Patent Application
20090130410
This invention relates to a stainless steel sheet coated on at least one of its faces with a self-cleaning coating, and the method for manufacture of such a coated sheet.
For reasons of both cleanliness and hygiene, it is essential to prevent soiling and to reduce the adherence of microorganisms on the surfaces, for example, of buildings and equipment in the food-processing industry or in the pharmaceutical industry. Stainless steel generally is used for this type of application, because this material has a good resistance to corrosion and can be cleaned easily, for example with water with detergent added.
In order to reduce the maintenance of such surfaces, and to avoid the use of detergent harmful to the environment, it is known to coat them with a coating of titanium dioxide TiO2, preferably in its anatase crystalline form. In fact, when it is subjected to UV radiation (radiation having a wavelength less than 380 nm), for example during exposure to the light from a fluorescent source or to sunlight, the titanium dioxide has an activity at once photo-catalytic and super-hydrophilic. The photo-catalytic activity makes possible the partial or total degradation of the organic compounds present on the surface. The photo-induced super-hydrophilic activity ensures the self-cleaning capability of the surface, insofar as it allows washing away of the residual organic compounds by mere rinsing with water without addition of detergents, or by the rain. In the absence of UV radiation, however, the surfaces treated with this type of coating rapidly lose their photo-catalytic and super-hydrophilic activity.
Titanium dioxide doped with nitrogen, obtained through incorporation of a small quantity of nitrogen in the titanium dioxide in its anatase form, has a photo-catalytic and super-hydrophilic activity when it is exposed to a visible luminous radiation (wavelength ranging between 400 and 700 nm). In the absence of visible light, however, the surfaces coated with titanium dioxide doped with nitrogen also rapidly lose their photo-catalytic and super-hydrophilic activity.
The coatings of the prior art therefore have the drawback of losing their self-cleaning nature in the absence of exposure to a UV radiation or to a visible luminous radiation, as the case may be, which can be restored only after another exposure either to a UV radiation or to a visible luminous radiation.
It just so happens that most of the equipment used in the food-processing industry, such as, for example, collective cooking installations, domestic appliances and electrical household appliances often are used or stored in rooms devoid of UV light, or even of visible light, and the coatings cited previously are ineffective for reducing or facilitating the maintenance thereof.
The purpose of this invention is to remedy the drawbacks of the prior-art coatings and to make available a stainless steel sheet coated with a coating having a super-hydrophily lasting for at least three weeks, without its being necessary to subject it to an exposure to UV radiation or to visible luminous radiation in order to restore the super-hydrophily of the coating.
The super-hydrophily of a surface is quantified by the evaluation of the angle of contact of pure water at the surface. Stainless steel has an angle of contact of pure water on the order of 600. Thus, if water is poured over stainless steel, droplets of water form. On a surface having a superior hydrophily, the droplets of water flatten out. This is what is seen on certain types of glass having an angle of contact of pure water on the order of 30°. In the sense of this invention, there is understood by super-hydrophilic surface a surface having an angle of contact of water equal to 0°, which allows the water to form a uniform film of water on the surface.
The invention therefore has as an object a stainless steel sheet coated on at least one of its faces with a coating comprising, in the order starting from the surface of the said sheet:
The coating according to the invention increases the wetting capability of the water without its being necessary to expose it to UV radiation or visible luminous radiation. Because of the super-hydrophilic nature of the said coating, the water is distributed uniformly over the surface of the treated stainless steel, and forms a uniform film of water. Moreover, if the surface is vertical or oblique, the film of water eliminates a portion of the impurities that are deposited on the surface, by flowing along the surface.
Finally, when the surface dries, the traces of water that usually are found on untreated surfaces are avoided, still because of the super-hydrophilic nature of the coating.
The sheet according to the invention also may comprise the following characteristics:
The invention also has as an object a method for manufacture of this coated stainless steel sheet, comprising the successive steps consisting in:
The method according to the invention also may comprise the following characteristics:
The invention also has as an object an installation for the food-processing industry or a prefabricated section for a building made from this coated stainless steel sheet. It likewise has as an object the use of this coated stainless steel sheet in order to remove the dirt adhering to the coating by washing with water or with rainwater, without its being necessary to add a detergent to the water, and without its being necessary to subject the said sheet to a UV radiation or to a visible luminous radiation.
