WO2005075112A1 - Revetement de surface aux proprietes inhibant la formation de rosee et de glace - Google Patents

Revetement de surface aux proprietes inhibant la formation de rosee et de glace Download PDF

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Publication number
WO2005075112A1
WO2005075112A1 PCT/DK2005/000088 DK2005000088W WO2005075112A1 WO 2005075112 A1 WO2005075112 A1 WO 2005075112A1 DK 2005000088 W DK2005000088 W DK 2005000088W WO 2005075112 A1 WO2005075112 A1 WO 2005075112A1
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WO
WIPO (PCT)
Prior art keywords
property
coating
energy level
area
hydrophobic
Prior art date
Application number
PCT/DK2005/000088
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English (en)
Inventor
Thomas Zweig
Original Assignee
Multi Sign A/S
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Multi Sign A/S filed Critical Multi Sign A/S
Publication of WO2005075112A1 publication Critical patent/WO2005075112A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • 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

Definitions

  • the present invention relates to surface coatings with anti-dew, dirt repellent, anti-graffiti and ice non-stick properties.
  • Dew is created when a surface temperature is low and the air chills to the dew point so that the water vapour condenses to a liquid.
  • very small water droplets are formed at the surface structure.
  • the contact angle and drop diameter depend strongly from the surface energy at the surface structure.
  • the negative effect of dew formation at surfaces is due to the water droplets created and their influence on the optical properties.
  • One way to undergo dew formation at technical surfaces is by heating these surfaces up to more than 3 °C above the actual dew point. This may be difficult to realize in practise and is very uneconomical.
  • Another way to undergo dew formation at such technical surfaces is to use high energetic surfaces with hydrophilic property, so that the droplets formation becomes evenly distributed on the surface and therefore do not affect the contact angle.
  • Ice is formed at a surface when the surface temperature is below the freezing point, and the ambient temperature is close to or below the freezing point too.
  • the characteristics and form of ice depend on the surface temperature, the super cooling rate, the ambient temperature, the relative humidity and the air convection around the surfaces. Hydrophobic surfaces with low surface energy have often been selected for the design of surfaces with ice non-stick property.
  • a relative large amount of coating systems have been developed, wherein mainly water repellent materials with a very low surface tension, such as PTFE (Teflon) or Polyethylene have been chosen. Besides from being ice repellent materials, they have also shown to have dirt and graffiti repellent properties.
  • US 6,696,225 and WO 99/57185 describe surfaces which consist of a combination of surface areas having hydrophilic and hydrophobic properties, where the hydrophilic areas are embedded into the pre-fabricated surface layers having hydrophobic properties. Through such a combination the surfaces have both anti dew as well as anti ice properties, where the hydrophilic areas act as a nucleation sites with anti-dew property, and the hydrophobic areas there between as anti ice areas.
  • the problem with the surfaces as dis- closed in these references it the weak binding energy between the areas having the hydrophilic properties and the substrate since these are embedded into the surface.
  • the present invention relates to a heterogeneous surface structure having hydrophobic and simultaneously hydrophilic properties adapted to maintain high optical property of the surface under different conditions, comprising:
  • said at least first and second surface areas are hybrid layers, containing covalently bounded organic and inorganic phase.
  • the energy level of at least a first surface area is significantly or much higher than the surface energy of water, 72,8mJ/meter, thereby having anti-dew property since the dew will be uniformly distributed on the surface.
  • the negative effect of dew water droplets onto optical properties of surfaces may therefore be avoided. If the surface has a retroreflective pattern, the property of said pattern is obtained. It is essential that the distance between the nucleation areas is large enough so that the ice crystals at the nucleation areas do not get in contact and form a compact ice layer.
  • the surface energy of at least a second surface area is signifi- cantly lower than the surface energy of water, thereby having ice non-stick property with simultaneous dirt repellent and anti-graffiti property.
  • the arrangement of said areas is predefined, e.g. has a matrix like structure, so that a homogeneous property of the surface structure is obtained.
  • said at least second surface area is a heterogeneous surface with nucleation points having higher surface energy than at the area between said nucleation points, preferably higher than the surface energy of water, 72,8mJ/meter.
  • the ice crystallisation at said areas is thereby further localized and the possible ice adhesion reduced.
