Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby
Abstract
A method of coating a substrate, comprising the steps of: forming a first coating layer having an orthorhombic or cubic zirconium crystalline phase on at least a part of the surface of a substrate as a first stage of formation; and - forming a second coating layer of a photoactive material selected from at least one metal oxide or semiconductor metal oxide on the first coating layer defined as a second forming step to provide a coated substrate, in which in the second Forming stage a material with a predetermined crystalline phase is formed and the first coating layer will enhance the development of the predetermined crystalline phase.

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24 claims: 18 independent, 6 dependent
- 1ES 2 301 569 T3 REIVINDICACIONES 1. Un procedimiento de revestir un sustrato, que comprende las etapas de:- formar una primera capa de revestimiento que tiene una fase cristalina ortorrómbica o cúbica de óxido de circonio sobre al menos una parte de la superficie de un sustrato como una primera etapa de formación;y - formar una segunda capa de revestimiento de un material fotoactivo seleccionado de al menos un óxido de metal u óxido de metal semiconductor sobre la primera capa de revestimiento definida como una segunda etapa de formación para proporcionar un sustrato revestido, en el que en la segunda etapa de formación se forma un material con una fase cristalina predeterminada y la primera capa de revestimiento potenciará el desarrollo de la fase cristalina predeterminada.
- 2El procedimiento de la reivindicación 1, en el que la segunda capa de revestimiento comprende óxido de titanio.
- 3El procedimiento de cualquiera de las reivindicaciones precedentes, en el que la segunda etapa de formación incluye la formación de una película de óxido de titanio sobre la película de óxido de circonio, teniendo la película de óxido de titanio fase(s) anatasa y/o rutilo y/o amorfa después de calentamiento.
- 4El procedimiento de la reivindicación 1 que comprende el calentamiento de al menos uno de los sustratos, la primera capa de revestimiento o la segunda capa de revestimiento para que el material de la segunda capa de revestimiento tenga al menos una fase cristalina predeterminada.
- 5El procedimiento de cualquiera de las reivindicaciones precedentes, en el que la primera etapa de formación incluye depositar una película de óxido de circonio en la fase cúbica.
- 6El procedimiento de cualquiera de las reivindicaciones precedentes, en el que la primera y la segunda etapas de formación se llevan a cabo por deposición por pulverización iónica.
- 7El procedimiento de cualquiera de las reivindicaciones precedentes, incluyendo el calentamiento del sustrato a una temperatura en uno o más de los intervalos de temperatura siguientes antes de la formación de la primera capa de revestimiento:21°C a 259°C (70°F a 500°F), más de o igual a 65°C (150°F);93°C a 537°C (200°F a 1000°F);ó 148°C a 259°C (300°F a 500°F).
- 8El procedimiento de cualquiera de las reivindicaciones precedentes, en el que la primera capa de revestimiento tiene un espesor en uno o más de los siguientes intervalos de espesor:mayor o igual a 15 A;mayor o igual a 25 A;mayor de 0 A y menor o igual a 150 A;40 A a 80 A;60 A a 70 A;mayor de o igual a 100 A;mayor de 0 A y menor de 500 A;o mayor de o igual a 400 A.
- 9El procedimiento de cualquiera de las reivindicaciones precedentes, incluyendo el calentamiento del sustrato revestido a una temperatura en uno o más de los intervalos de temperatura:204°C (400°F);mayor o igual a 259°C (500°F), o mayor o igual a 315°C (600°F).
- 10El procedimiento de cualquiera de las reivindicaciones precedentes, en el que la segunda capa de revestimiento tiene un espesor en uno de los siguientes intervalos de espesor:mayor de o igual a 100 A;mayor de o igual 200 A;100 A a 500 A;ó 300 A a 400 A.
- 11El procedimiento de cualquiera de las reivindicaciones precedentes, en el que el sustrato es vidrio.
- 12El procedimiento de cualquiera de las reivindicaciones precedentes, que además incluye la formación de un revestimiento funcional sobre al menos una parte de la superficie de la segunda capa de revestimiento definida como una tercera etapa de formación.
- 13El procedimiento de la reivindicación 12, en el que la segunda y tercera etapa de formación se realizan en el mismo revestidor.
- 14Un artículo que se puede obtener por un procedimiento de cualquiera de las reivindicaciones 1 - 13.
- 15Un artículo, que comprende:- un sustrato;- una primera capa de revestimiento con fase cristalina cúbica u ortorrómbica de óxido de circonio sobre al menos una parte de la superficie del sustrato;y ES 2 301 569 T3 - una segunda capa de revestimiento de un material fotoactivo seleccionado de al menos un óxido de metal u óxido de metal semiconductor sobre la primera capa de revestimiento.
- 16El artículo de la reivindicación 15, en el que la segunda capa de revestimiento tiene un espesor de 100 A a 400 A, preferiblemente de 150 A a 300 A.
- 17El artículo de cualquiera de las reivindicaciones 15 y 16, en el que la segunda capa de revestimiento comprende óxido de titanio.
- 18El artículo de 17, en el que la capa de óxido de titanio está en la(s) fase(s) anatasa, y/o rutilo, y/o amorfa.
- 19El artículo de cualquiera de las reivindicaciones 15 a 18, en el que la capa de óxido de circonio tiene un espesor de 10 A a 200 A, preferiblemente de 25 A a 150 A.
- 20El artículo de cualquiera de las reivindicaciones 15 a 19, en el que la segunda capa de revestimiento es un revestimiento fotoactivo que es fotohidrófilo o fotocatalítico.
- 21El artículo de cualquiera de las reivindicaciones 15 a 20, en el que el sustrato revestido tiene un ángulo de contacto con agua de menos de o igual a 20° después de 60 a 90 minutos de exposición a la radiación electromagnética con una longitud de onda de 340 nm a una intensidad de 24 w/m 2 en la superficie de revestimiento.
- 22El artículo de la reivindicación 21, en el que el ángulo de contacto es inferior a 10°.
- 23El artículo de cualquiera de las reivindicaciones 15-22, en el que el sustrato es vidrio, y el artículo es una luna.
- 24El artículo de la reivindicación 23, siendo éste una ventana.
Independent claims24
340 paragraphs in 27 sections, as filed
ES 2 301 569 T3
DESCRIPTION
Procedures to obtain photoactive coatings and / or crystalline anatase phase of titanium oxides and articles made in this way.
Background of the invention
1. Field of the invention
This invention relates to photoactive coatings and processes for changing or obtaining the phase of a material, for example a crystalline anatase phase of titanium oxide from an amorphous phase of titanium oxide or from titanium metal and, more particularly, to processes for obtaining a photoactively hydrophilic and / or photocatalytic coating, and / or to articles made in this way.
2. Technical considerations
For many substrates, for example glass substrates such as architectural windows, clear car glass, and airplane windows, it is desirable for good visibility that the surface of the substrate is substantially free of surface contaminants, such as organic and inorganic surface contaminants. common, so that their duration is as long as possible. Traditionally, this means that such surfaces are cleaned frequently. This cleaning operation is normally carried out by manually cleaning the surface with or without the aid of chemical cleaning solutions. This approach can be labor, time, and / or cost intensive. Accordingly, procedures are needed for cleaning glass substrates that reduce the frequency and / or need for such manual cleaning operations.
It is known that certain semiconductor metal oxides provide a photoactive coating (hereinafter "PA"). The terms "photoactive" or "photoactively" refer to the photogeneration of a hole-electron pair when illuminated by electromagnetic radiation of a particular frequency, typically ultraviolet ("UV") light. Above a certain minimum thickness, these PA coatings are typically photocatalytic (hereinafter "PC"). By "photocatalytic" is meant a coating that, upon exposure to certain electromagnetic radiation, such as UV, interacts with organic contaminants on the surface of the coating to degrade or decompose organic contaminants. With sufficient PC activity, these PC coatings are also self-cleaning. By "self-cleaning" is meant that they have sufficient PC activity to break down organic contaminants quickly enough that manual cleaning is not required to remove organic contaminants. Furthermore, PC coatings are also typically hydrophilic. By "hydrophilic" it is meant that they are wetted with water at a water contact angle of generally less than 20 degrees. The hydrophilicity of PC coatings helps reduce haze, that is, the accumulation of water droplets on the coating, which can decrease visible light transmission and visibility through the coated substrate.
Titanium dioxide (TiO<sub>2</sub>) have hydrophilic and / or self-cleaning properties. However, not all titanium dioxide phases are acceptable to provide self-cleaning and / or hydrophilic coatings. At present it is preferred to use the crystalline anatase phase rather than the amorphous or crystalline rutile phase of titanium dioxide to form PC coatings.
Titanium dioxide sputter coating, for example, as a protective coating, has been used and described in US Patent No. 4,716,086. A limitation of conventionally sputtering titanium dioxide deposition is that the crystalline anatase phase is not obtained. Another limitation is that sputtering deposition of a metal film is more efficient than depositing a metal oxide film. In the case where a metal oxide film is desired, an effective procedure is to sputter deposit a metal film onto a substrate, and then heat the deposited metal film in air. In the case of sputter-deposited titanium metal film, the oxide film formed after heating is generally not the anatase phase, but rather the rutile phase of titanium dioxide. Publications directed to the formation of titanium dioxide coatings on a glass substrate include US Patent Nos. 5,595,813 and 6,027,766, and Photooxidative Self-cleaning transparent Titanium Dioxide Films on Glass, Paz et al., J. Mater. Res., Vol. 10, No. 11, p. 2842-48 (November 1995). WO 00/15571 describes amorphous metallic barrier layers of titanium oxide, zirconium oxide and tin / zinc oxide as effective alkali metal ion barrier layers at thicknesses below 180 Angstroms. Amorphous metal oxide barrier layers are most effective when the density of the layers is equal to or greater than 75% of the crystalline density.
As can be appreciated, it would be advantageous to provide a process for making a sputter-deposited hydrophilic and / or photocatalytic coating, for example by heating sputter-deposited titanium metal films to convert the films to titanium dioxide films which are at least in part in anatase phase.
ES 2 301 569 T3
Summary of the invention
The present invention refers to a process for coating a substrate, comprising the steps of:
- forming a first coating layer having an orthorhombic or cubic zirconium oxide crystalline phase on at least a part of the surface of a substrate as a first formation step; Y
- forming a second coating layer of a photoactive material selected from at least one metal oxide or semiconductor metal oxide on the first coating layer defined as a second formation step to provide a coated substrate, wherein in the second step Upon formation, a material is formed having a predetermined crystalline phase and the first coating layer will enhance the development of the predetermined crystal phase.
Furthermore, the invention relates to an article comprising:
- a substrate;
- a first coating layer having cubic or orthorhombic phase of zirconium oxide on at least a part of the surface of the substrate; Y
- a second coating layer of a photoactive material selected from at least one metal oxide or semiconductor metal oxide on the first coating layer.
In one embodiment of the invention, the deposited titanium oxide film is in the anatase phase. In another embodiment, a titanium metal film is deposited on a cubic or orthorhombic phase zirconium oxide film and the titanium metal film is heated in the presence of oxygen to provide a titanium oxide, eg, titanium dioxide. , the film being at least in part in the anatase phase.
In another embodiment of the invention, methods are provided for making a photoactive, eg, photoactively hydrophilic and / or photocatalytic coating.
The invention also relates to articles, for example windows for residential and commercial use, windows for vehicles by land, air, sea, space and submarines, made using coated substrates of the invention. In one embodiment, the article includes a substrate, a zirconium oxide layer having a thickness of 10 A to 200 A deposited on at least a portion of the substrate, and a titanium oxide layer deposited on the zirconium oxide layer. .
Brief description of the drawings
Fig. 1 is a fragmentary, side sectional view (not to scale) of a substrate having a coating stack incorporating features of the invention;
Fig. 2 is a side sectional view (not to scale) of an insulating glass unit having a coating stack of the invention;
FIG. 3 is a graph having curves of film thickness versus peak height counts for cubic zirconia phase, rutile titanium oxide phase, and anatase titanium oxide pass.
Figs. 4-11 are graphs showing the contact angle of a drop of water versus minutes of exposure to ultraviolet radiation for titanium dioxide coatings (Fig. 4-7) and various coatings incorporating features of the invention. (Figs. 8-11);
Fig. 12 is a graph showing contact angle versus post-heating temperature for a coating similar to that of Fig. 10;
Fig. 13 is a graph showing contact angle versus preheat temperature for a coating similar to Fig. 10;
Figs. 14-21 are graphs showing the results of the Cleveland Condensation Tests for coatings similar to Figs. 4-11, respectively.