Finally, the intervention has as an object the intermediate product that can be obtained, that is, a stainless steel sheet coated on at least one of its faces, with a coating comprising, in the order starting from the surface of the said sheet:
The characteristics and advantages of the invention will become more apparent in the course of the description that will follow, given by way of non-limitative example.
The stainless steel sheet according to the invention is coated with a coating having a natural super-hydrophily lasting over time, even if it is kept in darkness for more than three weeks, without its being necessary to subject it to a UV or visible luminous radiation in order to activate the super-hydrophily or to restore it. For this purpose, the sheet is coated on at least one of its faces with a coating comprising, in the order starting from the surface of the steel, a barrier layer having a thickness in excess of 5 nm, a porous TiOx oxide layer having a thickness ranging between 5 and 1000 nm and an upper layer of silicon oxide or oxy-hydroxide SiOx having a thickness in excess of 5 nm.
The inventors demonstrated that in order to impart to the sheet a super-hydrophilic nature lasting over time, the porous layer of TiOx should have a voluminal porosity ranging between 10 and 50% and a mean pore size ranging between 0.5 and 100 nm. Preferably, the voluminal porosity of the TiOx layer ranges between 20 and 40% and the mean pore size ranges between 1 and 20 nm.
The voluminal porosity is estimated from the index of refraction of the TiOx layer using the following Lorentz-Lorenz formula:
1−P/100=(n2−1)/(N2−1)×(N2+2)/(n2+2),
The index of refraction is measured at the wavelength of 632 nm by means of a Sentech ellipsometer.
The pore size is estimated by a surface imaging using a scanning electron microscope with ZEISS Ultra 55 field effect.
Not wishing to be bound by any theory, the inventors believe that the enhanced super-hydrophilic properties obtained according to the invention are based on the combined SiOx—TiOx planar interface effects between the upper SiOx layer and the lower TiOx layer. As it happens, prior to deposition of the upper SiOx layer, the TiOx layer has an RMS roughness ranging between 0.5 and 50 nm, and preferably between 1 and 20 nm. Thus, by increasing the RMS roughness and the porosity of the TiOx layer, the contact surface at the interface is increased, and the planar interface effects can be enhanced. The inventors established, however, that for an RMS roughness in excess of 50 nm, a voluminal porosity in excess of 50%, and a pore size in excess of 100 nm, the optical quality and the mechanical resistance of the TiOx layer decrease markedly. A high optical quality of the TiOx layer means that the said layer does not lead to any optical loss through diffusion of the light, which makes it possible to preserve the surface appearance of the steel and, for example, to preserve the shiny appearance of a steel sheet that might have been polished beforehand. According to the invention, the mechanical resistance of the said TiOx layer preferably is at least equal to that of the steel sheet; that makes it possible, in particular, to obtain a coating resistant to scratches and impacts. When the RMS roughness is less than 5 nm, the voluminal porosity less than 10% and the mean pore size less than 0.5 nm, the inventors did not observe any significant long-term lasting quality of the super-hydrophily.
The RMS roughness corresponds to a mean quadratic roughness defined as being the quadratic mean of the variations in the roughness profile in relation to a mean line within a base length. The RMS roughness is measured by means of a Digital Atomic Power Multimode Nanoscope Instrument.
The titanium oxide TiOx may be titanium dioxide, and may be in its amorphous form, or its rutile or anatase crystalline form, or a combination of these forms. The best results in terms of super-hydrophily, however, were obtained when the titanium dioxide was in its anatase crystalline form. The layer of titanium oxide TiOx is deposited on the barrier layer, preferably by a sol-gel deposition method. The sol-gel deposition method has the advantage of making it possible to form, in a single deposition step, a TiOx layer having a uniform thickness ranging between 20 and 200 nm, and not having any cracks. It also has the advantage of making it possible to control the porosity of the TiOx layer as well as the mean size of the pores. In addition, this deposition method makes it possible to produce coatings having a high homogeneity and a high purity.