  • said at least one first surface area is comprised in a sur- face layer having said hydrophilic property onto which said at least one second surface area is coated. In that way, as strong bounding is obtained be- tween the hydrophilic areas since these areas are a part of a complete hydrophilic layer.
  • the area ratio between the first and the second areas can play an important role.
  • the area with hydrophobic property ice non-stick
  • hydrophilic property anti-dew
  • the present invention relates to a method for coating a heterogeneous surface structure having hydrophobic and simultaneously hydrophilic property adapted to maintain high optical property of the surface under different conditions, the method comprising the following steps:
  • said at least first and second surface areas are hybrid layers cova- lently cross linked to each other.
  • coating the surface area with said first material comprises coating the whole surface area with said first material and subse- quently coating the surface with said second material such that said heterogeneous surface structure is obtained.
  • said first material is a material having high surface energy and anti-dew property
  • said second material is a material having low surface energy having ice non-stick prop- erty.
  • the coating comprises coating the surface area with said first material such that a predefined area of said first material is obtained, and subsequently coating the surface with said second material such that a predefined area of said second material is obtained, thereby defining said heterogeneous surface structure.
  • the coating comprises coating the surface areas with said first and second materials simultaneously.
  • the present invention relates to a printing device adapted for printing and coating a surface of a material such that a heterogeneous surface structure having hydrophobic and simultaneously hydro- philic property is obtained, comprising:
  • a computer system is adapted to control said printing and said coating sections based on instructions relating to the printing and the coating of the surface.
  • the printing section is a laser printer and the coating section is based on an ink jet printing, whereby the inkjet patrons comprise a material having a low and high surface energy level, and thereby ice non-stick and anti-dew properties.
  • the surface of said material can be a metal surface or any other kind of material, such as all types of plastic material, and may have a retroreflective pattern.
  • Figs. 1-3 show heterogeneous surface structures having both ice nonstick, and simultaneously anti-dew properties in connection with dirt deposition and graffiti
  • Figs. 4-6 show the surface structures from Figs. 1-3, wherein the structures are implemented as traffic signs, and
  • Fig. 7 shows a printing device adapted for printing and coating a surface structure with anti-dew and ice non-stick property
  • Figs. 1-3 show three different types of heterogeneous surface structures having both ice non-stick properties, and simultaneously anti-dew properties in connection with dirt deposition and graffiti. This property is obtained by creating a surface structure comprising surface areas of different surface energy levels by means of adding different type of coatings on the surface.
  • nucleation areas By creating a surface structure with surface areas 2-7 having a high or very high surface energy in combination with creation of surface areas having a low or very low surface energy, nucleation areas are created where ice crys- tallization mainly takes place. At these nucleation areas the ice crystallization becomes localized. This is because the Gibbs free energy is lower at the areas having higher surface energy, which makes the ice crystallization more favorable.
  • a low or very low surface energy is lower or much lower than the surface energy of water, 72,8mJ/meter, whereas a high or very high surface energy is higher or much higher than the surface energy of water.
  • the adhesion of the generated ice crystals is reduced both in strength and contact area compared to the generation of a compact ice layer.
  • the areas of high surface energy cause the formation of a thin water layer instead of forming water droplets under dew conditions, which prevents the negative effect of the dew water droplets on the optical properties of the surfaces.
  • the different areas of different energy levels 2, 3 are distributed in a predefined way forming a matrix-like surface structure, wherein area 2 could have a second energy level and area 3 a first energy level having a higher energy than that at the first energy levels, and thereby defining the nucleation areas.
  • the energy level at area 3 has a surface energy being significantly or much higher than the surface energy of water, 72,8mJ/meter, thereby having an anti-dew property since the dew will be uniformly distributed on the surface, whereas the surface energy at area 2 is lower or much lower than the surface energy of water, thereby having ice non-stick property.
  • the surface energies at the surface areas 3 could be in the range of 500-5000mJ/meter, whereas the surface energy at areas 2 could be in the range of 5-40mJ7meter. Other energy levels are of course also possi- ble.