Fig. 22-24 are graphs showing reflectance versus Cleveland Condensation Test (CCC) exposure time for a coating similar to Fig. 10 at preheat temperatures of 250 ° F (121 ° C) , 300 ° F (149 ° C), and 370 ° F (188 ° C), respectively, and
Fig. 25 is a graph showing CCC reflectance results versus preheat temperatures for coatings similar to that shown in Fig. 10.
ES 2 301 569 T3
Detailed description of the invention
As used herein, spatial or directional terms, such as "inside", "outside", "top", "bottom", "top", "bottom", and the like, refer to the invention as It is represented in the figures of the drawings. However, it is to be understood that the invention may assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. Furthermore, all numbers expressing dimensions, physical characteristics, processing parameters, amounts of ingredients, reaction conditions, and the like used in the specification and in the claims are to be understood as being modified in all cases by the term " about". Accordingly, unless otherwise indicated, the numerical values set forth in the following specification and claims are approximations that may vary depending on the desired properties that are intended to be obtained by means of the present invention. Finally, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be considered in light of the number of significant digits reported and through the application of standard rounding techniques. Furthermore, all ranges described herein are to be understood to include initial and final values and to encompass any and all subranges subsumed therein. For example, a set range of “1 to 10” should be considered to include any and all subranges between (and including) the minimum value of 1 and the maximum value of 10; that is, all subintervals that start with a minimum value of 1 or more and end with a maximum value of 10 or less, for example, 5.5 to 10. Furthermore, as used herein, the terms "deposited on" or "disposed on" mean deposited or disposed on, but not necessarily in contact with, the surface. For example, a coating "deposited on" a substrate does not exclude the presence of one or more coating films of the same or different composition located between the deposited coating and the substrate. Additionally, all percentages described herein are "by weight" unless otherwise indicated. All values of photocatalytic activity discussed herein are those determined by the conventional stearic acid test described in US Patent No. 6,027,766.
Referring now to FIG. 1, an article 20 having features of the present invention is depicted. Article 20 includes a substrate 22 having a first surface 24 and an opposite or second surface 26. The substrate 22 is not limiting of the invention and may be of any desired material having any desired characteristics, such as opaque, translucent, transparent or transparent substrates. substantially transparent. By "substantially transparent" is meant having a visible light transmittance of 60% or greater. By "translucent" is meant having a visible light transmittance of greater than 0% to less than 60%. By "opaque" is meant having a visible light transmittance of 0%. Additionally, the substrate 22 can be of any desired shape, such as smooth or curved. Examples of suitable substrates include, but are not limited to, plastic substrates (such as polyacrylates, polycarbonates, and polyethylene terephthalate (PET); metal substrates; ceramic substrates; glass substrates; or mixtures or combinations thereof. For example, the substrate may be conventional non-tinted soda-lime-silica glass, ie "clear glass", or it may be tinted or other colored glass, borosilicate glass, lead glass, and / or tempered, not tempered , annealed, or heat-strengthened glass. The glass can be of any type, such as conventional float glass, flat glass, or a float glass tape, and it can be of any composition having any optical property, for example, any value of visible transmission, ultraviolet transmission, infrared transmission. , and / or total transmission of solar energy. Suitable types of glass for the practice of the invention are described, for example, but are not to be construed as limiting, in US Patent Nos. 4,746,347, 4,792,536, 5,240,886, 5,385,872, and 5,393,593. . For example, the substrate 22 may be an architectural window pane, a skylight, an insulating glass unit pane, or a coating for a conventional automobile windshield, side or rear window, sunroof, or moon. transparent for airplanes, to name just a few.
The substrate 22 may have a coating stack or coating 28 of the invention deposited over all or at least a portion of the substrate 22, for example, on all or a portion of the surface 24 to make a substantially transparent article, a substantially translucent article , or a substantially opaque article. As used herein, the terms "coating" or "coating stack" include one or more coating films or layers. The terms "layer" or "film" refer to a region of the coating that has a selected or desired coating composition. Coating 28 can be photocatalytic, photoactively hydrophilic, or both. By "photoactively hydrophilic" is meant a coating in which the contact angle of a drop of water on the coating decreases with time as a result of exposure of the coating to electromagnetic radiation within the photoabsorption band of the coating. If it is photoactively hydrophilic, the coating 28 may not necessarily be photocatalytic.
The illustrative coating 28 of the invention depicted in FIG. 1 includes a first film 30 deposited on, for example, at least a portion of the surface 24 of the substrate 22 and a second film 32 deposited on, for example, at, at least a part of the first movie 30. In this illustrative coating 28, the first and second films 30, 32 are discrete coating layers, that is, the coating 28 is not a mixture of the materials of the first and second films 30, 32. In one embodiment, the first film 30 includes a material that enhances the photoactivity, eg, hydrophilically photoactive and / or photocatalytic activity, of the second film 32 over that of the second film 32 alone. In another embodiment, the first film 30 includes a material that facilitates or enhances the development of a particular crystalline phase of the second film 32. The first film 30 can be the same film (i.e., it can be of the same material) to achieve the two lenses or different materials can be used.
ES 2 301 569 T3
The first film 30 is zirconium oxide (ZrO<sub>2</sub>). The zirconium oxide film should be thick enough to achieve one or more of the objectives described above. In one embodiment, the first zirconium oxide layer 30 may have a thickness greater than 0 A, such as greater than or equal to 15 A, such as greater than or equal to 25 A, such as in the range of 25 A to 500 A For example, the zirconium oxide film 30 may have a thickness in the ranges of 25 A to 150 A; 40 A to 80 A; and / or 60 A to 70 A. In another illustrative embodiment, the zirconium oxide film 30 may have a thickness greater than or equal to 100 A, for example, in the range of 100 A to 500 A, for example, 120 A to 200 A, for example, 140 A at 160 A.
The second film 32 includes a photoactive material. The photoactive material can include at least one metal oxide, such as, but not limited to, one or more metal oxides or semiconductor metal oxides. Suitable metal oxides include titanium oxides, silicon oxides, iron oxides, tungsten oxides, zinc oxides, tin oxides, zinc-tin oxides, calcium oxides of titanium, oxides of molybdenum, oxides of niobium, and mixtures thereof, just to name a few. The second film 32 can be crystalline or at least partially crystalline. However, crystallinity is not necessarily necessary to achieve photoactive hydrophilicity.
In an illustrative coating 28 of the invention, the photoactive coating material of the second film 32 is titanium dioxide (TiO<sub>2</sub>). Titanium dioxide can exist in an amorphous form or one of three crystalline forms, that is, the anatase, rutile, and broochite crystalline forms. Titanium dioxide in the anatase phase is particularly useful because it exhibits strong photoactivity, while also possessing excellent resistance to chemical attack and excellent physical durability. The second film 32 can have any desired thickness. In an illustrative embodiment, a second film of titanium dioxide has a thickness greater than or equal to 100 A, for example, greater than or equal to 200 A, for example in the range of 100 A to 500 A, for example 300 A to 400 TO.
The first and second films 30, 32 of coating 28 should be thick enough to provide an acceptable level of photoactivity, eg, photocatalytic activity and / or photoactive hydrophilicity, for a desired purpose. There is no absolute value that makes coating 28 "acceptable" or "unacceptable" because whether coating 28 has an acceptable level of photoactivity varies largely depending on the purpose and conditions under which the coated article is being used and the standards. selected performance benchmarks to achieve that purpose. However, the thickness of the coating 28 to achieve photoactive hydrophilicity may be much less than necessary to achieve a commercially acceptable level of photocatalytic activity. For example, the titanium oxide / zirconium oxide coating described above can be of any desired thickness. However, for most automotive uses, the liner 28 should not be so thick that it cannot be seen through. For example, coating 28 may have a total thickness of 50 A to 5,000 A. As the coating thickness decreases in such ranges as 50 A to 3,000 A, for example 100 A to 1,000 A, for example 200 A to 600 A, for example 200 A to 300 A, the photocatalytic activity can be very low or even immeasurable by means of the conventional stearic acid test, but photoactive hydrophilicity can still be present in the presence of electromagnetic radiation within the photoabsorption band of the photoactive material.
The liner 28 may be an outer or end liner of a multi-layer stack of coatings present on the substrate 22 or the liner 28 may be embedded as one of the coatings other than the end liner within said multi-layer stack. For example, as shown in FIG. 1, an optional removable or temporary protective material or protective film 36 may be applied over all or a portion of the coating 28. The protective film 36 may include, for example, an organic material such that upon exposure of the coated substrate 22 to electromagnetic energy within the photo-absorbing band of the photoactive material of the second film 32, the protective film 36 will be photocatalytically removed from the surface of the coating 28. This protective film 36 can be applied to form a desired pattern on the coating 28 and can be transparent, translucent or opaque.
The coating 28 may be deposited directly on, ie, in surface contact with, the surface 24 of the substrate 22. Alternatively, one or more optional functional coatings 38 may be interposed between the coating 28 and the substrate 22. As used herein, the term "functional coating" refers to a coating that modifies one or more physical properties of the substrate on which it is deposited, eg, optical, thermal, chemical, or mechanical properties, and is not intended to remove from substrate during post-processing. The functional coating 38 may have one or more functional coating films of the same or a different composition or functionality. The functional coating 38 may be an electrically conductive coating, such as, for example, an electrically conductive heated window coating as described in U.S. Patent Nos. 5,653,903 and 5,028,759, or a single film or single film coating. multiple film. Similarly, the functional coating 38 may be a solar control coating, for example, a visible, infrared, or ultraviolet energy absorbing or reflectance coating. Examples of suitable solar control coatings are found, for example, in US Patent Nos. 4,898,789, 5,821,001, 4,716,086, 4,610,771,4,902,580,4,716,086,4,806,220,4,898. 790,4,834,857,4,948,677, 5,059,295, and 5,028,759, and also in US Patent Application number 09 / 058,440. Similarly, functional coating 38 can be a low-emissivity coating. "Low-emissivity coatings" allow visible wavelength energy, for example 400nm to about 800nm (for example to about 780nm), to be transmitted through the coating, but reflect solar infrared energy of longer wavelength. long and / or infrared thermal energy and have typically been intended to improve the thermal insulation properties of architectural glazing. By "low emissivity" is meant emissivity less than 0.4, preferably less than 0.3, plus pre
ES 2 301 569 T3 is probably less than 0.2. Examples of low-emissivity coatings are found, for example, in US Patent Nos. 4,952,423 and 4,504,109 and British reference GB 2,302,102. The functional coating 38 can be a single or multi-layer coating and can comprise one or more metals, non-metals, semimetals, semiconductors, and / or alloys, compounds, compositions, combinations, or mixtures thereof. For example, functional coating 38 can be a single layer metal oxide coating, a multilayer metal oxide coating, a non-metallic oxide coating, or a multilayer coating. The functional coating 38 may include one or more transparent conductive oxides (such as indium tin oxide or tin oxide) or doped metal oxides (such as fluorine or antimony doped tin oxide). In addition, functional coating 38 can include one or more nitrides (such as titanium nitride, silicon nitride, or zirconium nitride), borides (such as titanium diboride), or carbides (such as titanium carbide). Additionally or alternatively, another optional functional coating 40 may be deposited over all or part of the second surface 26.
Examples of functional coatings suitable for use with the invention are commercially available from PPG Industries, Inc., of Pittsburgh, Pennsylvania under the SUNGATE coatings families.<sup>®</sup> and SOLARBAN<sup>®</sup>. Such functional coatings typically include one or more anti-reflective coating films comprising dielectric or anti-reflective materials, such as metal oxides or metal alloy oxides, which are preferably transparent or substantially transparent to visible light. The functional coating (s) may also include infrared reflective films comprising a metal reflector, for example, a noble metal such as gold, copper or silver, or combinations or alloys thereof, and may further comprise a first barrier film or film, such as titanium, as is known in the art, positioned on and / or below the reflective metal layer.
An illustrative article of manufacture of the invention is depicted in Figure 2 in the form of an insulating glass (IG) unit 42. The insulating glass unit has a first sheet 44 spaced from a second sheet 46 by a spacer assembly (not shown ) and held in position by a sealing system to form a chamber between the two sheets 44,46. The first sheet 44 has a first surface 48 (surface number 1) and a second surface 50 (surface number 2). The second sheet 46 has a first surface 52 (surface number 3) and a second surface 54 (surface number 4). The first surface 48 may be the outer surface of the IG unit 42, that is, the surface exposed to the environment, and the second surface 54 may be the inner surface, that is, the surface that forms the interior of the structure. Examples of IG units are described in US Patent Nos. 4,193,236, 4,464,874, 5,088,258, and 5,106,663, incorporated herein by reference. A coating 28 of the invention may be deposited on one or more of the surfaces (any one or more of surfaces number 1 - number 4). In the non-limiting embodiment depicted in FIG. 2, liner 28 is placed on surface 48 number 1. The liner 28 reduces haze formation and makes the IG 42 unit easier to clean and maintain. One or more optional functional coatings 62 may be deposited as described above on one or more of the surfaces (number 1 - number 4), eg, the number 2, number 3 or number 4 surfaces.