For this purpose, a liquid solution that may be either a polymeric sol, or advantageously a crystalline suspension, is deposited on the surface of the said barrier layer. In fact, the inventors observed that at equal TiOx layer thickness, the use of crystalline suspension made it possible to impart to the sheet a super-hydrophily superior to that obtained with a polymeric sol.
The polymeric sol may comprise 0.1 to 0.6 mole/l of an organometallic precursor of titanium and a solvent. The organometallic precursor of titanium may be a titanium alkoxide Ti(OR)4 in which R is an alkyl chain containing 1 to 4 carbon atoms. The organometallic precursor of titanium preferably is titanium isopropoxide.
The crystalline suspension may comprise 0.1 to 0.4 mole/l of nano-crystallites of titanium dioxide dispersed in a dispersive solvent such as, for example, water or an alcohol. The crystallites of titanium dioxide preferably are in the anatase crystalline form.
The deposition of the polymeric sol or of the crystalline suspension is performed by a liquid-phase coating technique, for example by dipping, by spraying or by centrifugal application. In order to accelerate the crystallization of the TiOx layer into its anatase or rutile crystalline form, in the case of a polymeric sol, or to evaporate the solvent more rapidly in the case of a crystalline suspension, the TiOx layer furthermore may be subjected to a thermal treatment by bringing the sheet to a temperature ranging between 100 and 600° C., and maintaining it at this temperature for a period ranging between 5 and 120 minutes.
The thickness of the SiOx upper layer is not particularly limited; the inventors, however, noted that beyond 1000 nm, the super-hydrophilic nature of the coating is not improved.
Insofar as the upper layer of the coating is likely to be subjected to friction, it is advantageous that the SiOx upper layer be dense, that is, that it have a voluminal porosity close to 0%, which imparts a markedly improved abrasion resistance to the coating. In fact, the more porous the SiOx layer, the weaker its mechanical resistance and the more sensitive it is to scratches.
The upper layer of silicon oxide SiOx preferably is a layer of silicon dioxide SiO2.
After having formed the TiOx layer on the barrier layer, the upper layer of silicon oxide or oxy-hydroxide SiOx preferably is deposited by a sol-gel method. This sol-gel method of deposition has the advantage of making it possible to form, in a single deposition step, an SiOx layer having a uniform thickness ranging between 20 and 850 nm, and not having any cracks. For this purpose, a liquid solution consisting of a polymeric sol comprising 0.2 to 2 mole/l of a precursor and a solvent is deposited on the surface of the said TiOx layer.
The precursor may be an organometallic compound of silicon, or even a silicon salt. It reacts by hydrolysis and by polycondensation to form SiOx.
The organometallic compound of silicon may be a silicon alkoxide Si(OR)4 in which R is an alkyl chain containing 1 to 4 carbon atoms. The preferred precursor is tetraethoxy orthosilicate.
The silicon salt may be, for example, a nitrate or a chloride of silicon.
The deposition of the liquid solution is performed by a liquid-phase coating technique, for example by dipping, by spraying or by centrifugal application of the solution.
The sol-gel deposition method by the polymeric process furthermore has the advantage of forming a dense SiOx layer, that is, an SiOx layer the voluminal porosity of which is close to 0%, having an excellent mechanical resistance.
In order to accelerate the densification of the layer and to evaporate the solvent more rapidly, the SiOx layer furthermore can be subjected to a thermal treatment by bringing the sheet to a temperature ranging between 300 and 600° C., and maintaining it at this temperature for a period ranging between 5 and 120 minutes.
The barrier layer included between the steel sheet and the layer of titanium oxide TiOx makes it possible to avoid diffusion of the metallic elements of the steel into the TiOx layer. In fact, the inventors became aware that, in the absence of this barrier layer, the metallic elements of the steel, such as iron, for example, contaminate the titanium oxide layer and that the effectiveness of the coating in terms of super-hydrophily thereby are rapidly reduced over the course of time. The inventors also noted that, apart from its role as a diffusion barrier, this layer also contributes to an enhanced super-hydrophily by creating an additional planar interface with the titanium oxide layer.
