EP2308607B1 - Coating structure - Google Patents
Coating structure Download PDFInfo
- Publication number
- EP2308607B1 EP2308607B1 EP10187278.6A EP10187278A EP2308607B1 EP 2308607 B1 EP2308607 B1 EP 2308607B1 EP 10187278 A EP10187278 A EP 10187278A EP 2308607 B1 EP2308607 B1 EP 2308607B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- microstructured
- fluoropolymer
- substrate
- subsurface
- 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.)
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- 238000000576 coating method Methods 0.000 title claims description 44
- 239000011248 coating agent Substances 0.000 title claims description 39
- 239000000758 substrate Substances 0.000 claims description 55
- 229920002313 fluoropolymer Polymers 0.000 claims description 45
- 239000004811 fluoropolymer Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 6
- 238000010285 flame spraying Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000010954 inorganic particle Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 239000011146 organic particle Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 238000007751 thermal spraying Methods 0.000 claims description 3
- 230000000181 anti-adherent effect Effects 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 239000011224 oxide ceramic Substances 0.000 claims description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 95
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 16
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 9
- 240000002853 Nelumbo nucifera Species 0.000 description 9
- 229920009441 perflouroethylene propylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000010431 corundum Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000005488 sandblasting Methods 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- -1 for example Polymers 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical compound FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 241001422033 Thestylus Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005493 condensed matter Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
- B05D5/02—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a matt or rough surface
-
- 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
- B05D2350/30—Change of the surface
- B05D2350/33—Roughening
- B05D2350/38—Roughening by mechanical means
-
- 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
- B05D2350/65—Adding a layer before coating metal 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
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
-
- 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
- B05D2602/00—Organic fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the invention relates to a non-stick coating for a surface of a substrate containing at least one fluoropolymer and to a process for its preparation.
- a non-stick coating is to be understood as meaning a layer structure which is such that it is particularly suitable, in particular, for rolls or other machine parts in the adhesive, rubber and / or paint-processing industry.
- Good non-stick properties are particularly relevant where certain areas, such as labels, adhesive tapes, diapers and other products, are said to have the property of preventing adhesion of adhesive or other sticky media. This allows targeted adhesive areas to be created while the neighboring areas can not stick. That is, the adhesive or other sticky media can be applied by machine targeted and localized.
- the corresponding coated tools such as rolls in the paper industry for producing multilayer or laminated paper remain adhesive-free.
- the silicone-coated surfaces in this way have no resistance to solvents and corrosion. Furthermore, these surfaces are not approved for food applications. Finally, due to the material properties of the silicone, a corresponding surface is also out of the question for some applications. In coating applications (eg in car painting) such a coated surface is unsuitable because the paint is repelled by the silicone and so it comes to the formation of so-called "fish eyes". The disadvantage is finally that the hardness of the surface is relatively low.
- fluoroplastics for example Teflon
- Teflon fluoroplastics
- the fluoroplastic is sintered on a carrier layer at elevated temperatures (about 400 ° C) in order to obtain a stable composite. Due to the flow of the fluoropolymer in the course of the sintering process, however, the basic structure of the substrate is leveled; a lotus effect can not be obtained in this way.
- EP 0 485 801 B1 discloses a heat exchanger having a plurality of plate-shaped ribs. On the fin surface is applied a mixture consisting of a silicone resin compound-containing solution and finely divided inorganic particles. Silicon is used as base layer. Furthermore, it is provided that the surface of the layer has regularly distributed micro-elevations.
- the DE 35 44 211 A1 discloses a method of making an iron sole. As a result of the sequence of different method steps, a metallic carrier substrate is provided with a low-adhesion plastic surface which is as smooth as possible and sealed. For sealing a binder of organic type is used.
- an article which consists of metal, ceramic, enamel or glass and which is provided with an at least single-layer coating, the inorganic and / or organic pigment, fluoropolymer and as binder resin at least one of the type of polyamide-imides, polyimides, polyetherimides and similar substances having.
- the specification of the coating is predetermined both with regard to the amounts of the constituents and with regard to their particle size.
- a method is known in which a layer of a plastic material is applied to a substrate with a structured surface, wherein the surface of the layer is provided with a plurality of substantially regularly distributed micro-bumps by the plastic material before application to the substrate components in an amount of 10 to 30 wt .-% and a particle size of 2 to 200 microns are added.
- a water contact angle of 128 ° is given.
- the WO 2008/035347 A2 discloses a process for coating a substrate wherein a surface structure having superhydrophobic properties is formed with polymeric material consisting of particles of different sizes.
- the polymer material contains PVDF or PTFE with particle sizes of 0.1 - 2 ⁇ m and a polycarbonate-based polymer with particle sizes of 2 - 20 ⁇ m.
- a solvent is used to dissolve the polycarbonate-based polymer and into which the fluoropolymer particles are mixed.
- a structure is impressed in which the average distance of notches generated is 20-200 microns.
- Substrates here and below are understood in particular to be those which at least partially consist of metal, ceramic, glass, enamel or a composite material thereof, but also those of other suitable materials. Materials are particularly suitable as part of a substrate, provided that they are sufficiently thermally stable at temperatures that occur in an optionally provided sintering process.
- An anti-adhesive plastic is understood here and below as meaning in particular a fluoropolymer such as, for example, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene-propylene copolymer (FEP), but also other suitable materials which contain perfluorinated carbon chains and have comparable hydrophobic properties.
- a fluoropolymer such as, for example, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene-propylene copolymer (FEP), but also other suitable materials which contain perfluorinated carbon chains and have comparable hydrophobic properties.
- a microstructured substrate is understood here and below to mean one having a roughness in the micrometer range, in particular in the range from 2 to 50 ⁇ m Ra.
- the substrate may be formed by the substrate itself, but also by a layer applied or applied to the substrate.
- a hierarchical layer structure is understood to be one in which a second surface structure of a second layer is superimposed on a first layer having a first surface structure, without the first surface structure being leveled out in the process.
- a first microstructured layer of the hierarchical layer structure is understood to be one with micro-elevations in the range of 2 to 50 ⁇ m, under a submicrostructured second layer, which overlays the first one, with elevations, in particular in a range of 0.1 to 5 ⁇ m, of which Elevations are smaller than the elevations of the first microstructured layer.
- PPSO 2 polyphenylene sulfone
- SiC silicon carbide
- Water contact angle of> 165 ° with a hysteresis and a drain angle, which go to 0, are possible with the non-stick coating according to the invention. This is how the pull-off force of a Tesa® - Tapes of a surface coated with the non-stick coating according to the invention go to zero.
- the microstructured substrate is preferably produced by applying a microstructured layer to a macrostructured surface.
- the surface of the substrate may already have a macrostructure of its own if it has a corresponding roughness.
- the macrostructure can also be predetermined by the nature of the substrate, as for example in the case of a fine wire mesh. It is also possible to produce a suitable macrostructure of the substrate surface, for example by sand blasting or else by placing and fastening a macrostructured grid fabric.
- a macrostructured surface can be produced by thermal spraying of a macrostructured layer onto the substrate, in particular by flame spraying of a metal wire or metal powder such as chromium / nickel wire or molten chromium / nickel powder.
- the microstructured layer of the microstructured substrate is preferably formed on the macrostructured surface by application of oxide ceramics, in particular titanium oxide (TiO 2 ) and / or aluminum oxide (Al 2 O 3 ), more preferably by thermal spraying.
- oxide ceramics in particular titanium oxide (TiO 2 ) and / or aluminum oxide (Al 2 O 3 ), more preferably by thermal spraying.
- the microstructured layer of the microstructured substrate can also be applied to a microstructured substrate surface, the structure of which is preferably produced by sandblasting, wherein the roughness of the surface, as in the production of a macrostructured substrate surface, can be influenced by the grain size of the selected corundum (from FIG Fine corundum to coarse corundum).
- At least one first microstructured layer is formed on the microstructured substrate by applying a powder containing at least one fluoropolymer having a particle size in the range of 500 nm-30 ⁇ m, the powder preferably being heated exactly after application, that the powder grains melt on the ground and combine with it, but essentially retain their shape. This prevents the valleys and cavities resulting from the microstructure of the subsurface from being added by the microstructured fluoropolymer layer.