One or both of the films 30, 32 of the coating 28 of the invention can be formed on the substrate 22 by any conventional method, such as, but not limited to spray pyrolysis, chemical vapor deposition (CVd), or deposition. Magnetron Spraying Steam (MSVD). For example, both films 30, 32 can be deposited by the same process or one film can be deposited by one process and one or more of the other films on coating 28 can be deposited by one or more other processes. . Each of the procedures has advantages and limitations depending on the desired characteristics of the coating 28 and the type of glass manufacturing process. For example, for a conventional float glass process, the CVD and spray pyrolysis processes may be preferable to the MSVD process because they are more compatible with continuous coating substrates, such as float glass ribbons, at elevated temperatures. Illustrative CVD coating and spray pyrolysis procedures are described in US Patent Nos. 4,344,986, 4,393,095, 4,400,412, 4,719,126, 4,853,257, 5,536,718; 5,464,657; 5,714,199; 5,599,387; and 4,971,843.
US Patent Nos. 4,379,040; 4,861,669; 4,900,633; 4,920,006; 4,938,857; 5,328,768; and 5,492,750, describe MSVD apparatus and methods for sputtering metal oxide coated films on a substrate, including a glass substrate. The MSVD process is acceptable for depositing one or more coating films 30, 32 on the substrate 22, eg, a glass sheet. In one embodiment, the substrate 22 may be heated prior to the deposition of one or more of the coating films, for example, films 30 and / or 32. Alternatively or in addition to this, the substrate 22 may be heated during the own spraying process.
In one embodiment, the coating 28 can be sputtered onto the first surface 24 of the substrate 22 and the functional coating 40 onto the second surface 26 in the same coater. International publication WO 00/37377 describes a sputtering process that is suitable for this embodiment. As will be appreciated, since sputtering takes place in a vacuum, substrate 22 may be in any orientation during the sputtering process of this embodiment of the invention, as long as the targets for deposition of coating 28 and functional coating 40 are on opposite sides of substrate 22.
ES 2 301 569 T3
An illustrative process for providing a coating 28 by means of an MSVD process will now be described. A substrate 22, such as a glass substrate, can be preheated prior to deposition of the coating 28. For example, the substrate can be heated to a temperature greater than or equal to 100 ° F (38 ° C), such as in the range of about 100 ° F to 1000 ° F (38 ° C to 537 ° C), such as greater than or equal to 150 ° F (65 ° C), 200 ° F to 500 ° F (93 ° C to 260 ° C), such as 300 ° F to 400 ° F (149 ° C to 204 ° C), before deposition of coating 28 (ie, the temperature of the substrate at the beginning of the coating process is within one of these temperature ranges. The heated substrate can then be placed in a conventional MSDV coating device having an argon / oxygen atmosphere, eg 5 vol% oxygen. at 100 vol.%, for example, 5 vol.% oxygen. at 50% vol., oxygen at 20% vol., at a pressure of 5 to 10 millitorr. To deposit a first zirconium oxide film 30, a zirconium-containing target can be sprayed in a conventional manner to form a first zirconium oxide film 30 of a desired thickness. The zirconium-containing target preferably includes 50% by weight or more zirconium, for example 80% by weight or more zirconium. However, the zirconium target can also include one or more other metals or stabilizers, such as boron, strontium, titanium, lead, barium, silicon, calcium, hafnium, lanthanum, chromium, vanadium, manganese, copper, iron, magnesium. , scandium, yttrium, niobium, molybdenum, ruthenium, tantalum, tungsten, silver, nickel, rhenium, aluminum, or mixtures thereof, or the zirconium target may be a zirconium oxide target.
A titanium-containing target can then be used to form a second film 32 of titanium oxide (eg, titanium dioxide) on the first film 30 of zirconium oxide. If the coating does not crystallize, the coated substrate can be removed from the coater and heated to a temperature sufficient to form a crystalline coating. For example, the coated substrate can be heated to a temperature in the range of 100 ° C (212 ° F) to 650 ° C (1200 ° F), such as 400 ° C (752 ° F) to 650 ° C (1200 ° F), for a period of time sufficient to promote the formation of a crystalline form of titanium dioxide. Generally, less than one hour at a temperature in the range of 100 ° C (212 ° F) to 600 ° C (1112 ° F) is sufficient. When the substrate 22 is a glass sheet cut from a floating glass ribbon, the coating 28 can be spray deposited on the air part and / or the tin part of the glass. Alternatively, substrate 22 can be coated without preheating substrate 22 prior to coating.
Substrate 22 having coating 28 deposited via CVD, spray pyrolysis or mSvd procedures may subsequently be subjected to one or more post-coating heating operations, such as hybridization or tempering. As can be appreciated, post-heating time and temperatures can be affected by several factors, including preparation of substrate 22, preparation of coating 28, thickness of coating 28, and whether coating 28 is in direct contact with substrate 22 or is a single layer of a multilayer stack on substrate 22. Alternatively, in an illustrative embodiment of the invention described below under the heading of Feature 2, a photoactive hydrophilic coating 28 can be formed by practicing the invention without the need for any post-heating step.
In the embodiment described immediately above, the coating films 30, 32 were sprayed in an oxygen-containing atmosphere to form a metal oxide-containing coating 28. However, it is to be understood that the first 30 and / or second 32 film can be sprayed as metal films in a non-reactive atmosphere , or in an active atmosphere below the material's switch point, as defined in US Patent No. United States No. 5,830,252 and United States Patent Application No. 09 / 156,730, for oxidizing metal films to metal oxide films.
The coatings 28 of the present invention are preferably photoactive, eg, photocatalytic and / or photoactively hydrophilic, upon exposure to radiation in the ultraviolet range, eg, 300 nm to 400 nm, and / or the visible range, eg. , 400 nm to 700 nm, of the electromagnetic spectrum. Sources of ultraviolet radiation include natural sources, for example solar radiation, and man-made sources such as a black light source or an ultraviolet light such as a commercially available UVA-340 light source from Q-Panel Comany of Cleveland, Ohio.
The present invention provides several features that make it advantageous for use in various industrial fields. Four of these characteristics will now be explained (crystalline phase selection, hydrophilicity, chemical durability, and photocatalytic activity).
Feature 1
Crystal phase selection
The following is intended for techniques or procedures for altering or changing the phase of a film. The term "phase" is used to describe the crystallinity or non-crystallinity of the film. For example, the term "amorphous phase" means that the film is totally or partially amorphous, that is, it does not exhibit a detectable intensity when measured in counts of a diffraction maximum for the amorphous phase when measured by means of ray diffraction. X conventional (XRD). The term "rutile phase" means that the film or coating has wholly or substantially a rutile crystal structure (that is, it exhibits detectable intensity when measured in counts of a maximum diffraction for the rutile phase when measured by XRD). and the term "anatase phase" means that the film or coating has wholly or substantially an anatase crystal structure (ie
ES 2 301 569 T3 (ie, it exhibits a detectable intensity when measured in counts of a maximum diffraction for the anatase phase when measured by XRD). A further aspect of the invention is directed to changing the phase of a titanium oxide film, for example changing the phase (s) of a spray-deposited film from the amorphous phase to a film including the (s) ) anatase and / or rutile phase (s). This aspect of the invention will be appreciated from the following study.
In the following study, unless otherwise stated, the following conditions apply. The substrates were 12-inch (30-centimeter ("cm")) or 6-inch by 12-inch (15-cm by 30-cm) square pieces of clear glass with a thickness of approximately 0.088 inches (2.3 millimeters ("mm") made by means of the flotation process The aerial part of the glass pieces were coated. The aerial part of glass made by means of the flotation process is the opposite part of the floating part of the molten metal bath as the glass ribbon moves through the forming chamber. Reference can be made to US Patent Nos. 6,027,766 and 4,091,156 for a study on the formation of a flat glass ribbon. The glass pieces were cut from glass sheets cut from a glass tape. As can be appreciated, the composition, type, configuration, and dimensions of the substrates do not limit the invention and any type of substrate can be used, for example, colored glass, plastics, metal, ceramics, and wood to name a few types of materials that can be used. Each of the glass pieces were spray coated on an Airco ILS 1600 magnetron spray vapor coater. As can be appreciated, the invention is not limited to the type of spray or the apparatus used. For example, all types of sputtering techniques can be used. A titanium metal film was sputtered onto a piece of glass or substrate by feeding a titanium metal target contained in a chamber with a 100% argon gas atmosphere; A zirconium metal film was sputtered onto a piece of glass or substrate by feeding a zirconium metal target contained in a chamber with a 100% argon gas atmosphere. A titanium oxide film was deposited on a piece of glass or substrate by feeding a titanium target contained in a chamber with an atmosphere of approximately 50% argon gas and 50% oxygen. The term "titanium oxide" used herein when referring to the anatase phase, rutile phase and amorphous phase, includes a film having titanium dioxide and / or sub-oxides and / or super-oxides of titanium. . A zirconium oxide film was deposited on a piece of glass or substrate by feeding a zirconium metal target contained in a chamber with an atmosphere of approximately 50% argon gas and 50% oxygen. The percentages of oxygen and argon in the chamber when the titanium oxide and zirconium oxide films were spray deposited were based on the combined flow of argon and oxygen gases in the chamber. A film of titanium nitride was deposited on a piece of glass or substrate by feeding a titanium metal target contained in a chamber with an atmosphere of approximately 100% nitrogen gas. The operating gas pressure of all atmospheres was 4 microns. Before filling the chamber with the desired atmosphere, the chamber was emptied by pumping, that is, evacuating the atmosphere from the chamber to a value within the range of approximately 5 to 9 x 10 <sup>6</sup> Torr.
Table I, below, shows the power in kilowatts and the number of passes of the samples made at a linear speed of 120 inches (304.8 cm) per minute. The sputter coated substrates were cut into 4 inch (10.2 cm) square pieces and heated in an oven. The pieces were moved in the oven assembly at a temperature of approximately 1300 ° F (704.4 ° C) and heated for a period of approximately 2-1 / 2 minutes. The oven temperature was calculated using a piece of uncoated glass similar in size to the coated pieces. The temperature was measured using a thermocouple that was in contact with the surface of the stone; the measured temperature was about 1216 ° F (657.8 ° C) after about 2-1 / 2 minutes. After heating, the pieces were removed and placed in an oven heated to approximately 275 ° F (135 ° C) for approximately 4 minutes and removed. The pieces were placed in the oven to hybridize the glass pieces to prevent fracturing of the glass pieces and to facilitate cutting. The crystalline phases of the sputter deposited films of titanium metal, titanium oxide, titanium nitride and titanium oxynitride, and zirconium oxide and zirconium metal were measured using X-ray diffraction (XRD). The measured samples were an approximately one inch (2.54 cm) square cut from the four inch (10.2 cm) square pieces. X-ray diffraction analysis was performed using a Philips X-Pert MPD using the grazing angle procedure and comparing the peaks with commercially available X-ray diffraction identification cards (PDF cards) from JCPDS International Center for Diffraction Data. . The pattern or curve generated has on the "x" axis 2-Theta (degree) and on the "y" axis intensity in counts. For zirconium oxide in the cubic phase, the (1,1,1) plane has a 2-Theta maximum of approximately 30.484 degrees (PDF # 27-0997). Although orthorhombic zirconia has a peak at a 2-Theta of 30.537 (PDF # 34-1084), the peaks observed in the present invention are thought to be for cubic zirconia rather than orthorhombic. However, orthorhombic zirconia could be present. Alternatively, in another embodiment the zirconium oxide may be in the baddeleyite framework (PDF # 37-1484). For titanium oxide in the rutile phase, the (1,1,0) plane has a 2-Theta maximum of about 27.446 degrees and for titanium oxide in the anatase phase, the (1,0,1 ) has a 2-Theta maximum of approximately 25.281 degrees. Amorphous titanium oxide and amorphous zirconium oxide show no peaks when analyzed using X-ray diffraction. The intensity count to detect the peaks was determined either using software that is part of the Philips equipment or by estimating the height of the peaks. Peak count indicates the presence of a phase - the higher the count, the more dominant the presence of the phase. A count was performed every 10 seconds or equivalent to a 10 second count. The values presented in the present specification, unless otherwise indicated, are values relative to each other since the equipment was not calculated using a standard before the measurements were made. When estimating the maximum, the judgment of the operator is used to determine the counting interval, more particularly, the operator selects
ES 2 301 569 T3 sets a point on the curve or pattern as the starting point and another point on the curve as the ending point of the maximum and interpolates the height of the parts of the curve between the starting and ending points. Although operator judgment is involved, the object is to identify the presence of anatase crystalline phase and the relative amount. For the purposes of appreciation of the invention, the X-ray diffraction technique is acceptable for determining the presence of different phases of zirconium oxide and titanium oxide. Using this technique to determine the presence, type, and intensity of the phases present, it should be appreciated that the absence of a maximum is not an indication that the oxide is amorphous. To determine if crystals are present, a more sensitive technique is needed, for example electron diffraction.