  • the surface area 2 is a heterogeneous surface with a plurality of very small nucleation points with dimensions less than 10 microns. Thereby, a stress is created in this area 2 which enhances the ice repelling property. Besides from that it makes the ice crystals at the nuclea- tion areas more localized and thereby hinders a generation of a compact ice layer at the surface.
  • the surfaces can be designed in their anti-dew and ice non-stick, dirt and graffiti non-stick behavior in dependency of the necessary actual conditions. If dew formation is the dominating problem, the area having high surface energy is larger. If ice formation, dirt deposition or graffiti is the dominating problem, the area having high surface energy will be reduced in size and localized in order to achieve the described non-stick effect.
  • Figs. 2 and 3 show similar surface structures as shown in Fig. 1 , wherein in Fig. 2 the areas 5, 6 have different symmetry, but are arranged in a predefined way, whereas in Fig. 3 the areas 6, 7 are distributed randomly.
  • the ice formation at the surfaces is, as an example, the main problem. Therefore, the total anti-dew area 5, having a high energy level, is larger than the low energy level for ice non-stick area 6.
  • Other symmetries of the anti-dew or non-stick areas are of course also possible.
  • the energy levels have been chosen such that surface structures each have two different energy levels.
  • the num- ber of energy levels may also be more than two in the same surface structure.
  • Figs. 4-6 show the surface structures from Figs. 1-3, wherein the structures are implemented as traffic signs, showing Aarhus 39 km 8.
  • the coatings can, in one embodiment, be synthesized by sol-gel technology, involving hydrolysis, condensation and additional reactions from a combination of polymerized molecular metal alkoxides Me(OR)4, silicon alkoxides Si(OR)4, organic modified silicone alkoxides (R- Si(OR)3) and furthermore organic polymers.
  • the metal atom can be found in the group of Ti, Al, Zr.
  • hydrophilic surface area or segments metal alkoxides and silicon alkoxides with reactive hydrophilic functional end groups like amino, carboxyl or hydroxyl are applied.
  • the hydrophobic surface areas are achieved with silicone alkoxides with non-polar hydrophobic functional end groups like alkyl, aryl or fluoralkyl.
  • the different sols are blended together in a certain amount and time. Blending different sols together can be done with different ratios, e.g. ratios 100/1 , 10/1 , 1/1 , 1/2, 1/10 etc., depending on whether dew or ice is the main problem. As an example, if dew is the main problem it would be preferred to have sol with dominating hydrophilic property, whereas where ice is the main problem it would be preferred to use sol having dominantly hydrophobic property (e.g. ratio 10/1 of sols with hydrophobic property and sol with hydrophilic property). Afterwards, the sol blending is cross-linked by condensation reaction due to coating the surface with the blended sols.
  • this can be done by spraying the surface with said blended sols, by rolling the surface with said blended sols, by printing it on the surface or by using a brush.
  • cross-linking with additional polymers, with other reactive functional groups, hydrophilic or hydrophobic is possible.
  • Another method to obtain such a surface structure is by using a printing technology e.g. laser printer or inkjet printer.
  • a printing technology e.g. laser printer or inkjet printer.
  • Fig. 7 shows a laser printer adapted for printing on metal surfaces and coat- ing the surface structure with anti-dew and ice non-stick property, comprising a printing section 10 and a coating section 11.
  • the first step would be to print the sign, i.e. Aar- hus 39 km in the printing section.
  • the second step is coating the surface at the coating section 11 of the printing device, so that the surface becomes said structure having anti-dew and ice non-stick property. As an example this could be done by using ink jet printing.
  • the coating could be based on different kind of criteria.
  • One criterion could be that the surface is to be used as a traffic sign.
  • Another criterion could be the size of the sign, the number of letters in the sign, the size of the letters and the location of the letters on the surface.
  • the surface is initially coated with a material having anti- dew property (hydrophilic property). Subsequently, the material having ice non-stick property (hydrophobic property) is printed on the anti-dew layer, such that a surface structure having a predefined structure is obtained, such as the one shown in Fig. 1-3.
  • a material having anti- dew property hydrophilic property
  • the material having ice non-stick property hydrophobic property
  • the materials having anti-dew property and ice nonstick property are printed on the surface in a predefined way, either sepa- rately or simultaneously.
  • the thickness of the applied coatings is in one embodiment less than 10 microns. Due to the formation of an inorganic-organic network covalent cross- linked to the metal or polymer surface, a very good mechanical and abrasion resistant surface is realized. Also, due to the covalent bonding, a coating de- laminating will not occur.