- Fillers in the microstructured fluoropolymer layer additionally structure the microstructured layer. It is advantageous if the powder is an admixture of inorganic particles such as in particular of SiC or Al 2 SO 3 and / or organic particles such as polyamides or PPSO 2 , or mixtures thereof, preferably in a proportion of 5 to 30 wt .-%. , contains. The particles provide for an improved microstructure and at the same time for a sufficient mechanical stability of the coating.
- the first microstructured fluoropolymer layer is preferably applied in coating thicknesses of 5 to 15 ⁇ m per application. Multiple application is possible and useful, a preferred layer thickness is 20 microns - 50 microns.
- the second sub-microstructured layer which preferably has a nanostructure whose protrusions are smaller than 1 ⁇ m, is preferably formed by applying a finely dispersed fluoropolymer having a grain size of 90-300 nm to the microstructured first fluoropolymer layer. Also, when baking this second layer, it is advantageous if the coating is just heated so that the particles of the second layer are merely fused so that they combine with the underlying layer, but essentially retain their shape.
- the finely dispersed fluoropolymer contains a supplement of whiskers, in particular of potassium titanate whiskers, and / or of carbon nanotubes, preferably in a proportion of from 5 to 40% by weight, in particular with respect to potassium titanate whiskers preferably in a proportion of 10 to 40 wt .-%.
- whiskers in particular of potassium titanate whiskers, and / or of carbon nanotubes, preferably in a proportion of from 5 to 40% by weight, in particular with respect to potassium titanate whiskers preferably in a proportion of 10 to 40 wt .-%.
- a primer layer may be provided whose thickness is preferably not more than 5 ⁇ m and not less than 1 ⁇ m.
- the hierarchical layer structure is applied to a microstructured substrate.
- This microstructured substrate may already be present through the substrate surface, but is usually produced by a treatment and / or coating of the substrate surface, in particular by producing a hard base layer.
- the surfaces of an aluminum body, a stainless steel body and a normal steel body after they have been degreased, first sandblasted with coarse corundum (Al 2 O 3 ). Sandblasting removed surfaces from any oxide layers and other contaminants. In addition, the surfaces have been given a first structure that allows mechanical bonding to the body surface of a subsequent coating applied by, for example, thermal spray as described below.
- Table 1 Coarse corundum radiation on aluminum Coarse corundum radiation on stainless steel Coarse corundum radiation on normal steel
- R a ( ⁇ m) 5.67 2.78 4.53
- R z ( ⁇ m) 35.43 17.45 29,47
- R max ( ⁇ m) 43.48 20.59 32.06
- R Sk -0.53 0.24 0.19
- the surfaces were flame-sprayed with a ceramic powder of the type AC130 (Metco 130) from Sulzer-Metco. This produces a finer surface structure, which already results from the particle size of the powder, which is in the range of 5 to 30 ⁇ m.
- the roughness values of the resulting surface are shown in Table 3.
- the roughness is constructed according to the Gaussian normal distribution and is quite uniform according to the procedure.
- Table 3 R a ( ⁇ m) 5.08 R z (microns) 31,99 R max ( ⁇ m) 46.58 R Sk 0.37 R Ku 3.96
- a hydrophobic layer structure was then applied to the microstructured substrate produced in the present case.
- fluoropolymers PTFE, PFA and also FEP were used. All three materials are fully fluorinated plastics, which in some properties, such. B. in the melting point, different.
- the fluoropolymer was applied as a powder by electrostatic coating. Coating took place in several processes up to a layer thickness of 20 ⁇ m-50 ⁇ m. The powder layers follow the contour of the basic structure after application.
- the fluoropolymers After application of the fluoropolymers, they were sintered, i. H. they were brought above their melting point to achieve a fusion.
- the temperature during sintering is usually at least 20 ° C, usually usually at least above 50 ° C above the melting point.
- a supplement of 5% PPSO 2 , 5% SiC or 20% PPSO 2 was added to the fluoropolymer powder used for coating.
- PPSO 2 is particularly well because of its high melting point, which is above 400 ° C, particularly good.
- the PPSO 2 used had a mean diameter of 20 ⁇ m.
- a fluoropolymer dispersion was then sprayed onto a pattern with a hierarchically constructed hard base structure of Metco 36C and Metco 130 applied in the manner described above and onto which a microstructured first layer of PFA fluoropolymer powder with 20% PPSO 2 aggregate was applied.
- a grain size of 90 nm - 150 nm at a surface temperature of the first microstructured layer of 100 ° C and then sintering the layer at a temperature of 360 ° C for 10 minutes has been achieved that solidified particles in the size of about 500 nm to 5 microns form at the surface. These so-called clusters are firmly fused to the underlying fluoropolymer.
- the resulting microstructures have a diameter of about 25 microns and a height of about 20 microns. In other test patterns microstructures with a diameter of approx. 25 ⁇ m and a height of up to 100 ⁇ m were achieved. The distances of the elevations are about 30 - 50 microns and can be up to about 100 microns.
- the submicrostructures formed by the clusters are approximately 2 to 5 ⁇ m high and approximately 10 to 15 ⁇ m long. Scanning electron micrographs of the surface are in FIG. 3 (250x magnification) and FIG. 3a (1000x magnification) to see.
- a Fluoropolymerdispersion was sprayed with 30 wt % of a whisker, here a potassium titanate whisker.
- the whiskers had a diameter of the order of 150 to 300 nm and a length of the order of 1 to 5 ⁇ m.
- the PFA dispersion had a particle size of 90-150 nm.
- the dispersion mixture was applied to the over 100 ° hot surface of the sample under high atomization pressure with a spray gun.
- the water of the dispersion evaporated immediately upon impact with the workpiece, and the Whisker PFA particles were thrown onto the surface. Subsequently, the layer was firmly bonded to the underlying PFA layer by sintering at a temperature of 360 ° C for 10 minutes. The embedded whisker creates the desired structure.
- the whisker structure is mechanically stable. Over a 90 ° -Peeltest with a Tesa ® -Testklebeband (Tesa test tape for testing surfaces no. 07475) can not remove the structure.
- the generated surface (see FIG. 4 (250x magnification) and FIG. 4a (1000 times magnification)) has microstructures with a diameter in the range of 30 microns, which are at a distance of about 50-100 microns to each other and whose height is about 20-70 microns.
- the superimposed submicron coating has structures that are oriented based on the fibers.
- the diameter of the fibers is about 300-500 nm, their length is about 1 - 5 microns.
- the water contact angle of the coating thus produced is 175 °, the outlet angle 0 °.
- the roughness characteristics of this surface structure are particularly high.
- the coated plate When determining the rolling angle, the coated plate was covered with a water droplet with a volume of 60 ⁇ l. The plate, or the entire device, was tilted until the drop began to roll off. This angle is the roll-off angle.
- test plate was covered with a water drop with a volume of 60 ⁇ l. The plate was tilted until just before the roll-off angle. In this case, two different contact angles are formed. The one on the slope facing, the other on the opposite side. The contact angles were determined in the manner described above, but the method Tangent 2 was used for the calculation.
- FIG. 4b The surface structure shown was produced substantially the same as that in FIGS. 4 and 4a surface structure shown with the only difference that instead of potassium titanate whiskers carbon nanotubes were added to the fluoropolymer dispersion in the same amount.
- FIG. 5 By way of example, a cross section of a surface coated according to the invention is shown schematically.
- a sandblasted metal substrate which has a microstructure with elevations of about 40 microns, a first layer of the material Metco® 36C and thereon a second layer of the material Metco 130 by flame spraying applied, thereon a primer layer.
- the two flame-sprayed layers and the primer layer form a microstructured substrate, to which a hierarchical structure of a microstructured first layer of PFA or FEP, which is mixed with PPSO 2 fillers, and a superimposed sub-microstructured second layer of individual clusters of PFA / FEP are applied ,
- the Metco 36 layer has a thickness of about 40-80 ⁇ m
- the Metco 130 layer has a thickness of about 30-80 ⁇ m
- the primer layer has a thickness of about 5 ⁇ m.