The area under the curve between the starting and ending points provides the crystal size for a calibrated instrument. In the present case, the area under the curve gives the relative size. The interest in this investigation was to determine the presence of the anatase phase and, therefore, the height of the peaks was of main interest. Table I lists the peak heights in counts for samples with their X-ray diffraction patterns analyzed using the software. The peak heights for the other samples were not made using the software but were estimated from an X-ray diffraction curve. The estimate for those samples is provided in the study of the samples and is identified as an estimate by means of a check mark "V" in Table I.
Table I lists the target material; the atmosphere (gas) in the chamber during coating; power in kilowatts; the number of passes; the thickness of the spray deposited film after coating; the thickness of the spray-deposited metal films after heating; and the height of the peaks in counts of 10 seconds for each of the phases that were identified as being present, when the height of the maximum was determined by an operator the value is provided in the study of the sample and is shown as a check mark "V" in Table I. The value determined using the software is given in numerical value in Table I. Reported thicknesses of the sputter-deposited coatings and / or films (except for samples 19 and 25) were measured by means of conventional X-ray fluorescence measurements and needle profilometer. The thicknesses reported for samples 19 and 25 were estimated using curves developed from previous coater runs.
When no peaks were observed for the zirconium oxide and titanium oxide films, a check mark "V" is placed on the amorphous column. When referring to the presence of peaks, it is the presence of peaks at 2-Theta angles. Furthermore, the samples were not performed in the order presented. Samples are presented for comparison as coatings when practical.
Sample 1 (Reference)
A zirconium oxide film with a thickness of approximately 68 Angstroms was deposited on a glass substrate. The X-ray diffraction pattern of the zirconium oxide film after heating showed the cubic phase. The height of the peak in counts is estimated to vary between approximately 250 and 350 counts.
Sample 2 (Reference)
A zirconium oxide film with a thickness of approximately 187 Angstroms was deposited on a glass substrate. The X-ray diffraction pattern of zirconium oxide after heating showed the cubic phase. The height of the peak in counts is estimated to vary between approximately 1,000 and 1,100 counts.
Sample 3 (Reference)
A film of zirconium metal with a thickness of 177 Angstroms was deposited on a glass substrate; the coated glass substrate was heated. The zirconium oxide film formed during heating was approximately 256 Angstroms thick. The X-ray diffraction pattern of the zirconium oxide film showed the cubic phase. The height of the peak in counts is estimated to vary between approximately 250 and 350 counts. An additional peak was observed at approximately 28.5 2-Theta degrees. The peak or its cause has not been identified; however, the peak was not present in the X-ray diffraction curve for sample 2.
Samples 1-3 were made, and the films were analyzed to determine if zirconium metal and / or zirconium metal oxide peak at the same 2-Theta value as an anatase peak for titanium oxide. The zirconium oxide films did not show any peak in the 2-Theta value.
ES 2 301 569 T3
Sample 4 (Comparative)
A film of titanium oxide with a thickness of 218 Angstroms was deposited on a glass substrate. After heating, the film was analyzed by X-ray diffraction. No peaks were observed.
Sample 5 (Comparative)
A film of titanium with a thickness of 109 Angstroms was deposited on a glass substrate and the coated glass substrate was heated. The film thickness after heating was 207 Angstroms. The titanium oxide film was analyzed by X-ray diffraction. No peaks were observed.
Sample 6 (Comparative)
A film of zirconium oxide with a thickness of 20 Angstroms was deposited on a glass substrate and a film of titanium oxide with a thickness of 220 Angstroms was deposited on the film of zirconium oxide. The X-ray diffraction pattern did not show peaks for the zirconium oxide film or for the titanium oxide film. Neither peak indicated that the zirconium oxide film and the titanium oxide film were amorphous.
Sample 7 (Comparative)
Sample 7 was a repeat of sample 6 and it was confirmed that neither the zirconium oxide film nor the titanium oxide film had peaks.
Sample 8 (Comparative)
A film of zirconium oxide with a thickness of 31 Angstroms was deposited on a glass substrate and a film of titanium oxide with a thickness of 221 Angstroms was deposited on the film of zirconia. After heating, the coated substrate was analyzed by X-ray diffraction. The zirconium oxide film had no peaks to indicate the presence of cubic zirconia. The titanium oxide had the rutile phase with a peak height of approximately 94 counts. Anatase was not observed.
Sample 9 (Comparative)
A film of zirconium oxide with a thickness of 45 Angstroms was deposited on a glass substrate and a film of titanium oxide with a thickness of 215 Angstroms was deposited on the film of zirconium oxide. After heating, the coated substrate was analyzed by X-ray diffraction. No cubic zirconia peaks were observed. Titanium oxide had a rutile peak height of 171 counts and an anatase peak height of 310 counts.
Sample 10 (Comparative)
A film of zirconium oxide with a thickness of 45 Angstroms was deposited on a glass substrate and a film of titanium oxide with a thickness of 215 Angstroms was deposited on the film of zirconium oxide. The X-ray diffraction pattern of the heated substrate did not have any cubic zirconia peaks. The standard showed a rutile peak of titanium oxide with a peak height of 235 counts and an anatase peak height of 475 counts. Samples 9 and 10 are similar and the differences in value between the peak counts are within the expected variations.
ES 2 301 569 T3
Sample 11
A film of zirconium oxide with a thickness of 65 Angstroms was deposited on a glass substrate and a film of titanium oxide with a thickness of 215 Angstroms was deposited on the film of zirconium oxide. The X-ray diffraction pattern had a peak height measured for cubic zirconia of 283 counts and a peak height measured for the rutile titanium oxide phase of 158 counts and for the anatase phase of 665 counts.
Sample 12
A film of zirconium oxide with a thickness of 91 Angstroms was deposited on a glass substrate and a film of titanium oxide with a thickness of 217 Angstroms was deposited on the film of zirconium oxide. The X-ray diffraction pattern had a peak height measured for cubic zirconia of 416 counts and a peak height measured for the rutile titanium oxide phase of 210 counts and a peak height measured for the anatase phase of 258 count titanium oxide.
Sample 13
A zirconium oxide film with a thickness of 105 Angstroms was deposited on a glass substrate and a titanium oxide film with a thickness of 221 Angstroms was deposited on the titanium oxide film. The X-ray diffraction pattern had a peak height measured for cubic zirconium oxide of 548 counts, a peak height measured for the rutile phase of titanium oxide of 171 counts, and a peak height measured for the anatase phase of 62 count titanium oxide.
Sample 14
A film of zirconium oxide with a thickness of 153 Angstroms was deposited on a glass substrate and a film of titanium oxide with a thickness of 221 Angstroms was deposited on the film of zirconia. The X-ray diffraction pattern had a peak height measured for cubic zirconia of 555 counts and a peak height measured for rutile titanium oxide of 85 counts. No measurable anatase titanium oxide peak was observed.
Sample 15
A zirconium oxide film with a thickness of 190 Angstroms was deposited on a glass substrate and a titanium oxide film with a thickness of 215 Angstroms was deposited on the zirconium oxide film. The X-ray diffraction pattern had a peak height measured for cubic zirconia of 690 counts and a peak height measured for rutile titanium oxide of 19 counts. No measurable anatase titanium oxide peak was observed.
Sample 16
Sample 16 was a repeat of sample 15. The peak height measured for the maximum cubic zirconia was 687 counts and the peak height measured for the rutile titanium oxide was 206 counts. No anatase titanium oxide peak was observed. Although there is a difference in peak height counts for rutile titanium oxide in samples 15 and 16, the interest here is that no anatase peak was observed in samples 15 and 16.
Sample 17
A film of zirconium oxide with a thickness of 184 Angstroms was deposited on a glass substrate and a film of titanium metal with a thickness of 106 Angstroms was deposited on the film of zirconium oxide. After heating, the titanium oxide film had a thickness of 205 Angstroms. Cubic zirconia was expected by X-ray diffraction pattern to have a peak height between 1000 and 1100 counts. No peak was observed for rutile and anatase.
Sample 18
A zirconium metal film with a thickness of 64 Angstroms was deposited on a glass substrate. A film of titanium oxide was deposited on the zirconium metal film and had a thickness of 220 Angstroms. After heating, the zirconium oxide had a thickness of 93 Angstroms. X-ray diffraction pattern
ES 2 301 569 T3 had a peak height measured for cubic zirconia of 208 counts, and a peak height measured for the rutile phase of titanium oxide of 146 counts. No measurable anatase titanium oxide peak was observed.
Sample 19 (Comparison)
A film of zirconium metal with a thickness of 148 Angstroms was deposited on a glass substrate. A film of titanium oxide with a thickness of 215 Angstroms was deposited on the zirconium metal film. After heating, the zirconium oxide had a thickness of 264 Angstroms. In the X-ray diffraction curve, no cubic zirconia, or rutile titanium oxide, or anatase peaks were observed.
Sample 20
A zirconium metal film with a thickness of 87 Angstroms was deposited on a glass substrate. A 225 Angstrom thick titanium oxide film was deposited on the zirconium metal film. The zirconium oxide film after heating was 126 Angstroms thick. The X-ray diffraction pattern had a measured height for cubic zirconia of 259 counts, a measured peak height for rutile titanium oxide of 146 counts, and a measured peak height for anatase oxides of 80 counts.
Sample 21 (Comparison)
A zirconium metal film with a thickness of 182 Angstroms was deposited on a glass substrate, and a titanium metal film with a thickness of 113 Angstroms was deposited on the zirconium metal film. After heating, the zirconium oxide film was 263 Angstroms thick, and the titanium oxide film was 214 Angstroms thick. The X-ray diffraction pattern shows no measurable peaks for cubic zirconia and anatase titanium oxide. Rutile titanium oxide was expected from the X-ray diffraction pattern to have a peak height between 900 and 1000 counts.
Sample 22 (Comparison)
A zirconium metal film with a thickness of 87 Angstroms was deposited on a glass substrate, and a titanium metal film with a thickness of 115 Angstroms was deposited on the zirconia metal film. After heating, the zirconium oxide film was 126 Angstroms thick, and the titanium oxide film was 217 Angstroms thick. The X-ray diffraction pattern had no observable maxima for cubic zirconia and rutile titanium oxide and anatase.
Sample 23 (Comparison)
A film of titanium oxide with a thickness of 218 Angstroms was deposited on a glass substrate, and a film of titanium metal with a thickness of 110 Angstroms was deposited on the film of titanium oxide. After heating, the titanium metal film had a thickness of 208 Angstroms. The X-ray diffraction pattern had no peaks that could be observed for rutile titanium oxide and anatase.
Sample 24 (Comparison)
A titanium metal film with a thickness of 58 Angstroms was deposited on a glass substrate; after heating, it was a titanium oxide film with a thickness of 110 Angstroms. A 223 Angstrom thick titanium oxide film was deposited on the titanium metal film. The X-ray diffraction pattern had no peaks that could be observed for rutile titanium oxide and anatase.
ES 2 301 569 T3
Sample 25 (Comparative)
A film of titanium metal with a thickness of 119 Angstroms was deposited on a glass substrate; the film after heating was a 249 Angstrom thick titanium oxide film. A film of titanium oxide with a thickness of 215 Angstroms was deposited on the titanium metal film. The X-ray diffraction pattern had no measurable peaks for rutile titanium oxide and anatase.
Sample 26 (Comparison)
A film of titanium nitride with a thickness of 216 Angstroms was deposited on a glass substrate. The thickness of the film after heating was 384 Angstroms. The composition of the film was not analyzed. During heating the film was expected to oxidize but to what degree was not determined; therefore, the film can include titanium nitride, titanium oxynitride, or titanium oxide. A titanium film with a thickness of 119 Angstroms was deposited on the titanium nitride film. After heating, the titanium oxide film had a thickness of 223 Angstroms. The X-ray diffraction pattern showed a rutile maximum. It is not known whether the peak was from the heated rutile titanium film or the heated titanium metal film or combinations thereof. Rutile was expected to have a peak height between 100-250 counts. No anatase peak was observed.
