although the use of chemical vapour deposition (CVD) is usually preferred.
- the base material 1 was immersed in 1 H, 1 H,2H,2H-perfluorooctyltriethoxysilane (PFOTESi) containing solutions with different concentrations (1 vol%, 5 vol%, and 10 vol% in a fluorinated solvent (HFE-7100)) for different times (10 or 60 minutes). Thereby, one or more superhydrophobic top layer(s) 3 with different thicknesses is/are formed.
- PFOTESi perfluorooctyltriethoxysilane
- the base material 2 is placed in a dissecator with 10 drops of trichloro(1 H, 1 H,2H,2H- perfluorooctyl)silane (PFOTCSi) during 1 hour under a vacuum of approximately 100 mbar. Due to the reaction of PFOTCSi with the humidity of the remaining atmosphere, the fluorosilane is hydrolyzed, thereby forming silanols that undergo subsequent condensation reactions with other silanol molecules and free OH groups of the Si0 2 layer 2. The fluorosilane is thus covalently linked to the amorphous Si0 2 layer 2 previously produced by the pyrosil reaction and forms a superhydrophobic top layer 3.
- the fluorosilane layer 3 is a thin layer that follows the topography of the pyrosil granulate layer 2.
- the coated base material 1 is heated up to approximately 1 10 °C for about 10 minutes to promote the evaporation of water and the condensation of unreacted silanol groups. Finally, the base material 1 is cleaned with acetone in order to eliminate any unreacted silanes, silanols, or other compounds.
- the topography of the resulting layers 2, 3 can be analyzed by atomic/scanning force microscopy (AFM) in order to determine the size of the Si0 2 particles and to determine the roughness of layer 2 or layer 3.
- AFM atomic/scanning force microscopy
- Table 1 the quadratic average roughness values RRMS of the coated base material 1 are shown. It can be seen that the roughness of the surface increases with the number of passes of pyrosil depositions. For 4 passes of pyrosil depositions, the roughness is about 5 times bigger compared to 1 pass.
- Table 1 root mean squared roughness depending on the passes of pyrosil depositions
- the roughness of the surface is related to the amount and size of the Si0 2 particles and thus to the water contact angle and the wettability of the surface.
- the use of the controlled pyrosil deposition(s) by varying the number of passes and thus the amount of pyrosil/Si0 2 and the size and surface concentration of grains and roughness not only improves the adherence of the subsequent layer 3 but also leads to highly hydrophobic, even superhydrophbic surface properties. This effect is maximized if 3-4 passes of pyrosil are deposited and/or if the aggregated particles size of the desposited Si0 2 is approximately 100 nm to 200 nm and if the quadratic average roughness value R RM s is between approximately 50 nm and 80 nm.
- angle (°) adheres to adheres to surface with varying
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Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201631572 | 2016-12-12 | ||
| ES201631638A ES2673370B1 (es) | 2016-12-21 | 2016-12-21 | Método para recubrir un elemento base para un componente de aparato doméstico, y componente de aparato doméstico |
| PCT/IB2017/057684 WO2018109619A1 (en) | 2016-12-12 | 2017-12-06 | Method for coating a base element for a household appliance component and household appliance component |
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| Publication Number | Publication Date |
|---|---|
| EP3551779A1 true EP3551779A1 (de) | 2019-10-16 |
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| EP17821732.9A Pending EP3551779A1 (de) | 2016-12-12 | 2017-12-06 | Verfahren zur beschichtung eines basiselements für eine haushaltsgerätekomponente sowie haushaltsgerätekomponente |
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| Country | Link |
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| EP (1) | EP3551779A1 (de) |
| CN (1) | CN110050087A (de) |
| WO (1) | WO2018109619A1 (de) |
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| EP3628918B1 (de) * | 2018-09-27 | 2025-01-22 | BSH Hausgeräte GmbH | Verfahren zur herstellung einer optischen vorrichtung für ein haushaltsgerät und optische vorrichtung |
| CN112853313A (zh) * | 2019-11-28 | 2021-05-28 | 康宁股份有限公司 | 耐久的高接触角易清洁涂层 |
| DE102020101797A1 (de) | 2020-01-27 | 2021-07-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Verbund mit Barrierefunktion, dessen Herstellung und Verwendung |
| CN116496646B (zh) * | 2022-01-18 | 2024-12-27 | 苏州大学 | 一种超疏水光热涂层、其制备方法和应用 |
| WO2025137216A1 (en) * | 2023-12-19 | 2025-06-26 | Novelis Inc. | High magnesium content aluminum alloy products including oxide coating for controlled atmosphere brazing |
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| FR2866643B1 (fr) * | 2004-02-24 | 2006-05-26 | Saint Gobain | Substrat, notamment verrier, a surface hydrophobe, avec une durabilite amelioree des proprietes hydrophobes |
| FR2902422B1 (fr) * | 2006-06-16 | 2008-07-25 | Saint Gobain | Procede de depot par plasma atmopherique d'un revetement hydrophobe/oleophobe a durabilite amelioree |
| US8734929B2 (en) * | 2008-08-25 | 2014-05-27 | Snu R&Db Foundation | Hydrophobic composites and methods of making the same |
| US20120107558A1 (en) * | 2010-11-01 | 2012-05-03 | Shari Elizabeth Koval | Transparent substrate having durable hydrophobic/oleophobic surface |
| KR101359259B1 (ko) * | 2011-12-27 | 2014-02-06 | 주식회사 포스코 | 내흑변성 및 밀착력이 우수한 Zn-Mg 합금 코팅강판 및 그 제조방법 |
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| WO2018109619A1 (en) | 2018-06-21 |
| CN110050087A (zh) | 2019-07-23 |
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