- the microstructured fluoropolymer layer of the hierarchical layer structure has a thickness of 20-40 microns and the clusters of submicrostructured fluoropolymer layer has a height of about 5 microns.
- the roughness of the microstructured inorganic layer is not equalized by the microstructured fluoropolymer layer. Rather, the roughness of the first microstructured inorganic layer is complemented by the roughness of the second microstructured fluoropolymer layer. So have the elevations of the surface coating a height of about 50 - 100 microns, and their maxima are spaced about 50 - 150 microns apart.
- the clusters of the submicrostructured fluoropolymer layer additionally roughen the surface.
- FIG. 6 is one to which FIG. 5 similar layer structure shown schematically.
- the layer structure differs only in the submicrostructured layer which is formed in place of PFA / FEP clusters with potassium titanate whiskers.
- the elevations of the surface coating have a height of about 50 - 130 microns, and their maxima are spaced about 50 - 150 microns apart.
- the potassium titanate whiskers or the carbon nanotubes of the submicrostructured layer additionally roughen the surface.
- a rose structure is produced, which in the illustrated example has been produced with a layer structure on an aluminum-based substrate. It can be produced, for example, by applying a PTFE layer as a submicrostructured layer to a layer structure of microstructured substrate and first, microstructured layer.
- the microstructured substrate is produced by sandblasting (preferably with fine or coarse corundum) an aluminum or aluminum alloy surface, resulting in a microstructured substrate surface.
- the substrate surface is anodically oxidized, so that an anodized layer or, preferably, a hard-anodal layer is produced. This forms a substrate with an inorganic microstructure.
- a spray gun By means of a spray gun, dispersions of PFA, FEP or PTFE are applied to the inorganic structure to produce the first, microstructured layer.
- the application of the submicron and / or nanostructure is carried out in the same way as stainless steel substrates.
- the florets structure arises during a special time-temperature sintering cycle.
- PTFE is sintered at 380 to 400 ° C for 15 minutes.
- a significantly lower temperature preferably as in the present example of 340 ° C., is chosen over a much longer period of time, preferably 2 hours as in the present example.
- the elevations have a diameter of 1 to 3 microns.
- the height is about 500 nm to 2 microns.
- the distance from each other is 2 to 10 microns.
- the formation of these structures is reproducible and can be detected on various PTFE surfaces.
- the water contact angle is 168 ° with a drainage angle of 3 °.
- FIGS. 8a and 8b the scheme of the layer structure on an aluminum-containing substrate is shown with a Harteloxal harsh.
- the substrate surface is microstructured and has elevations in a height of about 40 microns.
- the hard-anodal layer produced on the substrate surface is approximately 50 ⁇ m thick.
- a primer layer having a thickness of about 2 ⁇ m is applied, whereupon a fluoropolymer layer having a thickness of about 5 ⁇ m is arranged.
- the microstructure of the fluoropolymer layer corresponds approximately to the microstructure of the metal substrate.
- FIGS. 8a and 8b Surface coatings shown differed by the submicrostructured layer applied to the microstructured fluoropolymer layer FIG. 8a formed by PFA or FEP cluster with a height of about 5 microns, while the surface in FIG. 8b whisker with a length of about 5 microns and a diameter of about 150 - 300 nm is additionally structured.
- the surface may also be referenced with reference to FIG. 7 be described submicrostructured Röschen Modell.
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Description
Die Erfindung betrifft eine Antihaftbeschichtung für eine Oberfläche eines Substrats, die mindestens ein Fluorpolymer enthält, sowie ein Verfahren zu seiner Herstellung.The invention relates to a non-stick coating for a surface of a substrate containing at least one fluoropolymer and to a process for its preparation.
Unter einer Antihaftbeschichtung ist im Rahmen der vorliegenden Erfindung ein Schichtaufbau zu verstehen, der so beschaffen ist, dass er sich insbesondere für Walzen oder andere Maschinenteile in der Klebstoff-, Gummi- und/oder lackverarbeitenden Industrie besonders gut eignet. Gute Antihafteigenschaften sind besonders dort relevant, wo bestimmte Flächenbereiche, beispielsweise von Etiketten, Klebebändern, Windeln und anderen Produkten, die Eigenschaft aufweisen sollen, dass dort Klebstoff oder andere klebrige Medien nicht haften. Damit können gezielt begrenzte Klebebereiche geschaffen werden, während die Nachbarbereiche nicht ankleben können. D.h., der Klebstoff bzw. andere klebrige Medien können maschinell gezielt und lokal begrenzt aufgebracht werden. Die entsprechend beschichteten Werkzeuge, wie beispielsweise Walzen in der Papierindustrie zur Herstellung mehrlagigen oder kaschierten Papiers bleiben kleberfrei.In the context of the present invention, a non-stick coating is to be understood as meaning a layer structure which is such that it is particularly suitable, in particular, for rolls or other machine parts in the adhesive, rubber and / or paint-processing industry. Good non-stick properties are particularly relevant where certain areas, such as labels, adhesive tapes, diapers and other products, are said to have the property of preventing adhesion of adhesive or other sticky media. This allows targeted adhesive areas to be created while the neighboring areas can not stick. That is, the adhesive or other sticky media can be applied by machine targeted and localized. The corresponding coated tools, such as rolls in the paper industry for producing multilayer or laminated paper remain adhesive-free.
Dieser Effekt wird auch industriell angewendet. Es sind Materialien mit einer Oberflächenstruktur bekannt, bei der die Struktur des Lotus-Blattes nachempfunden ist. Dabei wird als Oberflächenmaterial Silikon verwendet, das sich in der Weise verarbeiten bzw. behandeln lässt, dass sich eine Art "Doppelstruktur" an der Oberfläche ergibt. Die Oberfläche besteht aus einer noppenartigen Mikrostruktur, wobei die einzelnen Noppen wiederum Nanoerhebungen aufweisen.This effect is also applied industrially. There are known materials with a surface structure in which the structure of the lotus leaf is modeled. In this case, silicon is used as the surface material, which can be processed or treated in such a way that a kind of "double structure" results on the surface. The surface consists of a nub-like microstructure, with the individual nubs again having nano-elevations.
Nachteilig ist, dass die in dieser Weise mit Silikon beschichteten Oberflächen keine Resistenz gegenüber Lösungsmitteln und Korrosion aufweisen. Des Weiteren sind diese Oberflächen nicht für Lebensmittelanwendungen zugelassen. Schließlich kommt eine entsprechende Oberfläche auch aufgrund der Materialeigenschaft des Silikons für manche Anwendungen nicht in Frage. Bei Lackierungs-Anwendungen (z. B. bei der Autolackierung) ist eine so beschichtete Oberfläche untauglich, da der Lack vom Silikon abgestoßen wird und es so zur Ausbildung sog. "Fischaugen" kommt. Nachteilig ist schließlich, dass die Härte der Oberfläche relativ gering ist.The disadvantage is that the silicone-coated surfaces in this way have no resistance to solvents and corrosion. Furthermore, these surfaces are not approved for food applications. Finally, due to the material properties of the silicone, a corresponding surface is also out of the question for some applications. In coating applications (eg in car painting) such a coated surface is unsuitable because the paint is repelled by the silicone and so it comes to the formation of so-called "fish eyes". The disadvantage is finally that the hardness of the surface is relatively low.
Andererseits sind Oberflächenbeschichtungen unter Einsatz von Fluorkunststoffen (beispielsweise Teflon) bekannt, die zu einer härteren Oberfläche führen. Der Fluorkunststoff wird dabei auf einer Trägerschicht bei erhöhten Temperaturen (ca. 400 °C) eingesintert, um einen stabilen Verbund zu erhalten. Durch das Verfließen des Fluorpolymers im Zuge des Sinterprozesses wird jedoch die Grundstruktur des Substrats eingeebnet; ein Lotus-Effekt ist auf diese Weise nicht zu erhalten.On the other hand, surface coatings using fluoroplastics (for example Teflon) are known which lead to a harder surface. The fluoroplastic is sintered on a carrier layer at elevated temperatures (about 400 ° C) in order to obtain a stable composite. Due to the flow of the fluoropolymer in the course of the sintering process, however, the basic structure of the substrate is leveled; a lotus effect can not be obtained in this way.