Sample 27
A film of zirconium oxide with a thickness of 190 Angstroms was deposited on a glass substrate. A titanium nitride film of unknown thickness was deposited on the zirconium oxide film. The titanium nitride film after heating had a thickness of 364 A. See discussion of sample 26 regarding the composition of the heated titanium nitride film. It was expected from the X-ray diffraction pattern that the cubic zirconia would have a peak height between 900-1000. The rutile in the heated titanium nitride film would have a peak height between 250-300 counts.
Sample 28 (Comparison)
A 4 inch (10.2 cm) square piece of sample 2 was heated and a 220 Angstrom thick titanium oxide film was deposited on the heated coating of sample 2. The sample did not heat up after depositing the titanium oxide film. The peak for cubic zirconium oxide was observed as explained in sample 2. No peaks were observed for the anatase or rutile titanium oxides.
Sample 29 (Reference)
A 4 inch (10.2 cm) square piece of Sample 1 was heated and a 220 Angstrom thick titanium oxide film was deposited on the heated coating of Sample 1. After cooling, the coated piece did not got hot. The peak for cubic zirconium oxide was observed as explained in sample 1. No peaks were observed for the anatase or rutile titanium oxides.
Sample 30
Sample 30 was a repeat of sample 28, except that after the titanium oxide film was deposited, the coated sample was heated a second time. The X-ray diffraction pattern had a cubic zirconium oxide peak height of 1036 counts, and a rutile titanium oxide peak height of 167 counts. No anatase peak was observed.
Sample 31
Sample 31 was a repeat of Sample 29, except that after the titanium oxide film was deposited, the coated glass was heated a second time. The X-ray diffraction pattern had a cubic zirconium oxide peak height of 285 counts, and a rutile titanium oxide peak height of 246 counts. No anatase peak was observed.
ES 2 301 569 T3
Sample 32 (Reference)
A film of zirconium oxide with a thickness of 173 Angstroms was deposited on a glass substrate. The glass substrate was heated after which a 115 Angstrom thick titanium metal film was deposited on the heated zirconium oxide coated glass substrate. The coated glass substrate was heated, and the titanium oxide film was 217 Angstroms thick. The X-ray diffraction pattern had a cubic zirconium oxide peak height of 932 counts, and a rutile titanium oxide peak height of 246 counts. No peaks were observed for the rutile or anatase titanium oxides.
Sample 33 (Reference)
A 65 Angstrom thick zirconium oxide film was deposited on a glass substrate and a 115 Angstrom thick titanium metal was deposited on the zirconium oxide. The glass substrate became hot. After heating, a film of titanium oxide with a thickness of 217 Angstroms was deposited on the heated zirconium oxide coated glass substrate. The X-ray diffraction pattern had a cubic zirconia peak height of 288 counts. No peaks were observed for the rutile or anatase titanium oxides.
A study of samples 1-33 shows that the height of the peaks for the anatase titanium oxide phase and the rutile titanium oxide phase of samples 6-16 follows an approximate bell-shaped curve (See Fig. 3 ) when plotted as a function of zirconium oxide layer thickness. Table II below shows the peak counts for the cubic zirconia phase and the rutile titanium oxide anatase phase for samples 6 - 16. The first layer for each of samples 6 - 16 is oxide zirconium and the second layer for each of samples 6-16 is titanium dioxide. It should be appreciated that the thickness of the titanium oxide layer for samples 6-16 is the same. This is unexpected because the bell-shaped curve for peak height is a result of the change in the thickness of the zirconium oxide layer, not the thickness of the titanium oxide layer. Support for this conclusion is the fact that the shape of the increase in peak height for the zirconium oxide phase is not bell-shaped.
(Table goes to next page)
ES 2 301 569 T3
<td rowspan="4">I Peak count</td><td>Oxide</td><td>zirconium 1</td><td>8 15 OO</td><td colspan="2"></td><td></td><td></td><td>s</td><td>s</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CN</td><td></td><td></td><td></td><td> 283</td><td></td><td>co Tf</td><td></td><td> 548 ]</td>
<td rowspan="2">Titanium oxide</td><td rowspan="2"></td><td>CÜ tn 75 C <</td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>OR CO</td><td></td><td>LO N. Tt</td><td></td><td> 665</td><td></td><td>00 LO CN</td><td></td>
<td colspan="3">Rutile</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 02</td><td></td><td></td><td></td><td>235 I</td><td></td><td>oo LO</td><td></td><td> 210</td><td></td>
<td colspan="2"></td><td>1 Amorphous</td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td>s</td><td></td><td></td><td>s</td><td>s</td><td>s</td><td></td><td>s</td><td></td><td>s</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td rowspan="2"></td><td rowspan="2">Coating thickness (Anqstroms)</td><td rowspan="2"></td><td colspan="2">After</td><td>1 warm up 1</td><td></td><td></td><td></td><td>CO LO CN</td><td></td><td>I 207 |</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Π After</td><td>coating</td><td></td><td></td><td> 1 99</td><td>r * OO</td><td> 177 |</td><td>I 218 |</td><td>109</td><td>or CN</td><td>216 η</td><td>or CN</td><td> 220 |</td><td>CO</td><td> 221 |</td><td> 45 |</td><td>215 η</td><td>LO Tf</td><td>215 η</td><td>I 99</td><td>219 η</td><td> 05</td><td> 217 |</td><td>IT OR</td>
<td></td><td colspan="2"></td><td>No. of Ί</td><td>1 passes 1</td><td></td><td></td><td>co</td><td>CO</td><td> -</td><td></td><td> -</td><td></td><td>Tt</td><td> -</td><td>TF</td><td> -</td><td>You-</td><td>CN</td><td>Tt</td><td>CN</td><td>τΓ</td><td>CO</td><td>τΓ</td><td>tT</td><td>tF</td><td>IT</td>
<td></td><td colspan="2"></td><td>1 Power</td><td colspan="2"> ^1</td><td></td><td> 3,7 |</td><td>CN LO *</td><td> 2,3 |</td><td>I 0.9</td><td> 2,8 |</td><td>r * co *</td><td>CO</td><td>nCO *</td><td>CO</td><td>CN LO *</td><td>CO</td><td>N- CO*</td><td>OR CO *</td><td>N- CO*</td><td>CO</td><td>ΓΝco</td><td>CO</td><td>co*</td><td>co</td><td>h- CO*</td>
<td></td><td colspan="2"></td><td>1 Atmosphere 1</td><td>1 Camera 1</td><td></td><td></td><td>CN OR</td><td>CN OR</td><td></td><td>or</td><td> <</td><td> 6</td><td>CN OR</td><td>or</td><td>CN or</td><td>CN OR</td><td>CN or</td><td>CN OR</td><td>OR</td><td>CN OR</td><td>OR</td><td>CN or</td><td>CN OR</td><td>CN OR</td><td>OR</td><td>CN OR</td>
<td></td><td colspan="2"></td><td>1 Material 1</td><td colspan="2">Diana</td><td></td><td>N¡</td><td>ΓΝ</td><td>neither</td><td>I-</td><td> 1-</td><td>NEITHER</td><td>I—</td><td>ΓΝ</td><td> 1—</td><td>NEITHER</td><td>I-</td><td>N¡</td><td>I-</td><td>N¡</td><td>I-</td><td>NEITHER</td><td>I-</td><td>NEITHER</td><td> 1—</td><td>N</td>
<td></td><td colspan="2"></td><td>1 Layers</td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td>r</td><td>r—</td><td>CN</td><td></td><td>CN</td><td>r—</td><td>CN</td><td></td><td>CN</td><td>T—</td><td>CN</td><td>τ—</td><td>: n</td><td>T—</td><td>CN</td><td></td>
<td></td><td colspan="2"></td><td>1 Sample n.</td><td colspan="2"></td><td></td><td>T—</td><td>CN</td><td>CO</td><td></td><td>IT</td><td>4D</td><td></td><td> >-</td><td></td><td> 20</td><td></td><td> 35</td><td></td><td>OR</td><td></td><td></td><td></td><td>CN</td><td></td><td>Ό</td>
ES 2 301 569 T3
<td rowspan="6">A] (continued) |</td><td rowspan="4">1 Peak count 1</td><td>Oxide</td><td>1 zirconium 1</td><td>Cubic 1</td><td colspan="2"></td><td></td><td></td><td> 555</td><td></td><td>I 069 I</td><td></td><td>b * oo co</td><td></td><td>X</td><td></td><td>208 I</td><td></td><td></td><td></td><td>or> LO CXI</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td rowspan="2">Titanium oxide</td><td rowspan="2"></td><td>1 Anatase</td><td colspan="2"></td><td rowspan="10"></td><td>CXI CO</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>OR 0O</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td colspan="3">Rutile</td><td></td><td></td><td>Oo</td><td></td><td>σ></td><td></td><td> 206 |</td><td></td><td></td><td></td><td>co</td><td></td><td></td><td></td><td>CO</td><td></td><td>X</td><td></td><td></td><td></td><td></td>
<td colspan="2"></td><td>1 Amorphous I</td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>X</td><td></td><td></td><td>X</td><td>X</td><td></td><td></td><td>X</td><td></td><td>X</td><td>X</td><td>X</td><td>X</td>
<td rowspan="2"></td><td rowspan="2">Coating thickness (Anqstroms)</td><td rowspan="2"></td><td colspan="2">After</td><td>1 warm-up</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>205 η</td><td>r 93</td><td></td><td>I 264 |</td><td></td><td>co CXI</td><td></td><td>| 263 I</td><td>R 214 |</td><td>co CXI</td><td>R 217 |</td><td></td><td> 208 |</td>
<td>Γ After Ί</td><td>1 liner 1</td><td></td><td>cÑ CXI</td><td>CO lo</td><td>1 221 I</td><td>Or or</td><td>IT CXI</td><td>AND</td><td>223 η</td><td>1 W 1</td><td> 106 |</td><td>L 64 1</td><td> 220 |</td><td>I 8tn I</td><td>I 215 I</td><td>r- 00</td><td>I 225 |</td><td>CXI oo</td><td>CO V "</td><td>roo</td><td>IT</td><td>CO CXI</td><td>OR</td>
<td rowspan="5">TABL</td><td></td><td colspan="2"></td><td>No. of</td><td>1 passes l</td><td></td><td></td><td>r-</td><td></td><td>co</td><td></td><td>co</td><td></td><td>CO</td><td> -</td><td> -</td><td></td><td> -</td><td></td><td> -</td><td></td><td> -</td><td> -</td><td> -</td><td> -</td><td></td><td></td>
<td></td><td colspan="2"></td><td>Power 1</td><td colspan="2"></td><td>co</td><td>co ~</td><td>co</td><td>OJ in</td><td>CO</td><td>CXI LO</td><td> 0'9</td><td>CXI LO ~</td><td>co cxT</td><td> 9'0</td><td>co</td><td>co cxT</td><td>co</td><td> 8'0</td><td>co</td><td>co cxf</td><td>oo cxf</td><td>oo o</td><td>oo cxT</td><td> 0'9</td><td>oo cxT</td>
<td></td><td colspan="2"></td><td>1 Atmosphere 1</td><td>i Camera 1</td><td></td><td>C4 OR</td><td>04 OR</td><td>CM OR</td><td>C4 OR</td><td>04 OR</td><td>04 or</td><td>04 OR</td><td>I heard or</td><td> *</td><td> •5</td><td>04 OR</td><td> <</td><td>04 OR</td><td></td><td>04 OR</td><td></td><td></td><td> £</td><td> 1— <</td><td>04 OR</td><td> <</td>
<td></td><td colspan="2"></td><td>1 Material 1</td><td colspan="2">Diana</td><td> 1—</td><td>rki</td><td>h-</td><td></td><td>l -</td><td>rxj</td><td> 1—</td><td>ISJ</td><td>h-</td><td>IXI</td><td>h-</td><td></td><td>I—</td><td>isj</td><td>I—</td><td></td><td> 1—</td><td>l> 4</td><td>H-</td><td> 1-</td><td> 1—</td>
<td></td><td colspan="2"></td><td colspan="3">Layers</td><td>CX |</td><td></td><td>CXI</td><td> -</td><td>CXI</td><td> -</td><td>CXI</td><td></td><td>CXI</td><td></td><td>CXI</td><td></td><td>CXI</td><td></td><td>CXI</td><td></td><td>CXI</td><td></td><td>CXI</td><td></td><td>CXI</td>
<td></td><td></td><td colspan="2"></td><td>1 Sample # 1</td><td colspan="2"></td><td></td><td></td><td>Tt</td><td></td><td>IT</td><td></td><td>co</td><td></td><td>h *</td><td></td><td>oo</td><td></td><td>σ></td><td></td><td>N</td><td></td><td>cÑ</td><td></td><td>CXI cxj</td><td></td><td>co CXI</td><td></td>
ES 2 301 569 T3
<img file="ES2301569T3_D0001.tif" />
ES 2 301 569 T3
<td rowspan="9">TABLE 1 (continued) 1</td><td rowspan="4">1 Oico count 1</td><td>Oxide</td><td>zirconium</td><td>8 le c</td><td colspan="2"></td><td>CM CO</td><td></td><td>OO co CM</td><td></td>
<td rowspan="2">Titanium oxide</td><td rowspan="2"></td><td>03 CA as a 5</td><td colspan="2"></td><td></td><td></td><td></td><td></td>
<td colspan="3">Rutile</td><td></td><td></td><td></td><td></td>
<td colspan="2"></td><td>Amorphous</td><td colspan="2"></td><td></td><td></td><td></td><td></td>