The barrier layer has a thickness ranging between 5 and 1000 nm. In fact, the inventors noted that below 5 nm, the barrier effect is insufficient and the metallic elements of the steel migrate into the upper TiOx layer, which damages the super-hydrophily of the coating. Beyond 1000 nm, the effectiveness of the barrier layer is not improved.
The barrier layer may be made up of at least one layer of metallic oxide or oxy-hydroxide MOx, preferably chosen from among the oxides of silicon, tin, aluminum, alone or in combination, and advantageously chosen from among SiO2, SnO2, Al2O3, alone or in combination. It advantageously is made up of a layer of silicon oxide SiO2. The barrier layer also may be made up of at least one layer of metallic nitride or oxy-nitride NMx, such as, for example, a layer of silicon nitride or oxy-nitride.
The barrier layer of metallic oxide or oxy-hydroxide MOx preferably is deposited, on at least one of the faces of the sheet, by a sol-gel deposition method, after having subjected a stainless steel sheet to a thermal treatment of the bright-annealing or pickled-hardening type, depending on whether one is trying to obtain a bright surface or, on the contrary, a matte surface. The sol-gel deposition method is preferred to the other deposition methods because it makes it possible to form, in a single deposition step, an MOx layer having a uniform thickness ranging between 20 and 850 nm and not having any cracks. In addition, this deposition method makes it possible to produce coatings having a high homogeneity and a high purity. For this purpose, a liquid solution consisting of a polymeric sol comprising 0.2 to 2 mole/l of at least one precursor and a solvent is deposited on at least one of the faces of the sheet by a liquid-phase coating technique, for example by dipping, by spraying or by centrifugal application of the solution.
The precursor may be an organometallic compound, or even a metal nitrate or chloride. It reacts by hydrolysis and by polycondensation to form MOx.
The organometallic precursor may be a metal alkoxide M(OR)3 or M(OR)4, in which M is chosen from among silicon, tin and aluminum, and R is an alkyl chain containing 1 to 4 carbon atoms. The preferred organometallic precursor is tetraethoxy orthosilicate.
The precursor consisting of a metal nitrate or chloride may be a silicon nitrate or a silicon chloride.
In order to accelerate the densification of the layer and to evaporate the solvent more rapidly, the barrier layer furthermore may be subjected to a thermal treatment by bringing the sheet to a temperature ranging between 300 and 600° C., and maintaining it at this temperature for a period ranging between 5 and 120 minutes.
The barrier layer of metallic nitride or oxy-nitride NMx may be deposited by any conventional method making it possible to obtain a thin coating layer.
The invention now is going to be illustrated by examples presented by way of indication, not limitation.
For that, a first batch of samples (samples A) cut out in a sheet made of grade 304 2R stainless steel were coated with a layer of SiO2 by a centrifugal application method using a polymeric sol comprising 1.5 mole/l of tetraethoxy orthosilicate, absolute ethanol, 3/3 mole/l of deionized water and hydrochloric acid to adjust the pH of the polymeric sol to 3.5. The coated samples then were brought to 500° C., and maintained at this temperature for 120 minutes, in order to form a layer of silicon dioxide SiO2 with thickness 190 nm.
A second batch of samples (samples B and D) cut out in the same sheet made of grade 304 2R stainless steel which previously were coated with a two-layer coating comprising a first layer of TiO2 in contact with the surface of the steel, and an upper layer of SiO2.
A third batch of samples (samples C and E) also cut out in the same sheet made of grade 304 2R stainless steel were coated with a three-layer coating according to the invention comprising a first layer of SiO2 in contact with the surface of the steel, an intermediate layer of TiO2 and an upper layer of SiO2.
The thicknesses of the SiO2 layers are 190 nm for each of the batches B, C, D and E. The SiO2 layers of the two-layer and three-layer coatings are deposited according to the same procedure as that indicated previously for the first batch of samples, and they are treated thermally at 500° C. for 120 minutes after each layer deposition.