In der
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In der
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Eine Aufgabe der vorliegenden Erfindung besteht darin, Oberflächenbeschichtungen zur Verfügung zu stellen, die den Lotus-Effekt aufweisen, deren Antihafteigenschaften gegenüber den vorbekannten Oberflächenbeschichtungen deutlich verbessert sind und die ausreichend mechanisch stabil sind. Auch soll mit der vorliegenden Erfindung ein Verfahren zur Herstellung einer solchen Oberflächenbeschichtung zur Verfügung gestellt werden.It is an object of the present invention to provide surface coatings having the lotus effect, the anti-stick properties of which are markedly improved over the prior art surface coatings, and which are sufficiently mechanically stable. Also, the present invention provides a process for producing such a surface coating.
Diese Aufgabe wird mit einer Antihaftbeschichtung mit den Merkmalen des Anspruchs 1 sowie einem Verfahren zum Erzeugen einer Antihaftbeschichtung mit den Merkmalen des Anspruchs 4 gelöst.This object is achieved with a non-stick coating with the features of claim 1 and a method for producing a non-stick coating with the features of claim 4.
Als Substrate werden hier und im Folgenden insbesondere solche verstanden, die zumindest teilweise aus Metall, Keramik, Glas, Email oder einem Composite-Material hieraus bestehen, aber auch solche aus anderen geeigneten Materialien. Materialien sind insbesondere dann als Bestandteil eines Substrats geeignet, sofern sie bei Temperaturen, die bei einem gegebenenfalls vorgesehenen Sintervorgang auftreten, ausreichend thermisch stabil sind.Substrates here and below are understood in particular to be those which at least partially consist of metal, ceramic, glass, enamel or a composite material thereof, but also those of other suitable materials. Materials are particularly suitable as part of a substrate, provided that they are sufficiently thermally stable at temperatures that occur in an optionally provided sintering process.
Unter einem antiadhäsiven Kunststoff wird hier und im Folgenden insbesondere ein Fluorpolymer wie beispielsweise Polytetrafluorethylen (PTFE), Perfluoralkoxylalkan (PFA), Perfluorethylenpropylen-Copolymer (FEP), aber auch andere geeignete Materialien, die perfluorierte Kohlenstoffketten enthalten und vergleichbare hydrophobe Eigenschaften haben, verstanden.An anti-adhesive plastic is understood here and below as meaning in particular a fluoropolymer such as, for example, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene-propylene copolymer (FEP), but also other suitable materials which contain perfluorinated carbon chains and have comparable hydrophobic properties.
Unter einem mikrostrukturierten Untergrund wird hier und im Folgenden ein solcher mit einer Rauheit im Mikrometerbereich, insbesondere im Bereich von 2 bis 50 µm Ra, verstanden. Der Untergrund kann durch das Substrat selbst gebildet sein, aber auch durch eine auf das Substrat aufgebrachte oder aufgelegte Schicht, erzeugt werden.A microstructured substrate is understood here and below to mean one having a roughness in the micrometer range, in particular in the range from 2 to 50 μm Ra. The substrate may be formed by the substrate itself, but also by a layer applied or applied to the substrate.
Unter einem hierarchischen Schichtaufbau wird ein solcher verstanden, bei dem einer ersten Schicht mit einer ersten Oberflächenstruktur eine zweite Oberflächenstruktur einer zweiten Schicht überlagert wird, ohne dass die erste Oberflächenstruktur dabei egalisiert wird.A hierarchical layer structure is understood to be one in which a second surface structure of a second layer is superimposed on a first layer having a first surface structure, without the first surface structure being leveled out in the process.
Unter einer ersten mikrostrukturierten Schicht des hierarchischen Schichtaufbaus wird eine solche mit Mikroerhebungen im Bereich von 2 bis 50 µm verstanden, unter einer submikrostrukturierten zweiten Schicht, die die erste überlagert, eine solche mit Erhebungen insbesondere in einem Bereich von 0,1 bis 5 µm, deren Erhebungen kleiner sind als die Erhebungen der ersten mikrostrukturierten Schicht.A first microstructured layer of the hierarchical layer structure is understood to be one with micro-elevations in the range of 2 to 50 μm, under a submicrostructured second layer, which overlays the first one, with elevations, in particular in a range of 0.1 to 5 μm, of which Elevations are smaller than the elevations of the first microstructured layer.
Ein Zuschlag in der ersten mikrostrukturierten Schicht der erfindungsgemäßen Antihaftbeschichtung von 5 bis 30 Gew.-% organischen und/oder anorganischen Partikeln, insbesondere von Polyphenylensulfon (PPSO2) oder Siliziumkarbid (SiC), erzeugt eine zusätzliche Strukturierung der Schicht. Die Partikelgröße der Zuschlagsstoffe und der Füllgrad kann entsprechend dem gewünschten Effekt variiert werden. Es werden zum Beispiel gute Ergebnisse erzielt mit PPSO2 - Zuschlägen mit einem durchschnittlichen Partikeldurchmesser von 20 µm.A supplement in the first microstructured layer of the non-stick coating according to the invention of from 5 to 30% by weight of organic and / or inorganic particles, in particular polyphenylene sulfone (PPSO 2 ) or silicon carbide (SiC), produces additional structuring of the layer. The particle size of the additives and the degree of filling can be varied according to the desired effect. For example, good results are achieved with PPSO 2 aggregates with an average particle diameter of 20 μm.
Die erfindungsgemäße Antihaftbeschichtung zeichnet sich durch einen Wasserkontaktwinkel CA >= 150°, insbesondere in Verbindung mit einer Wasserkontaktwinkel- Hysterese CAH <= 8° und/oder einem Ablaufwinkel <= 10° aus. Wasserkontaktwinkel von >= 165° mit einer Hysterese und einem Ablaufwinkel, die gegen 0 gehen, sind mit der erfindungsgemäßen Antihaftbeschichtung möglich. So kann die Abzugskraft eines Tesa® - Tapes von einer mit der erfindungsgemäßen Antihaftbeschichtung beschichteten Oberfläche gegen Null gehen.The non-stick coating according to the invention is characterized by a water contact angle CA> = 150 °, in particular in conjunction with a water contact angle hysteresis CAH <= 8 ° and / or a discharge angle <= 10 °. Water contact angle of> = 165 ° with a hysteresis and a drain angle, which go to 0, are possible with the non-stick coating according to the invention. This is how the pull-off force of a Tesa® - Tapes of a surface coated with the non-stick coating according to the invention go to zero.
Zum Erzeugen einer erfindungsgemäßen Haftbeschichtung wird der mikrostrukturierte Untergrund vorzugsweise durch Aufbringen einer mikrostrukturierten Schicht auf eine makrostrukturierte Oberfläche erzeugt. Die Oberfläche des Substrats kann dabei bereits selbst eine Makrostruktur aufweisen, wenn sie eine entsprechende Rauheit hat. Die Makrostruktur kann aber auch durch die Art des Substrats vorgegeben sein, wie beispielsweise bei einem feinen Drahtgewebe. Auch kann eine geeignete Makrostruktur der Substratoberfläche erzeugt werden, beispielsweise durch Sandstrahlen oder aber durch Auflegen und Befestigen eines makrostrukturiertem Gittergewebes. Ergänzend und/oder alternativ hierzu kann durch thermisches Aufspritzen einer makrostrukturierten Schicht auf das Substrat, insbesondere durch Flammspritzen eines Metalldrahtes oder Metallpulvers wie beispielsweise Chrom/Nickel-Draht oder aufgeschmolzenes Chrom/Nickel-Pulver, eine makrostrukturierten Oberfläche erzeugt werden.To produce an adhesion coating according to the invention, the microstructured substrate is preferably produced by applying a microstructured layer to a macrostructured surface. The surface of the substrate may already have a macrostructure of its own if it has a corresponding roughness. However, the macrostructure can also be predetermined by the nature of the substrate, as for example in the case of a fine wire mesh. It is also possible to produce a suitable macrostructure of the substrate surface, for example by sand blasting or else by placing and fastening a macrostructured grid fabric. In addition and / or alternatively, a macrostructured surface can be produced by thermal spraying of a macrostructured layer onto the substrate, in particular by flame spraying of a metal wire or metal powder such as chromium / nickel wire or molten chromium / nickel powder.