<td rowspan="2"></td><td rowspan="2">Coating thickness (Anastroms)</td><td rowspan="2"></td><td colspan="2">After</td><td>1 warm up 1</td><td></td><td>1 zis 1</td><td></td><td> 217 |</td>
<td>1 After 1</td><td>1 coating i</td><td></td><td>co r *. V "</td><td>it</td><td> 65 |</td><td>IT</td>
<td></td><td colspan="2"></td><td>CD O o</td><td>1 passes 1</td><td></td><td></td><td> -</td><td>CO</td><td> -</td>
<td></td><td colspan="2"></td><td>1 Power 1</td><td>Kw</td><td></td><td> 5,2 |</td><td>co CM</td><td>co*</td><td>00 CM *</td>
<td></td><td colspan="2"></td><td>1 Atmosphere 1</td><td>Chamber 1</td><td></td><td><sup>2</sup>OR</td><td> <</td><td> 6</td><td> <</td>
<td></td><td></td><td colspan="2"></td><td>1 Material 1</td><td colspan="2">Diana</td><td></td><td>P</td><td>n¡</td><td>P</td>
<td></td><td></td><td colspan="2"></td><td>1 Layers 1</td><td colspan="2"></td><td>v *</td><td>CM</td><td>r—</td><td>CM</td>
<td></td><td></td><td colspan="2"></td><td>Sample No. "</td><td colspan="2"></td><td>Csl Ό</td><td></td><td>• or * O</td><td></td>
ES 2 301 569 T3
TABLE II
<td></td><td colspan="2">Anqstroms thickness</td><td colspan="3">Count</td>
<td>Sample iV</td><td>Layer 1</td><td>Layer 2</td><td>Rutile</td><td>Anatase</td><td>Cubic</td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td> 6</td><td> 20</td><td> 216</td><td> 0</td><td> 0</td><td> 0</td>
<td> 7</td><td> 20</td><td> 220</td><td> 0</td><td> 0</td><td> 0</td>
<td> 8</td><td> 31</td><td> 221</td><td> 94</td><td> 0</td><td> 0</td>
<td> 9</td><td> 45</td><td> 215</td><td> 171</td><td> 310</td><td> 0</td>
<td> 10</td><td> 45</td><td> 215</td><td> 235</td><td> 475</td><td> 0</td>
<td> 11</td><td> 65</td><td> 219</td><td> 158</td><td> 665</td><td> 283</td>
<td> 12</td><td> 91</td><td> 217</td><td> 210</td><td> 258</td><td> 416</td>
<td> 13</td><td> 105</td><td> 221</td><td> 171</td><td> 62</td><td> 548</td>
<td> 14</td><td> 153</td><td> 221</td><td> 85</td><td> 0</td><td> 555</td>
<td> 15</td><td> 190</td><td> 215</td><td> 19</td><td> 0</td><td> 690</td>
<td> 16</td><td> 181</td><td> 223</td><td> 206</td><td> 0</td><td> 687</td>
Furthermore it should be appreciated that the value for sample 16 was not plotted in the curves shown in Fig. 3 as the peak count for the rutile titanium oxide phase was exceptionally greater than the peak height for the oxide phase. titanium rutile from sample 15 and does not follow the bell-shaped pattern. The curves in Fig. 3 and the data in Table II shows an increase in the peak count for the anatase titanium oxide phase at a zirconium oxide thickness of approximately 65-75 Angstroms and thereafter the peak height count of the phase decreases. titanium oxide anatase. The rutile titanium oxide phase has an increase in the count for peak height in zirconium oxide to a thickness ranging from 51-102 Angstroms and thereafter the count for peak height decreases.
In the subsequent samples 34-37, the deposition parameters were monitored to attempt to deposit coatings with a thickness each of the zirconium oxide layers of approximately 65-75 Angstroms which appeared to provide the maximum peak height count for the phase of titanium oxide anatase (see Table II). The deposition parameters for samples 34-45 are shown in Table III below. In sample 38 below, the thickness of the titanium oxide layer was similar to the titanium oxide thickness of samples 34-37 with the thickness of the zirconium oxide layer increased. In samples 39-43 below, the thickness of the zirconium oxide layer and the first titanium oxide layer were held constant and the thickness of the second titanium oxide layer varied. In samples 44 and 45 below, the thickness of the zirconium oxide and titanium oxide layers was varied. Samples 38-45 were coated as explained above except that samples 34-45 were heated and after heating the samples were removed from the oven and allowed to cool to room temperature instead of being placed in an oven.
Sample 34
A film of zirconium oxide with a thickness of 71 Angstroms was deposited on a glass substrate, then a film of titanium oxide with a thickness of 130 Angstroms was deposited on the zirconium oxide film. The X-ray diffraction pattern had a peak height measured for the cubic zirconia phase of 241 counts and for the rutile titanium oxide phase of 164 counts. No anatase titanium oxide peak was observed.
ES 2 301 569 T3
Sample 35
A film of zirconium oxide with a thickness of 65 Angstroms was deposited on a glass substrate, then a film of titanium oxide with a film thickness of 65 Angstroms was deposited on the zirconium oxide film. The X-ray diffraction pattern had a peak height measured for the cubic zirconia phase of 267 counts. No peak of the rutile or anatase titanium oxide phase was observed.
(Note: for samples 36 and 37 the peak height count was performed using a different X-ray tube than the X-ray tube used for the samples. The peak count is significantly higher and should be taken into account when considering make comparisons).
Sample 36
A film of zirconium oxide with a thickness of 65 Angstroms was deposited on a glass substrate, then a film of titanium oxide with a thickness of 177 Angstroms was deposited on the zirconium oxide film. The X-ray diffraction pattern had a peak height measured for the cubic zirconium oxide phase of 1136 and for the rutile titanium oxide phase of 1169. A hint of the anatase titanium oxide peak was observed.
Sample 37
A 62 Angstrom thick zirconium oxide film was deposited on a glass substrate, then a 192 Angstrom thick titanium oxide film was deposited on the zirconium oxide film. The X-ray diffraction pattern had a peak height measured for the cubic zirconia phase of 1315, for the rutile titanium oxide phase of 845, and for the anatase titanium oxide phase of 2284.
Sample 38
A film of zirconium oxide with a thickness of 173 Angstroms was deposited on a glass substrate. A film of titanium oxide with a thickness of 114 Angstroms was deposited on the film of zirconium oxide. An X-ray diffraction pattern was made; however, the height of the peaks was not estimated or calculated. From the X-ray diffraction pattern, a peak was observed for the cubic zirconium oxide phase and what appears to be a displaced peak for the rutile titanium oxide phase. The zirconium oxide phase was more appreciated than the rutile titanium oxide phase. No peak was observed for the anatase titanium oxide phase.
Sample 39
Sample 39 is similar to Sample 34 except that prior to heating the zirconium oxide and titanium oxide film coated substrate, an additional 48 Angstrom thick titanium metal film was deposited on the titanium oxide film. . The coated substrate was heated and the heated titanium metal film was oxidized and the resulting titanium oxide film was 90 Angstroms thick. The X-ray diffraction pattern showed a cubic zirconia phase with a peak count of 240, a rutile titanium oxide phase with a peak count of 178, and an anatase titanium oxide phase with a count of peaks of 187 counts.
Sample 40
Sample 40 is similar to Sample 35 except that a titanium metal film with a thickness of 80 Angstroms was deposited on the titanium oxide film. The coated substrate was heated and the heated titanium metal film was oxidized and the resulting titanium oxide film was 151 Angstroms thick. The X-ray diffraction pattern had a peak count of 241 for a cubic zirconia phase. No rutile or anatase titanium oxide peak was observed.
Sample 41
Sample 41 is similar to Sample 35 except that a 25 Angstrom thick titanium metal was deposited on the titanium oxide film. The coated substrate was heated and the heated titanium metal film was oxidized and the resulting titanium oxide film was 47 Angstroms thick. An X-ray diffraction pattern was calculated; however, the height of the peaks was not estimated or realized. From the X-ray diffraction pattern, a peak was observed for the cubic zirconia phase. No peaks were observed for the rutile or anatase titanium oxide phases.
ES 2 301 569 T3
Sample 42
A film of zirconium oxide with a thickness of 62 Angstroms was deposited on a glass substrate, a film of titanium oxide with a thickness of 98 Angstroms was deposited on the zirconium oxide, and a film of titanium metal with a thickness of 46 Angstroms was deposited on the titanium oxide film. The coated substrate was heated and the thickness of the titanium oxide from the oxidation of the titanium metal was calculated to be 87 Angstroms. An X-ray diffraction pattern was calculated; however, the height of the peaks was not estimated or realized. From the X-ray diffraction pattern, a peak was observed for the cubic zirconia phase and for the rutile titanium oxide phase. No peak or slight hint was observed for the anatase titanium oxide phase.
Sample 43
Sample 43 is similar to sample 42 except that a titanium metal with a thickness of 61 Angstroms was deposited on the titanium oxide film. The calculated thickness of the titanium oxide film from oxidation of the titanium metal film was 116 Angstroms. An X-ray diffraction pattern was calculated; however, the height of the peaks was not estimated or realized. From the X-ray diffraction pattern, a peak was observed for the zirconium oxide phase and the rutile titanium oxide phase. No peak was observed for the anatase titanium oxide phase.
Sample 44
A film of zirconium oxide with a thickness of 57 Angstroms was deposited on a glass substrate; a titanium metal with a thickness of 25 Angstroms was deposited on the zirconium oxide, and a film of titanium oxide with a thickness of 65 Angstroms was deposited on the titanium metal. The coated substrate was heated in air and the calculated thickness of the titanium oxide film from the oxidation of the titanium metal was 47 Angstroms. An X-ray diffraction pattern was made; however, the height of the peaks was not estimated or calculated. From the X-ray diffraction pattern, a peak was observed for the cubic zirconia phase. No peaks were observed for the rutile or anatase titanium oxide phases.
Sample 45
Sample 45 is similar to Sample 38 except that a 48 Angstroms thick titanium metal was deposited on the titanium oxide film. The titanium oxide film after heating the titanium metal film had a calculated thickness of 91 Angstroms. An X-ray diffraction pattern was made; however, the height of the peaks was not estimated or calculated. From the X-ray diffraction pattern a peak was observed for the cubic zirconia phase and what appears to be a displaced peak for the rutile titanium oxide phase. No peak was observed for the anatase titanium oxide phase.
From the results of samples 34-37, it is observed that the anatase titanium oxide phase developed into titanium oxide films with a thickness of approximately 169 Angstroms. As can be seen, the thickness to which anatase titanium oxide can develop can be decreased. Sample 38 supports the conclusion from Table II that a thick zirconium oxide first layer is not effective for the development of the anatase titanium oxide phase for the titanium dioxide phase in this thickness range of the curve. Fig. 3. This could depend on the thickness of the titanium dioxide film. From the results of samples 37-45, it is concluded that an anatase titanium oxide phase can develop from a titanium metal film (see sample 39). However, if the zirconium oxide film is increased, the efficiency to develop a titanium oxide phase appears to decrease significantly (see sample 45).
The invention can be practiced to provide a rutile titanium oxide and / or anatase self-cleaning film for windows for residential and commercial use, clear car windows, for example side windows, rear windows, windshields, sunroofs, oven doors. , mirrors, etc.