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Abstract

L'invention porte sur une structure de surface hétérogène possédant des propriétés à la fois hydrophobes et hydrophiles qui permettent de préserver une propriété optique élevée de ladite surface dans des conditions différentes. La structure de surface de l'invention comprend au moins une première zone de surface possédant un premier niveau d'énergie de surface, le niveau d'énergie de surface étant tel que l'on obtient une propriété hydrophobe au moins sur ladite zone de surface, et au moins une seconde zone de surface possédant un second niveau d'énergie de surface, le second niveau d'énergie de surface étant supérieur au premier niveau d'énergie de surface, et le niveau d'énergie étant tel que l'on obtient une propriété hydrophobe au moins sur ladite seconde zone de surface, la différence de niveau d'énergie entre la première et la seconde zone de surface étant apte à empêcher la formation d'une couche de glace compacte, lesdites première et seconde zone de surface étant constituées de couches hybrides contenant des phases organique et inorganique liées par covalence.
PCT/DK2005/000088 2004-02-10 2005-02-10 Revetement de surface aux proprietes inhibant la formation de rosee et de glace WO2005075112A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA200400199 2004-02-10
DKPA200400199 2004-02-10

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WO2005075112A1 true WO2005075112A1 (fr) 2005-08-18

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2430201A (en) * 2005-09-20 2007-03-21 Seiko Epson Corp Substrate surface with different hydrophilic or oleophilic areas
DE102009024320A1 (de) 2009-06-03 2010-12-09 Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V. Beschichtungen mit eisabweisenden und gefrierpunktsenkenden Eigenschaften, Verfahren zu deren Herstellung und Verwendung
US7851344B2 (en) 2005-09-20 2010-12-14 Seiko Epson Corporation Method of producing a substrate having areas of different hydrophilicity and/or oleophilicity on the same surface
DE102012208653A1 (de) 2011-05-27 2012-11-29 Technische Universität Bergakademie Freiberg Oberflächenbeschichtung mit eisabweisenden Eigenschaften
US9029491B2 (en) 2010-12-22 2015-05-12 Teknologisk Institut Repellent coating composition and coating, method for making and uses thereof
WO2015166191A1 (fr) 2014-04-30 2015-11-05 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé d'épuration, de refroidissement et de séparation d'un mélange gazeux et appareil associé
EP2952266A1 (fr) * 2014-06-03 2015-12-09 Whirlpool Corporation Procédé de traitement de surfaces, notamment de surfaces de carreaux ou analogues et carreaux produits selon ce procédé

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903389A1 (fr) * 1996-05-31 1999-03-24 Toto Ltd. Element anti-encrassement et composition pour revetement anti-encrassement
WO1999057185A1 (fr) * 1998-05-04 1999-11-11 3M Innovative Properties Company Article a motifs comprenant des zones de surface alternees hydrophiles et hydrophobes
WO2002090459A1 (fr) * 2001-05-08 2002-11-14 Danish Technological Institute Energy, Refrigeration And Heat Pump Technology Revetement antiadhesif glaçogene
DE10128013A1 (de) * 2001-06-05 2002-12-12 Uwe Slabke Verfahren zur Verwendung von hydrophilen Schichten/Folien zur Verhinderung der Tau- und Reifbildung auf Verkehrszeichen
WO2004086150A1 (fr) * 2003-03-26 2004-10-07 Multi Sign A/S Impression sur du metal par poudrage electrostatique selectif
US20040241451A1 (en) * 2003-05-29 2004-12-02 3M Innovative Properties Company Method for modifying the surface of a substrate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903389A1 (fr) * 1996-05-31 1999-03-24 Toto Ltd. Element anti-encrassement et composition pour revetement anti-encrassement
WO1999057185A1 (fr) * 1998-05-04 1999-11-11 3M Innovative Properties Company Article a motifs comprenant des zones de surface alternees hydrophiles et hydrophobes
WO2002090459A1 (fr) * 2001-05-08 2002-11-14 Danish Technological Institute Energy, Refrigeration And Heat Pump Technology Revetement antiadhesif glaçogene
DE10128013A1 (de) * 2001-06-05 2002-12-12 Uwe Slabke Verfahren zur Verwendung von hydrophilen Schichten/Folien zur Verhinderung der Tau- und Reifbildung auf Verkehrszeichen
WO2004086150A1 (fr) * 2003-03-26 2004-10-07 Multi Sign A/S Impression sur du metal par poudrage electrostatique selectif
US20040241451A1 (en) * 2003-05-29 2004-12-02 3M Innovative Properties Company Method for modifying the surface of a substrate

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2430201A (en) * 2005-09-20 2007-03-21 Seiko Epson Corp Substrate surface with different hydrophilic or oleophilic areas
US7851344B2 (en) 2005-09-20 2010-12-14 Seiko Epson Corporation Method of producing a substrate having areas of different hydrophilicity and/or oleophilicity on the same surface
DE102009024320A1 (de) 2009-06-03 2010-12-09 Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V. Beschichtungen mit eisabweisenden und gefrierpunktsenkenden Eigenschaften, Verfahren zu deren Herstellung und Verwendung
US9029491B2 (en) 2010-12-22 2015-05-12 Teknologisk Institut Repellent coating composition and coating, method for making and uses thereof
DE102012208653A1 (de) 2011-05-27 2012-11-29 Technische Universität Bergakademie Freiberg Oberflächenbeschichtung mit eisabweisenden Eigenschaften
DE102012208653B4 (de) 2011-05-27 2019-04-25 Technische Universität Bergakademie Freiberg Verfahren zur Herstellung einer Oberflächenbeschichtung mit eisabweisenden Eigenschaften, Oberflächenbeschichtung und deren Verwendung
WO2015166191A1 (fr) 2014-04-30 2015-11-05 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé d'épuration, de refroidissement et de séparation d'un mélange gazeux et appareil associé
FR3020669A1 (fr) * 2014-04-30 2015-11-06 Air Liquide Procede et appareil d’epuration et de refroidissement d’un melange gazeux
EP2952266A1 (fr) * 2014-06-03 2015-12-09 Whirlpool Corporation Procédé de traitement de surfaces, notamment de surfaces de carreaux ou analogues et carreaux produits selon ce procédé

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