Die mikrostrukturierte Schicht des mikrostrukturierten Untergrunds wird auf der makrostrukturierten Oberfläche vorzugsweise durch Aufbringen von Oxidkeramiken, insbesondere Titaniumoxid (TiO2) und/oder Aluminiumoxid (Al2O3), erzeugt, besonderes bevorzugt durch thermisches Spritzen.The microstructured layer of the microstructured substrate is preferably formed on the macrostructured surface by application of oxide ceramics, in particular titanium oxide (TiO 2 ) and / or aluminum oxide (Al 2 O 3 ), more preferably by thermal spraying.
Alternativ kann die mikrostrukturierte Schicht des mikrostrukturierten Untergrunds auch auf eine mikrostrukturierte Substratoberfläche aufgebracht sein, deren Struktur vorzugsweise durch Sandstrahlen erzeugt wird, wobei die Rauigkeit der Oberfläche, ebenso wie bei dem Erzeugen einer makrostrukturierten Substratoberfläche, durch die Körnung des gewählten Korunds beeinflusst werden kann (von Feinkorund bis Grobkorund).Alternatively, the microstructured layer of the microstructured substrate can also be applied to a microstructured substrate surface, the structure of which is preferably produced by sandblasting, wherein the roughness of the surface, as in the production of a macrostructured substrate surface, can be influenced by the grain size of the selected corundum (from FIG Fine corundum to coarse corundum).
Gemäß dem erfindungsgemäßen Verfahren- wird mindestens eine erste mikrostrukturierte Schicht auf dem mikrostrukturierten Untergrund erzeugt, indem ein mindestens ein Fluorpolymer enthaltendes Pulver mit einer Korngröße im Bereich von 500 nm - 30 µm aufgetragen wird, wobei das Pulver nach dem Auftragen vorzugsweise genau so erhitzt wird, dass die Pulverkörner am Untergrund anschmelzen und sich damit verbinden, aber im Wesentlichen ihre Form beibehalten. Hierdurch wird verhindert, dass die sich durch die Mikrostruktur des Untergrundes ergebenden Täler und Kavitäten von der mikrostrukturierten Fluorpolymer-Schicht zugesetzt werden.According to the method of the invention, at least one first microstructured layer is formed on the microstructured substrate by applying a powder containing at least one fluoropolymer having a particle size in the range of 500 nm-30 μm, the powder preferably being heated exactly after application, that the powder grains melt on the ground and combine with it, but essentially retain their shape. This prevents the valleys and cavities resulting from the microstructure of the subsurface from being added by the microstructured fluoropolymer layer.
Durch Füllstoffe in der mikrostrukturierten Fluorpolymerschicht wird die mikrostrukturierte Schicht zusätzlich strukturiert. Dabei ist es von Vorteil, wenn das Pulver eine Beimischung von anorganische Partikeln wie insbesondere von SiC oder Al2SO3 und/oder organischen Partikeln wie Polyamide oder PPSO2, oder Mischungen hiervon, vorzugsweise mit einem Anteil von 5 bis 30 Gew.-%, enthält. Die Partikel sorgen für eine verbesserte Mikrostruktur und gleichzeitig für eine ausreichende mechanische Stabilität der Beschichtung.Fillers in the microstructured fluoropolymer layer additionally structure the microstructured layer. It is advantageous if the powder is an admixture of inorganic particles such as in particular of SiC or Al 2 SO 3 and / or organic particles such as polyamides or PPSO 2 , or mixtures thereof, preferably in a proportion of 5 to 30 wt .-%. , contains. The particles provide for an improved microstructure and at the same time for a sufficient mechanical stability of the coating.
Die erste mikrostrukturierte Fluorpolymerschicht wird vorzugsweise in Beschichtungsdikken von 5 bis 15 µm pro Auftrag aufgebracht. Ein Mehrfachauftrag ist möglich und sinnvoll, eine bevorzugte Schichtdicke liegt bei 20 µm - 50 µm.The first microstructured fluoropolymer layer is preferably applied in coating thicknesses of 5 to 15 μm per application. Multiple application is possible and useful, a preferred layer thickness is 20 microns - 50 microns.
Die zweite, submikrostrukturierte Schicht, die vorzugsweise eine Nanostruktur aufweist, deren Erhebungen kleiner als 1 µm sind, wird vorzugsweise durch Auftragen eines feindispersen Fluorpolymers mit einer Korngröße von 90 - 300 nm auf die mikrostrukturierte erste Fluorpolymer-Schicht erzeugt. Auch beim Einbrennen dieser zweiten Schicht ist es von Vorteil, wenn die Beschichtung gerade so erhitzt wird, dass die Partikel der zweiten Schicht lediglich angeschmolzen werden, so dass sie sich mit der darunter liegenden Schicht verbinden, ihre Form aber im Wesentlichen beibehalten.The second sub-microstructured layer, which preferably has a nanostructure whose protrusions are smaller than 1 μm, is preferably formed by applying a finely dispersed fluoropolymer having a grain size of 90-300 nm to the microstructured first fluoropolymer layer. Also, when baking this second layer, it is advantageous if the coating is just heated so that the particles of the second layer are merely fused so that they combine with the underlying layer, but essentially retain their shape.
In noch einer weiteren Ausgestaltung des erfindungsgemäßen Verfahrens enthält das feindisperse Fluorpolymer einen Zuschlag von Whiskern, insbesondere von Kaliumtitanat-Whiskern, und/oder von Kohlenstoffnanoröhrchen, vorzugsweise mit einem Anteil von 5 bis 40 Gew.-%, insbesondere in Bezug auf Kaliumtitanat-Whisker weiter bevorzugt mit einem Anteil von 10 bis 40 Gew.-%. Hierdurch bildet sich eine Oberflächenstruktur mit Whiskern bzw. Röhrchen aus, mit der größte Wasserkontaktwinkel erreicht werden können.In yet another embodiment of the method according to the invention, the finely dispersed fluoropolymer contains a supplement of whiskers, in particular of potassium titanate whiskers, and / or of carbon nanotubes, preferably in a proportion of from 5 to 40% by weight, in particular with respect to potassium titanate whiskers preferably in a proportion of 10 to 40 wt .-%. This forms a surface structure with whiskers or tubes, with the largest water contact angle can be achieved.
Schließlich kann zwischen dem hierarchischen Schichtaufbau aus erster und zweiter Schicht und dem mikrostrukturierten Untergrund noch eine Primerschicht vorgesehen sein, deren Dicke vorzugsweise 5 µm nicht über- und 1 µm nicht unterschreitet. Damit kann eine bessere Haftung des Fluorpolymers auf dem Untergrund und damit eine erhöhte mechanische Stabilität der Antihaftbeschichtung erzielt werden.Finally, between the hierarchical layer structure comprising the first and second layer and the microstructured substrate, a primer layer may be provided whose thickness is preferably not more than 5 μm and not less than 1 μm. Thus, a better adhesion of the fluoropolymer on the substrate and thus an increased mechanical stability of the non-stick coating can be achieved.
Im Folgenden werden das erfindungsgemäße Verfahren und die erfindungsgemäße Beschichtung anhand von verschiedenen bevorzugten Ausführungsbeispielen beschrieben.In the following, the method according to the invention and the coating according to the invention will be described with reference to various preferred exemplary embodiments.