ES 2 301 569 T3
<td rowspan="6">'ABLAIII --------------------------------- 1</td><td rowspan="4">> 1 Peak count 1</td><td>Oxide</td><td>zirconium</td><td>OR CJ heard it CJ</td><td colspan="2"></td><td></td><td> 3</td><td></td><td> 267</td><td></td><td>co co</td><td></td><td>* ITEM CO</td><td></td><td>s.</td><td></td><td>OR 3</td><td></td><td></td><td> 3</td><td></td><td></td><td></td><td>s</td><td></td><td>s</td>
<td rowspan="2">Titanium oxide</td><td rowspan="2"></td><td>1 Anatase</td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>«T 3 CM CM</td><td></td><td></td><td></td><td></td><td>NCO</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td colspan="3">Rutile</td><td></td><td></td><td> 3</td><td></td><td></td><td></td><td>I 1169 *</td><td></td><td> 845*</td><td></td><td>s</td><td></td><td></td><td> 178</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td colspan="2"></td><td>1 Amorphous</td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>s</td><td></td>
<td rowspan="2"></td><td colspan="2" rowspan="2">Cladding thickness (Anqstroms)</td><td colspan="2">-------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -----------, despues de</td><td>1 warm up 1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>O σ></td><td></td><td></td><td>ITEM</td><td></td><td></td><td>bM</td><td></td>
<td>1 After</td><td>coating</td><td></td><td></td><td></td><td> 1 130 |</td><td> 1 65 |</td><td>m co</td><td>mad</td><td>b-</td><td>I 29 I</td><td>CM σ></td><td>I 173 |</td><td>Tf</td><td>L 89 I</td><td>I 130 I</td><td>I 48 I</td><td>CO CO</td><td> 1 65 |</td><td>O oo</td><td>CM CO</td><td>MAD</td><td>LO CM</td><td>CM CO</td>
<td rowspan="4"></td><td></td><td colspan="2"></td><td>θΡοΝ</td><td>1 passes</td><td></td><td></td><td>co</td><td>CO</td><td>CO</td><td> ”4-</td><td>co</td><td> -</td><td>CO</td><td>CM</td><td>CO</td><td>co</td><td>co</td><td>co</td><td></td><td>co</td><td>xr</td><td> -</td><td>CO</td><td></td><td> -</td><td>CO</td>
<td></td><td colspan="2"></td><td>CU oc or CL</td><td colspan="2"></td><td></td><td>NCO</td><td> 1 0'9 1</td><td>r *. co'</td><td>Or co</td><td>rco</td><td> 0'9</td><td>bco</td><td>CM co</td><td>CM lo '</td><td>or co</td><td>bco</td><td>or co</td><td>CM_</td><td>bco</td><td> 0'9</td><td>or cm</td><td>bco</td><td>Or co</td><td>oo o</td><td>bco</td>
<td></td><td colspan="2"></td><td>l Atmosphere</td><td>1 Camera</td><td></td><td></td><td>CM OR</td><td>or</td><td>CM or</td><td>CM or</td><td>or</td><td>CM OR</td><td>δ</td><td>CM or</td><td>CM OR</td><td>CM or</td><td>CM or</td><td>δ</td><td> £</td><td>CM or</td><td>CM OR</td><td> <</td><td>CM O</td><td>CM or</td><td> £</td><td>δ</td>
<td></td><td colspan="2"></td><td>1 Material 1</td><td colspan="2">Diana</td><td></td><td>IM</td><td> —</td><td>NEITHER</td><td>l -</td><td>NEITHER</td><td>I—</td><td>N</td><td>h-</td><td>N</td><td>I—</td><td></td><td>I-</td><td>I-</td><td>N¡</td><td>h—</td><td> 1-</td><td>NEITHER</td><td>Η</td><td>h-</td><td>N</td>
<td></td><td></td><td colspan="2"></td><td>1 Layers 1</td><td colspan="2"></td><td></td><td></td><td>CM</td><td>V—</td><td>CM</td><td></td><td>CM</td><td></td><td>CM</td><td></td><td>CM</td><td></td><td>CM</td><td>co</td><td></td><td>CM</td><td>co</td><td>Mr-</td><td>CM</td><td>CO</td><td></td>
<td></td><td></td><td colspan="2"></td><td>1 Shows η. 1</td><td colspan="2"></td><td></td><td>co</td><td></td><td>it ΓΟ</td><td></td><td>CO co</td><td></td><td>* -Ό</td><td></td><td>90 Ό</td><td></td><td>*or</td><td></td><td></td><td>OR</td><td></td><td></td><td> 5</td><td></td><td></td><td>CM</td>
ES 2 301 569 T3
<td rowspan="6">Ή ”• o 'or cu 3 c Ή oo</td><td rowspan="4">1 Peak count 1</td><td>Oxide</td><td>1 zirconium 1</td><td>Cubic</td><td colspan="2"></td><td></td><td></td><td>X</td><td></td><td></td><td>X</td><td></td><td></td><td>X</td><td></td><td></td><td></td>
<td rowspan="2">Titanium oxide</td><td rowspan="2"></td><td>1 Anatase</td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td colspan="3">Rutile</td><td></td><td>x</td><td></td><td></td><td>X</td><td></td><td></td><td></td><td></td><td></td><td>X</td><td rowspan="10">Modified X-ray tube</td>
<td colspan="2"></td><td>1 Amorphous 1</td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>X</td><td></td><td></td><td></td>
<td rowspan="2"></td><td colspan="2" rowspan="2">Cladding thickness (Anqstroms)</td><td colspan="2">After</td><td>1 warm-up</td><td></td><td>1 ^. oo</td><td></td><td></td><td>co</td><td></td><td>1 do 1</td><td></td><td></td><td></td><td>σΐ</td>
<td>I After</td><td>1 coating</td><td></td><td>OO cu</td><td> 1 48 |</td><td>CXI co</td><td> 1 86</td><td>co</td><td> 1 57</td><td>LO CXI</td><td> 65 |</td><td>M 00 ΊΤ "</td><td> | 130 |</td><td>oo</td>
<td rowspan="5">TABL</td><td></td><td colspan="2"></td><td>Γ N.'de T</td><td>past 1</td><td></td><td>co</td><td> -</td><td>co</td><td>co</td><td> -</td><td>co</td><td> -</td><td> 3-</td><td>co</td><td>oo</td><td> -</td>
<td></td><td colspan="2"></td><td>1 Power 1</td><td>Kw</td><td></td><td> 1 6,0 |</td><td>CX | _</td><td>co</td><td>1 QÍ9</td><td>co</td><td>r *. eo</td><td> 1 9'0</td><td> 1 0'9</td><td>CXI</td><td>I 0.9</td><td></td>
<td></td><td colspan="2"></td><td>1 Atmosphere 1</td><td>1 Camera 1</td><td></td><td>1 Ό 1</td><td> <</td><td>CXI or</td><td>CM OR</td><td></td><td><sup>2</sup>0</td><td> £</td><td> 6</td><td>CN or</td><td>CXI or</td><td>I a /</td>
<td></td><td colspan="2"></td><td>1 Material i</td><td colspan="2">Diana</td><td>i-</td><td>P</td><td>rxi</td><td>P</td><td>P</td><td></td><td>P</td><td>P</td><td>ixj</td><td>P</td><td>i-</td>
<td></td><td colspan="2"></td><td>1 Layers 1</td><td colspan="2"></td><td>CXI</td><td>eo</td><td></td><td>CXI</td><td>co</td><td></td><td>CX |</td><td>ro</td><td>T—</td><td>CXI</td><td>co</td>
<td></td><td></td><td colspan="2"></td><td>1 Show. 1</td><td colspan="2"></td><td></td><td></td><td>co 'ζΓ</td><td></td><td></td><td></td><td></td><td></td><td>IT</td><td></td><td></td>
ES 2 301 569 T3
Additional glass substrates were coated with titanium oxide, zirconium oxide, and coatings of the invention with a titanium oxide coating deposited on zirconium oxide (samples 54-68 shown in Table IV). The deposition parameters and intensity measurements for these samples 54-68 are shown in Table IV.
Samples 54-57 show the influence of the zirconium oxide layer thickness on the anatase peak for the titanium oxide layer. The behavior is similar to the samples discussed above and shown in Fig. 3. However, samples 54-57 were post-heated to lower temperatures than previous samples 1-45.
Samples 58-62 show the influence of the thickness of the zirconium oxide layer (70 A-166 A) with the thickness of the titanium oxide layer (382 A-441 A). The thicker zirconium oxide layer does not decrease the intensity of the anatase peak intensity (1,0,1).
Samples 63 and 64 are comparative examples of titanium dioxide. Compared to samples 58-62, samples 58-62 of the invention show a markedly higher anatase peak intensity (1.0.1).
Samples 65 - 68 are zirconium oxide coatings and show the intensity of the zirconium oxide peak in the cubic phase (1,1,1), clearly show a distinction between the peak positions for the cubic, rutile and anatase for thin films.
Table IV also shows the presence of rutile, although of significantly lower intensity.
(Table goes to next page)
ES 2 301 569 T3
Table IV
<td></td><td></td><td></td><td>Noise</td><td></td><td colspan="2"> 26</td><td colspan="2"> 30</td><td colspan="2">OR CO</td><td colspan="2">CO</td><td colspan="2">CO</td><td colspan="2">CN CO</td><td colspan="2"> 36</td><td colspan="2">OR CO</td><td colspan="2">co CO</td><td> 30</td><td>Tico</td>
<td></td><td></td><td></td><td>or</td><td> 636</td><td>OR</td><td></td><td></td><td></td><td>CN</td><td></td><td> 388</td><td></td><td>IT OR</td><td></td><td> 157</td><td></td><td> 223</td><td></td><td> 73</td><td></td><td> 379</td><td></td><td>OR</td><td>or</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td>CN or</td><td> (1.1.1)</td><td>-heat.</td><td> 598</td><td colspan="2">OR</td><td colspan="2"> 158</td><td colspan="2">94 I</td><td colspan="2"> 412</td><td colspan="2">CO oo</td><td colspan="2">CN b-</td><td colspan="2"> 213</td><td colspan="2"> 73</td><td colspan="2"> 358</td><td>or</td><td>or</td>
<td></td><td>bj</td><td>Cubic</td><td rowspan="2">Temp. post</td><td> 524</td><td colspan="2">OR</td><td colspan="2"> 148</td><td colspan="2">MAD</td><td colspan="2"> 371</td><td colspan="2">or Ti-</td><td colspan="2"> 157</td><td colspan="2"> 184</td><td colspan="2">OR</td><td colspan="2"> 336</td><td>or</td><td>or</td>
<td> £5</td><td></td><td></td><td> 382</td><td colspan="2">OR</td><td colspan="2">OR</td><td colspan="2">OR</td><td colspan="2">IT</td><td colspan="2">or</td><td colspan="2">OR</td><td colspan="2">OR</td><td colspan="2">or</td><td colspan="2">or</td><td>or</td><td>or</td>
<td rowspan="2">Φ 3 I heard X CD Ό Φ</td><td></td><td></td><td>CJ</td><td> 636</td><td colspan="2">OR</td><td colspan="2">CO</td><td colspan="2">OR</td><td colspan="2"> 38</td><td colspan="2">CO CO</td><td colspan="2">or CO</td><td colspan="2"> 49</td><td colspan="2">or</td><td colspan="2">or</td><td>or</td><td>or</td>
<td></td><td>c></td><td>-heat.</td><td> 598</td><td colspan="2">or</td><td colspan="2">CO LO</td><td colspan="2">or</td><td colspan="2"> 38</td><td colspan="2"> 62</td><td colspan="2">You-</td><td colspan="2"> 49</td><td colspan="2">or</td><td colspan="2">or</td><td>or</td><td>or</td>
<td>T3 in c Jg c</td><td></td><td>Rutile</td><td>np. post</td><td> 524</td><td colspan="2">or</td><td colspan="2">CN</td><td colspan="2">or</td><td colspan="2">CO CO</td><td colspan="2"> 40</td><td colspan="2"> 40</td><td colspan="2"> 49</td><td colspan="2">or</td><td colspan="2">or</td><td>or</td><td>or</td>
<td></td><td>CN or</td><td></td><td>Have</td><td> 382</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">00 CN</td><td colspan="2">OR</td><td colspan="2">OR</td><td colspan="2">or</td><td colspan="2">or</td><td>or</td><td>or</td>
<td></td><td>i—</td><td></td><td>(□ J</td><td> 636</td><td colspan="2"> 317</td><td colspan="2"> 64</td><td colspan="2"> 279</td><td colspan="2">or</td><td colspan="2"> 453</td><td colspan="2"> 491</td><td colspan="2"> 552</td><td colspan="2"> 598</td><td colspan="2"> 554</td><td> 82</td><td>CN σ></td>
<td></td><td></td><td rowspan="2">Anatase (1,0,1)</td><td>-heat. |</td><td> 598</td><td colspan="2"> 360</td><td colspan="2">CO</td><td colspan="2"> 264</td><td colspan="2">or</td><td colspan="2"> 524</td><td colspan="2"> 561</td><td colspan="2"> 648</td><td colspan="2"> 592</td><td colspan="2"> 554</td><td> 159</td><td>bco</td>