The TiO2 layer is formed by sol-gel deposition from:
In both cases, the TiO2 layer was treated thermally at 500° C., for 120 minutes, and the characterizations by X-ray diffraction show that they are made up of crystallites of anatase.
The TiO2 layer obtained by deposition of the crystalline suspension and treated at 500° C. for 120 minutes, has a thickness of 40 nm, an RMS roughness of 5 nm (before deposition of the SiO2 upper layer), a mean pore size of 15 nm, and a voluminal porosity of 30%.
The TiO2 layer obtained by deposition of a polymeric sol and treated at 500° C. for 120 minutes, has a thickness of 160 nm, an RMS roughness of 1 nm (before deposition of the SiO2 upper layer), a mean pore size of 5 nm, and a voluminal porosity of 15%.
In this way, the following samples are obtained:
After having formed the one-, two- or three-layer coatings, the samples are allowed to age by keeping them in darkness, that is, in the absence of any luminous radiation for 84 days. Their super-hydrophily is evaluated regularly, by measuring the angle of contact that drops of pure water form on the coating, by means of a video camera connected to a KRUSS G 10 goniometer. The results of the measurements are consolidated in Table I.
The results of Table I clearly show that the stainless steel sheets coated with three-layer coatings according to the invention have a natural and long-lasting super-hydrophily which single SiO2 coatings deposited on stainless steel sheets do not possess. Not wishing to be bound by any theory, the inventors believe that this effect is linked to the presence of SiO2—TiO2-type planar interfaces.
The longer lasting quality of super-hydrophily of a stainless steel sheet coated with a three-layer coating from a crystalline suspension of TiO2 shows the influence of the method of production of the coatings which makes it possible to verify a porosity and a roughness appropriate to the SiO2—TiO2 interface and in this way to increase the surface specific to this interface.
Irrespective of the method of production, the shorter lasting quality of super hydrophily of the stainless steel sheet coated with two-layer coatings is attributed to the contamination of the TiO2 by elements deriving from the steel at the time of liquid-phase deposition of TiO2 and/or at the time of thermal treatment. The two-layer coatings formed in this way do not have enhanced hydrophilic properties in comparison with a single layer of SiO2 deposited on a stainless steel sheet. The contamination of the TiO2 layer in a two-layer coating by elements originating from the steel has no positive influence on the super-hydrophilic properties.
Furthermore, the inventors noted that natural super-hydrophily without UV radiation and without exposure to visible light disappears at the end of a certain period of ageing. The super hydrophily of the two-layer coating obtained from a crystalline suspension according to the invention is markedly reduced at the end of 14 days, and the angle of contact of water measured at the surface of this coating after 84 days of ageing is 14°. The super-hydrophily is far less reduced at the end of 84 days for the tree-layer coating obtained from a crystalline suspension according to the invention and the angle of contact measured after this ageing is 4.5°.
The reduction of the super-hydrophily is attributed to the contamination of the outer SiO2 layer by carbonaceous species deriving from the ambient atmosphere. The inventors became aware that the super-hydrophily of the three-layer coatings according to the invention could be restored easily by spraying of the coating, for at least one minute, with water at a temperature ranging between 20 and 30° C., without UV radiation and without exposure to visible light.
After 84 days of maintenance in darkness, samples B and C thus were sprayed with a flow of water at 25° C., for 1 min, then were dried with a compressed gas. The angle of contact formed by the drops of pure water deposited on the coating then was measured by means of a video camera connected to a KRUSS G 10 goniometer:
The results are consolidated in Table II
The difference in behavior of samples B and C clearly shows that a three-layer coating according to the invention cuts down carbonaceous contamination of the stainless steel during a prolonged ageing. That makes it possible to eliminate this slight contamination easily by a mere rinsing with water. In the case of a two-layer coating, the stainless steel sheet becomes contaminated more rapidly, which precludes effective elimination of the carbonaceous contamination under the same operating conditions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 06290367.9 | Mar 2006 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/FR2007/000070 | 1/15/2007 | WO | 00 | 12/10/2008 |