Es zeigen
- Figur 1
- eine Rasterelektronenmikroskopaufnahme einer erfindungsgemäß beschichteten Oberfläche mit anorganischer Mikrostruktur;
- Figur 2
- zeigt einen skizzierten Beschichtungsaufbau mit Grundstruktur und einer ersten, mehrlagig aufgetragenen Fluorpolymer-Schicht;
- Figuren 3 und 3a
- Rasterelektronenmikroskopaufnahmen einer weiteren erfindungsgemäß beschichteten Oberfläche mit einer Clusterstruktur in unterschiedlichen Auflösungen;
- Figuren 4, 4a und 4b
- Rasterelektronenmikroskopaufnahmen einer weiteren erfindungsgemäß beschichteten Oberfläche mit einer Whiskerstruktur (
Figuren 4 und4a mit Kaliumtitanat-Whisker,Figur 4b mit Kohlenstoffnanoröhrchen) in unterschiedlichen Auflösungen; - Figur 5
- eine schematische Darstellung einer erfindungsgemäß beschichteten Oberfläche auf einem Edelstahlsubstrat mit einer Clusterstruktur;
- Figur 6
- eine weitere schematische Darstellung einer erfindungsgemäß beschichteten Oberfläche auf einem Edelstahlsubstrat mit Whiskerstruktur;
- Figur 7
- eine Rasterelektronenmikroskopaufnahme einer weiteren erfindungsgemäß beschichteten Oberfläche mit einer Röschenstruktur; und
- Figuren 8a und 8b
- weitere schematische Darstellungen von erfindungsgemäß beschichteten Oberflächen auf Aluminiumsubstrat (
Figur 8a mit Cluster- undFigur 8b mit Whiskerstruktur)
- FIG. 1
- a scanning electron micrograph of an inventive surface coated with inorganic microstructure;
- FIG. 2
- shows a sketched coating structure with a basic structure and a first, multi-layer fluoropolymer layer applied;
- FIGS. 3 and 3a
- Scanning electron micrographs of another inventively coated surface with a cluster structure in different resolutions;
- Figures 4, 4a and 4b
- Scanning electron micrographs of another inventively coated surface with a whisker structure (
FIGS. 4 and4a with potassium titanate whisker,FIG. 4b with carbon nanotubes) in different resolutions; - FIG. 5
- a schematic representation of a coated surface according to the invention on a stainless steel substrate with a cluster structure;
- FIG. 6
- a further schematic representation of a coated surface according to the invention on a stainless steel substrate with whisker structure;
- FIG. 7
- a scanning electron micrograph of another inventively coated surface with a Röschenstruktur; and
- FIGS. 8a and 8b
- further schematic representations of surfaces coated according to the invention on aluminum substrate (
FIG. 8a with cluster andFIG. 8b with whisker structure)
Wie bereits eingangs erwähnt, wird der hierarchische Schichtaufbau auf einen mikrostrukturierten Untergrund aufgebracht. Dieser mikrostrukturierte Untergrund kann bereits durch die Substratoberfläche gegeben sein, wird aber üblicherweise durch eine Behandlung und/oder Beschichtung der Substratoberfläche erzeugt, insbesondere durch Erzeugen einer Hartgrundschicht.As already mentioned, the hierarchical layer structure is applied to a microstructured substrate. This microstructured substrate may already be present through the substrate surface, but is usually produced by a treatment and / or coating of the substrate surface, in particular by producing a hard base layer.
Zum Erzeugen einer Hartgrundschicht auf einem metallischen Substrat wurden die Oberflächen eines Aluminiumkörpers, eines Edelstahlkörpers und eines Normalstahlkörpers, nachdem sie entfettet worden sind, zunächst mit Grobkorund (Al2O3) gesandstrahlt. Durch das Sandstrahlen wurden die Oberflächen von etwaigen Oxidschichten und anderen Verunreinigungen befreit. Außerdem erhielten die Oberflächen eine erste Struktur, die einer nachfolgenden Beschichtung, die beispielsweise wie nachfolgend beschrieben durch thermisches Spritzen aufgetragen wird, eine mechanische Verklammerung mit der Körperoberfläche ermöglicht.For producing a hard base layer on a metallic substrate, the surfaces of an aluminum body, a stainless steel body and a normal steel body, after they have been degreased, first sandblasted with coarse corundum (Al 2 O 3 ). Sandblasting removed surfaces from any oxide layers and other contaminants. In addition, the surfaces have been given a first structure that allows mechanical bonding to the body surface of a subsequent coating applied by, for example, thermal spray as described below.
Die mit einem Tastschnitt-Messgerät der Firma Mahr gemessenen Rauheitswerte für mit Grobkorund gesandstrahlte Oberflächen, basierend auf einer Messstrecke von 5,6 mm mit einer Grenzwellenlänge von 0,8 mm, lassen sich der nachfolgenden Tabelle 1 entnehmen.
Nach dem Sandstrahlen wurden die Oberflächen mit Metco® 36C, ein Wolframkarbid enthaltendes Nickel-Chrom-Legierungspulver, flammgespritzt. Hierdurch erhält die Oberfläche eine Makrostruktur, die unabhängig ist von der Oberflächenstruktur des Substrats. Die mit dem Tastschnitt-Messgerät gemessenen Rauheitswerte der flammgespritzten Oberfläche sind in Tabelle 2 wiedergegeben (Messstrecke: 5,6mm, Grenzwellenlänge: 0,8mm).
In einer alternativen Beschichtung wurden die Oberflächen mit einem Keramikpulver des Typs AC130 (Metco 130) der Firma Sulzer-Metco flammgespritzt. Hierdurch wird eine feinere Oberflächenstruktur erzeugt, was sich bereits aus der Partikelgröße des Pulvers, die im Bereich von 5 bis 30 µm liegt, ergibt. Die Rauheitswerte der sich hieraus ergebenden Oberfläche sind in Tabelle 3 wiedergegeben.In an alternative coating, the surfaces were flame-sprayed with a ceramic powder of the type AC130 (Metco 130) from Sulzer-Metco. This produces a finer surface structure, which already results from the particle size of the powder, which is in the range of 5 to 30 μm. The roughness values of the resulting surface are shown in Table 3.
Die Rauheit ist nach der Gauß'schen Normalverteilung aufgebaut und entsprechend dem Verfahren recht gleichmäßig.
Eine Überlagerung der beiden Flammspritzsysteme, wobei zunächst Metco 36C und danach das Keramikpulver Metco 130 durch Flammspritzen aufgetragen wurde, führt zu einer festzustellenden hierarchischen Struktur mit einer Gesamtschichtdicke von 50 µm - 150 µm.A superposition of the two flame spraying systems, whereby first Metco 36C and then the
Zu der sich hieraus ergebenden Oberfläche wurden die in Tabelle 4 wiedergegebenen Rauheitswerte gemessen. Die Oberflächenstruktur ist in
Das beschriebene Verfahren zum Erzeugen einer Hartgrundschicht ist zwar ein bevorzugtes Verfahren, es können aber auch andere Verfahren verwendet werden, sofern mit diesem eine vergleichbare mikrostrukturierte Schicht erzeugt wird.Although the described method for producing a hard base layer is a preferred method, it is also possible to use other methods if a comparable microstructured layer is produced therewith.
Auf den vorliegend erzeugten, mikrostrukturierten Untergrund wurde dann ein hydrophober Schichtaufbau aufgebracht. Zum Beschichten wurden die Fluorpolymere PTFE, PFA und auch FEP verwendet. Alle drei Materialien sind vollfluorierte Kunststoffe, die sich in einigen Eigenschaften, wie z. B. im Schmelzpunkt, unterscheiden.A hydrophobic layer structure was then applied to the microstructured substrate produced in the present case. For coating the fluoropolymers PTFE, PFA and also FEP were used. All three materials are fully fluorinated plastics, which in some properties, such. B. in the melting point, different.
Wesentliche Eigenschaften der verwendeten Fluorpolymere und anderer, grundsätzlich verwendbarer hydrophober Beschichtungsmaterialien sind in Tabelle 5 dargestellt.
Zum Auftragen einer ersten mikrostrukturierten Fluorpolymer-Schicht wurde es als wichtig erachtet, die Mikrostruktur des Untergrunds beizubehalten. Um dies sicherzustellen, wurde das Fluorpolymer als Pulver aufgetragen, und zwar durch elektrostatisches Beschichten. Das Beschichten erfolgte in mehreren Vorgängen bis zu einer Schichtdicke von 20µm - 50 µm. Die Pulverschichten folgen nach dem Auftrag der Kontur der Grundstruktur.For applying a first microstructured fluoropolymer layer, it has been considered important to maintain the microstructure of the substrate. To ensure this, the fluoropolymer was applied as a powder by electrostatic coating. Coating took place in several processes up to a layer thickness of 20 μm-50 μm. The powder layers follow the contour of the basic structure after application.
Nach dem Auftragen der Fluorpolymere wurden diese versintert, d. h. sie wurden über ihren Schmelzpunkt gebracht, um eine Verschmelzung zu erreichen. Die Temperatur beim Versintern liegt üblicherweise mindestens 20°C, meist üblicherweise mindestens über 50 °C über dem Schmelzpunkt.After application of the fluoropolymers, they were sintered, i. H. they were brought above their melting point to achieve a fusion. The temperature during sintering is usually at least 20 ° C, usually usually at least above 50 ° C above the melting point.
Um die Schmelzviskosität heraufzusetzen, so dass die Struktur des Untergrunds nicht egalisiert wird, und gleichzeitig der Beschichtung eine eigene Struktur zu verleihen, wurde dem zum beschichten verwendeten Fluorpolymerpulver ein Zuschlag von 5% PPSO2, 5% SiC bzw. 20 % PPSO2 beigemischt. Von den grundsätzlich geeigneten organischen Zuschlagstoffen eignet sich PPSO2 wegen seines hohen Schmelzpunktes, der über 400°C liegt, besonders gut. Das verwendete PPSO2 hatte einen mittleren Durchmesser von 20 µm.In order to increase the melt viscosity, so that the structure of the substrate is not equalized, and at the same time to give the coating its own structure, a supplement of 5% PPSO 2 , 5% SiC or 20% PPSO 2 was added to the fluoropolymer powder used for coating. Of the generally suitable organic additives PPSO 2 is particularly well because of its high melting point, which is above 400 ° C, particularly good. The PPSO 2 used had a mean diameter of 20 μm.
Beim Verschmelzen, d. h. Sintern der Schicht war die Viskosität der Schmelze so hoch, dass sie nicht in die Täler des mikrostrukturierten Untergrundes abfließen konnte. Die sich ergebende Schichtstruktur ist in
Mit der Auswahl der verwendeten Fluorpolymere, deren Füllstoffe und der gewählten Schichtdicke wurde eine mikrostrukturierte erste Schicht mit bereits sehr guten Gebrauchseigenschaften erzielt, nämlich mit einer hohen mechanischen Stabilität, leichter Applizierbarkeit auf Substrate verschiedenster Größen und Geometrien und guten Antihafteigenschaften.With the selection of the fluoropolymers used, their fillers and the selected layer thickness, a microstructured first layer with already very good performance properties was achieved, namely with a high mechanical stability, easy applicability to substrates of various sizes and geometries and good non-stick properties.
Bei einem Muster mit einer hierarchisch aufgebauten anorganischer Hartgrundstruktur aus Metco 36C und Metco 130, die mit einem PFA Fluorpolymer mit einem Zuschlag von 5 % PPSO2 beschichtet wurde, wurde ein Wasserkontaktwinkel von 140 ° und ein Ablaufwinkel von 12° gemessen. Bei einem Muster mit gleicher Hartgrundstruktur, die mit einem PFA Fluorpolymerpulver mit einem Zuschlag von 5% SiC beschichtet wurde, wurde ein Wasserkontaktwinkel von 144 ° und ein Ablaufwinkel von 12° gemessen. Bei einem weiteren Muster mit gleicher, hierarchisch aufgebauter Hartgrundstruktur, die mit einem PFA Fluorpolymerpulver mit einem Zuschlag von 20% PPSO2 beschichtet wurde, wurde ein Wasserkontaktwinkel von 156° und ein Ablaufwinkel von 21° gemessen.In a pattern having a hierarchical inorganic hard base structure of Metco 36C and
Auf ein Muster mit hierarchisch aufgebauter Hartgrundstruktur aus Metco 36C und Metco 130, die in der oben beschriebenen Weise appliziert und auf die eine mikrostrukturierte erste Schicht aus einem PFA Fluorpolymerpulver mit 20% PPSO2 Zuschlag aufgebracht wurde, wurde dann eine Fluorpolymerdispersion aufgespritzt. Durch eine hohe Zerstäubung (Atomisierung) beim Aufspritzen der Dispersion mit einer Korngröße von 90 nm - 150 nm bei einer Oberflächentemperatur der ersten mikrostrukturierten Schicht von 100°C und durch anschließendes Sintern der Schicht bei einer Temperatur von 360°C für die Dauer von 10 Minuten wurde erreicht, dass sich festgeschmolzene Partikel in der Größe von etwa 500 nm bis 5 µm an der Oberfläche ausbilden. Diese sogenannten Cluster sind fest mit dem darunterliegenden Fluorpolymer verschmolzen. Dadurch sind sie beachtlich stabil und lassen sich nicht mit einem Klebeband-Abzugstest, einem sogenannten 90°-Peeltest, bei dem ein Tesa® - Klebeband (Tesa Testband zum Testen von Oberflächen Nr. 07475) auf die Oberfläche aufgebracht und danach wieder abgezogen wird, entfernen. Der Wasserkontaktwinkel der so hergestellten Oberfläche lag bei 165°, der Ablaufwinkel bei 5°.A fluoropolymer dispersion was then sprayed onto a pattern with a hierarchically constructed hard base structure of Metco 36C and
Die so erzielten Mikrostrukturen haben einen Durchmesser von ca. 25 µm und eine Höhe von ca. 20 µm. In anderen Testmustern wurden Mikrostrukturen mit einem Durchmesser von ca. 25 µm und einer Höhe bis zu 100 µm erzielt. Die Abstände der Erhebungen liegen bei ca. 30 - 50 µm und können bis etwa 100 µm betragen. Die durch die Cluster gebildeten Submikrostrukturen sind ungefähr 2 bis 5 µm hoch und ca. 10 - 15 µm lang. Rasterelektronenmikroskop-Aufnahmen der Oberfläche sind in
Weitestgehend gleiche Ergebnisse wurden erzielt bei Verwendung von FEP als Fluorpolymer.Largely the same results were obtained using FEP as the fluoropolymer.
Auf ein anderes Muster mit hierarchisch aufgebauter Hartgrundstruktur aus Metco 36C und Metco 130, die in der oben beschriebenen Weise appliziert wurde, und mikrostrukturierter erster Schicht aus einem PFA Fluorpolymerpulver mit 20% PPSO2 darauf aufgebrachten Zuschlag wurde dann eine Fluorpolymerdispersion aufgespritzt, die mit 30 Gew.-% eines Whiskers, hier eines Kaliumtitanat-Whiskers, gefüllt war. Die Whisker hatten einen Durchmesser in der Größenordnung von 150 bis 300 nm und eine Länge in der Größenordnung von 1 - 5 µm. Die PFA-Dispersion hatte eine Partikelgröße von 90 - 150 nm. Das Dispersionsgemisch wurde auf die über 100° heiße Oberfläche des Musters bei hohem Zerstäubungsdruck mit einer Spritzpistole aufgetragen. Dabei verdampfte das Wasser der Dispersion sofort bei Auftreffen auf das Werkstück, und die PFA-Partikel mit den Whiskern wurden auf die Oberfläche geschleudert. Anschließend wurde die Schicht durch Sintern bei einer Temperatur von 360°C für die Dauer von 10 Minuten mit der darunter liegenden PFA-Schicht fest verbunden. Durch die eingelagerten Whisker entsteht die gewünschte Struktur.To another pattern with a hierarchically constructed hard base structure of Metco 36C and
Ebenso wie die Clusterstruktur ist die Whiskerstruktur mechanisch stabil. Über einen 90°-Peeltest mit einem Tesa®-Testklebeband (Tesa Testband zum Testen von Oberflächen Nr. 07475) lässt sich die Struktur nicht entfernen.Like the cluster structure, the whisker structure is mechanically stable. Over a 90 ° -Peeltest with a Tesa ® -Testklebeband (Tesa test tape for testing surfaces no. 07475) can not remove the structure.
Die erzeugte Oberfläche (siehe
Bei sämtlichen Messungen zu Wasserkontaktwinkel, Abrollwinkel und Hysterese wurden Dreifach-Messungen durchgeführt. Dazu wurden auf einer beschichteten Platte drei gleichmäßig verteilte Punkte gewählt.All measurements for water contact angle, roll-off angle and hysteresis were performed in triplicate. For this purpose, three uniformly distributed points were selected on a coated plate.
Zur Messung des Kontaktwinkels wurden Wassertropfen mit einem Volumen von 10 µl verwendet. Eine Fotoaufnahme des Tropfens auf der Oberfläche wurde mit Hilfe einer Software ausgewertet. Die Berechnung des Kontaktwinkels erfolgt über die als Tangente 1 (ggf. Laplace) bezeichnete Methode.To measure the contact angle, water drops with a volume of 10 μl were used. A photo of the drop on the surface was evaluated using software. The calculation of the contact angle via the method called tangent 1 (possibly Laplace).
Bei der Abrollwinkelbestimmung wurde die beschichtete Platte mit einem Wassertropfen mit 60 µl Volumen belegt. Die Platte, bzw. das gesamte Gerät, wurde gekippt, bis der Tropfen begann abzurollen. Dieser Winkel ist der Abrollwinkel.When determining the rolling angle, the coated plate was covered with a water droplet with a volume of 60 μl. The plate, or the entire device, was tilted until the drop began to roll off. This angle is the roll-off angle.
Zur Bestimmung der Hysterese wurde die Versuchsplatte mit einem Wassertropfen mit 60 µl Volumen belegt. Die Platte wurde bis kurz vor den Abrollwinkel gekippt. Dabei bilden sich zwei verschiedene Kontaktwinkel aus. Der eine an der dem Gefälle zugewandten, der Andere an der abgewandten Seite. Die Kontaktwinkel wurden auf die oben beschrieben Art bestimmt, jedoch wurde die Methode Tangente 2 zur Berechnung verwendet.To determine the hysteresis, the test plate was covered with a water drop with a volume of 60 μl. The plate was tilted until just before the roll-off angle. In this case, two different contact angles are formed. The one on the slope facing, the other on the opposite side. The contact angles were determined in the manner described above, but the method Tangent 2 was used for the calculation.
Zur Bestimmung von Wasserkontaktwinkel, Abrollwinkel und Hysterese wurden das Tropfenkonturanalyse-System DSA 100 und die Software zur Tropfenkonturanalyse "Drop Shape Analysis 3" für Windows 2000/XP Version 1.50, beides von der Firma Krüss, Hamburg, Deutschland, verwendet.To determine the water contact angle, roll-off angle and hysteresis, the drop contour
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Claims (10)
- Non-stick coating for a surface of a substrate which contains at least one fluoropolymer as an anti-adhesive plastic, characterised by a hierarchical layer structure applied to a microstructured subsurface having a roughness of 2 to 50µm Ra, said hierarchical layer structure having at least one microstructured first layer having microelevations in the range from 2 to 50µm, said first layer containing the at least one fluoropolymer as well as a supplement of 5 to 30% by weight of organic or inorganic particles of SiC, Al2SO3, polyamides and/or PPSO2, and having at least one submicrostructured second layer which overlaps this, the elevations of which are smaller than the elevations of the first microstructured layer.
- Non-stick coating according to claim 1 having a water contact angle CA >= 150°, in particular in connection with a water contact angle hysteresis CAH <= 8° and/or a drainage angle <= 10°.
- Non-stick coating according to claim 1 or 2 having an adhesive tape extraction force which approaches 0.
- Method to generate a non-stick coating in which at least one first microstructured layer having microelevations in the range from 2 to 50µm is applied to a microstructured subsurface having a roughness of 2 to 50µm Ra and a submicrostructured layer is applied thereto, the elevations of which are smaller than the elevations of the first microstructured layer, wherein the at least one first layer is applied by a powder containing at least one fluoropolymer, having a particle size in the range from 500nm - 30µm and which contains an admixture of SiC, Al2SO3, polyamides und/oder PPSO2 with a proportion of 5 to 30% by weight, being applied and heated such that the powder is melted on the subsurface, but the powder particles substantially retain their shape, and wherein a second layer in the form of a finely dispersed fluoropolymer having a particle size of 90 - 300nm is applied to the first layer and the coating is heated such that the particles of the second layer are only melted such that they are connected to the layer lying thereunder, but substantially retain their shape.
- Method according to claim 4, characterised in that the microstructured subsurface is generated by applying a microstructured layer to a macrostructured surface.
- Method according to claim 5, characterised in that the substrate surface is sandblasted to generate the macrostructured surface.
- Method according to claim 5 or 6, characterised in that to generate the macrostructured surface, a macrostructured layer is applied to the substrate, in particular by flame spraying of a metal wire or metal powder, in particular of chromium/nickel wire or of melted chromium/nickel powder.
- Method according to any one of claims 5 to 7, characterised in that the microstructured subsurface is generated by applying oxide ceramics, in particular TiO2 and/or Al2O3, to the macrostructured surface, preferably by thermal spraying.
- Method according to any one of claims 4 to 8, characterised in that the finely dispersed fluoropolymer contains a supplement of whiskers, in particular potassium titanate whiskers, preferably with a proportion of 10 to 40% by weight.
- Method according to any one of claims 4 to 9, characterised in that, before application of the layer structure, a primer layer is applied to the microstructured subsurface, the thickness of which does not exceed 5µm, in particular 1µm.
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DE102009049137A DE102009049137A1 (en) | 2009-10-12 | 2009-10-12 | coating System |
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FR2978340A1 (en) * | 2011-07-25 | 2013-02-01 | Seb Sa | HEATING ARTICLE COMPRISING A THERMOSTABLE COATING MICROSTRUCTURE AND METHOD OF MANUFACTURING SUCH A ARTICLE |
DE102011119731A1 (en) * | 2011-11-30 | 2013-06-06 | Rhenotherm Kunststoffbeschichtungs Gmbh | PEK and / or PEEK-containing coating |
DE102012002608B4 (en) * | 2012-02-13 | 2017-01-19 | Warimex Waren-Import Export Handels-Gmbh | Pan or saucepan |
KR101821324B1 (en) * | 2012-07-13 | 2018-03-08 | 도요세이칸 그룹 홀딩스 가부시키가이샤 | Packaging container with excellent content slipperiness |
DE202012103416U1 (en) | 2012-09-07 | 2012-10-09 | Balluff Gmbh | Coated sensor or RFID housing |
DE202012103420U1 (en) | 2012-09-07 | 2012-10-09 | Balluff Gmbh | Coated sensor or RFID housing |
US20140069708A1 (en) * | 2012-09-07 | 2014-03-13 | Jörg Gross | Coated sensor or rfid-housing |
DE202012103418U1 (en) | 2012-09-07 | 2012-10-09 | Balluff Gmbh | Coated sensor or RFID housing |
DE202012103419U1 (en) | 2012-09-07 | 2012-10-09 | Balluff Gmbh | Coated sensor or RFID housing |
DE102013104646A1 (en) | 2013-05-06 | 2014-11-06 | Saeed Isfahani | Ceramic coating of plastic |
US9809712B2 (en) * | 2013-11-26 | 2017-11-07 | Baker Hughes, A Ge Company, Llc | Hydrophobic and oleophobic coatings |
KR101490321B1 (en) * | 2014-06-16 | 2015-02-11 | 김영 | Kitchen apparatus coated dot and preparing thereof |
DE102016205318A1 (en) * | 2016-03-31 | 2017-10-05 | BSH Hausgeräte GmbH | Surface coating for high-quality white and / or gray goods |
DE102022121015B3 (en) | 2022-08-19 | 2024-02-15 | Stc Spinnzwirn Gmbh | Fibrillation roller and fibrillation process |
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