<td></td><td></td><td>np. post</td><td> 524</td><td colspan="2"> 333</td><td colspan="2">CN</td><td colspan="2"> 286</td><td colspan="2">or</td><td colspan="2"> 500</td><td colspan="2"> 387</td><td colspan="2"> 507</td><td colspan="2"> 584</td><td colspan="2"> 532</td><td>CO oo</td><td>or LO</td>
<td></td><td></td><td></td><td>Ter</td><td> 328</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2"> 194</td><td colspan="2">or</td><td colspan="2"> 258</td><td colspan="2"> 387</td><td colspan="2">MAD</td><td colspan="2"> 120</td><td colspan="2"> 261</td><td>or</td><td>OR</td>
<td></td><td></td><td></td><td colspan="2">Temp. precal. (° F)</td><td colspan="2">-OR</td><td colspan="2">Amb.</td><td colspan="2">Amb.</td><td colspan="2">_cí</td><td colspan="2">-Q</td><td colspan="2"></td><td colspan="2">Amb.</td><td colspan="2">Amb.</td><td colspan="2">Amb.</td><td>-Q</td><td>Amb.</td>
<td></td><td></td><td></td><td colspan="2">Thickness (TO)</td><td> 48</td><td> 183</td><td> 93</td><td> 183</td><td>Or b-</td><td> 186</td><td> 158</td><td> 185</td><td>Or b</td><td> 382</td><td> 127</td><td> 391</td><td> 132</td><td> 427</td><td>MAD</td><td> 399</td><td> 166</td><td> 441</td><td> 347</td><td> 392</td>
<td></td><td></td><td></td><td colspan="2">No. of passes</td><td>CN</td><td> -</td><td>Ν '</td><td> -</td><td>CO</td><td> -</td><td>CO</td><td> -</td><td>CO</td><td> -</td><td>CO</td><td> -</td><td>CO</td><td> -</td><td>CO</td><td> -</td><td>CO</td><td> -</td><td> -</td><td> -</td>
<td></td><td></td><td></td><td colspan="2">Energ. Kw</td><td> 3,7</td><td> 5,9</td><td> 3,7</td><td> 5,9</td><td> 3,2</td><td> 5,9</td><td> 3,6</td><td> 5,9</td><td>bco</td><td> 5,9</td><td> 3,7</td><td> 5,9</td><td> 3,7</td><td> 6'9</td><td> 3,2</td><td>CD it</td><td> 3,7</td><td> 6'5</td><td> 6'9</td><td> 5,9</td>
<td></td><td></td><td></td><td>or*"</td><td> 02</td><td> 50</td><td>OR WHAT</td><td>OR WHAT</td><td>OR WHAT</td><td>Or CN</td><td>OR WHAT</td><td>Or CN</td><td>OR WHAT</td><td>or LO</td><td>Or CN</td><td> 50</td><td> 20</td><td>OR WHAT</td><td>Or CN</td><td>Or CN</td><td>Or CN</td><td>Or CN</td><td>Or CN</td><td>Or CN</td><td>Or CN</td>
<td></td><td></td><td></td><td>Gas</td><td> £</td><td>OR 10</td><td> 50</td><td>OR WHAT</td><td>or LO</td><td> 80</td><td> 50</td><td> 80</td><td>OR WHAT</td><td>or LO</td><td>O oo</td><td>OR WHAT</td><td>OR 00</td><td>or LO</td><td>O oo</td><td>OR 00</td><td> 80</td><td> 80</td><td> 80</td><td>Or co</td><td> 80</td>
<td></td><td></td><td></td><td colspan="2">Target material</td><td>bj</td><td>P</td><td>bj</td><td>P</td><td>N</td><td>i-</td><td>ΓΜ</td><td>P</td><td>N</td><td>P</td><td>bj</td><td>P</td><td>bj</td><td>P</td><td>bj</td><td>P</td><td>bj</td><td>P</td><td>P</td><td>P</td>
<td></td><td></td><td></td><td colspan="2">Layers</td><td> -</td><td>CN</td><td> -</td><td>CN</td><td> -</td><td>CN</td><td> -</td><td>CN</td><td> -</td><td>CN</td><td> -</td><td>CN</td><td> -</td><td>CN</td><td> -</td><td>CN</td><td> -</td><td>CN</td><td> -</td><td> -</td>
<td></td><td></td><td></td><td colspan="2">Sample Do not.</td><td colspan="2">ITEM</td><td colspan="2">LO LO</td><td colspan="2">CO LO</td><td colspan="2">b- ITEM</td><td colspan="2"> 58</td><td colspan="2"> 59</td><td colspan="2">or CO</td><td colspan="2">CO</td><td> 62</td><td></td><td>co co</td><td>Tt CO</td>
ES 2 301 569 T3
Table IV
<td></td><td></td><td></td><td>Noise</td><td></td><td> 23</td><td> 26</td><td> 04</td><td> 26</td>
<td></td><td></td><td></td><td>CJ</td><td> 636</td><td> 435</td><td> 333</td><td> 177</td><td>ITEM 03</td>
<td></td><td>CXI O</td><td></td><td>c CD Cü O</td><td> 598</td><td> 469</td><td> 291</td><td>I ------------------------------------------------- -------------------------------------------------- ---------------- 177</td><td> £</td>
<td></td><td>ΓΜ</td><td>8 lo '3 O</td><td rowspan="2">OQ O Q. Q. AND CD 1—</td><td> 524</td><td> 418</td><td> 289</td><td>CN CD T "</td><td>tr 00</td>
<td>"Σ) £ 5 tr ·</td><td></td><td></td><td> 382</td><td> 52</td><td>OR</td><td>OR</td><td>or</td>
<td rowspan="3">XRD intensity (Cuei</td><td></td><td></td><td>(or.)</td><td> 636</td><td>OR</td><td>or</td><td>OR</td><td>or</td>
<td></td><td>OR</td><td>-heat.</td><td> 598</td><td>or</td><td>or</td><td>OR</td><td>or</td>
<td></td><td>O * 4 = 3 QT</td><td>np. post</td><td> 524</td><td>or</td><td>or</td><td>or</td><td>or</td>
<td></td><td rowspan="2">T02</td><td></td><td>Have</td><td> 382</td><td>or</td><td>or</td><td>or</td><td>or</td>
<td></td><td></td><td>or</td><td> 636</td><td>or</td><td>or</td><td>or</td><td>or</td>
<td></td><td></td><td rowspan="2">Anatase (1,0,1)</td><td>-heat.</td><td> 598</td><td>or</td><td>or</td><td>or</td><td>or</td>
<td></td><td></td><td>np. post</td><td> 524</td><td>or</td><td>or</td><td>or</td><td>or</td>
<td></td><td></td><td></td><td>Have</td><td> 328</td><td>or</td><td>or</td><td>or</td><td>or</td>
<td></td><td></td><td></td><td>Temp. Dreca-</td><td>Έ jZ * cd</td><td>Amb.</td><td>-Q</td><td>-Q</td><td></td>
<td></td><td></td><td></td><td colspan="2">Thickness (TO)</td><td> 144</td><td> 135</td><td> 82</td><td> 73</td>
<td></td><td></td><td></td><td colspan="2">No. of passes</td><td>CD</td><td>co</td><td>in</td><td>CO</td>
<td></td><td></td><td></td><td>Energ. ÍZIAJ</td><td></td><td> 3,7</td><td> 3,7</td><td>hσί</td><td> 3.7</td>
<td></td><td></td><td></td><td> (%) 1------------------------'----------------------------------</td><td>CN OR</td><td> 20</td><td> 50</td><td> 20</td><td> 50</td>
<td></td><td></td><td></td><td>Gas</td><td> <</td><td> 80</td><td> 50</td><td> 80</td><td>OR WHAT</td>
<td></td><td></td><td></td><td colspan="2">Target material -</td><td>rsl</td><td>or. NEITHER</td><td>NJ</td><td>NEITHER</td>
<td></td><td></td><td></td><td colspan="2">Layers</td><td> -</td><td> -</td><td></td><td>V "</td>
<td></td><td></td><td></td><td colspan="2">Sample No.</td><td>LO CD</td><td>CD CD</td><td>r> CD</td><td>oo CD</td>
ES 2 301 569 T3
Feature 2
Hydrophilicity
The coatings of the invention were compared to conventional titanium dioxide coatings under various conditions to determine the impact of the invention on the hydrophilicity of the coating.
Clear glass substrates having a thickness of 2.3 nm were coated using a commercially available Airco ILS 1600 magnetron sputtering vapor coater. Samples 46-49 were coated only with a titanium coating as comparative samples. Samples 50-53 were coated with a coating of the invention with a zirconium oxide film (first layer) deposited on the glass substrate and a titanium dioxide film (second layer) deposited on the zirconium oxide film. The deposition parameters for samples 46-53 are shown in Table V below. As shown in Table V, the substrates for samples 48, 49, 52, and 53 were preheated in an oven external to the steam coater such that the substrates had a temperature of approximately 370 ° F (188 ° C) at start of the coating operation. The substrates were not heated further during the coating process. After coating, the samples were evaluated at room temperature of 70 ° F (21 ° C) and post-heated to temperatures of 47 0 ° F (243 ° C), 579 ° F (304 ° C), and 686 ° F (363 ° C) to evaluate the effect of post-coating heat treatment on the hydrophilicity of coatings.
The peak count of the phases was also measured as described above in Feature 1. It should be appreciated that the peak count of the phases in the present specification can be directly compared within a given Table but care is necessary when the counts from different Tables are compared since no attempt has been made to normalize the measurements for the different sets of samples. It should be appreciated that the post-heating temperatures of samples 46-53 were much lower than those of the samples discussed in Feature 1 and that samples 48, 49, 52 and 53 were preheated. Samples 46 and (titanium oxide, not preheated) were amorphous. While the preheating of the substrate showed an XRD intensity for the anatase peak (1,0,1) at the maximum preheating temperatures (363 ° C) for the samples and 49. Coatings with zirconium oxide first layer and without preheating (samples 50 and 51) showed an anatase peak (1.0.1) at 363 ° C (sample 50) and 304 ° C (sample 51), which are temperatures lower than for the samples described in Characteristic 1. In samples 48-51 no other maximum intensity was present at these temperatures. This indicates that the first layer of zirconium oxide influenced the presence of anatase.
Surprisingly, for the first layer of titanium oxide with zirconium oxide that was preheated to 370 ° F (188 ° C), sample 52 shows that the coating is amorphous and sample 53 appears to have small peaks of rutile and anatase. Most notably, the peaks are present at approximately equal intensity over the range from room temperature to 363 ° C. Also, for sample 53, the intensity of the rutile peak appears to shift to a higher 2-Theta value.
(Table goes to next page)
ES 2 301 569 T3
Table IV
<td rowspan="12">XRD Intensity (Accounts)</td><td rowspan="4">ZrO2</td><td rowspan="4">Cubic (1,1,1)</td><td rowspan="4">Temp. post-heating. fC)</td><td> 363</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td colspan="2">OR</td><td colspan="2">OR</td><td colspan="2">OR</td><td colspan="2">OR</td>
<td> 304</td><td>or</td><td>or</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">OR</td><td colspan="2">OR</td><td colspan="2">OR</td>
<td> 243</td><td>or</td><td>or</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">OR</td><td colspan="2">OR</td><td colspan="2">or</td>
<td>CM</td><td>or</td><td>α</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td>
<td rowspan="8">CM O i-</td><td rowspan="4">Rutile (1,1,0)</td><td rowspan="4">I Temp. post-heating. ('C)</td><td> 363</td><td>or</td><td>or</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2"> 58</td>
<td> 304 ¡</td><td>or</td><td>or</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2"> 1</td>
<td>243 I</td><td>or</td><td>or</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2"></td>
<td>CM</td><td>or</td><td>or</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2"> 99</td>
<td rowspan="4">Anatase (1,0,1)</td><td rowspan="4">Temp. post-heating. (C)</td><td> 363</td><td>or</td><td>or</td><td> 124</td><td> 417</td><td colspan="2"> 237</td><td colspan="2"> 363</td><td colspan="2">or</td><td colspan="2">25 i</td>
<td> 304</td><td>or</td><td>or</td><td>OR</td><td>OR</td><td colspan="2">OR</td><td colspan="2"> 254</td><td colspan="2">or</td><td colspan="2"></td>
<td> 243</td><td>or</td><td>or</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">OR</td><td colspan="2">or</td><td colspan="2"> •</td>
<td>CM</td><td>or</td><td>or</td><td>or</td><td>or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">or</td><td colspan="2">co CM</td>
<td></td><td></td><td></td><td colspan="2">or. rá,, .—. P oc Ll I— CL ~</td><td>CM</td><td>CM</td><td> 188</td><td> 188</td><td colspan="2">CM</td><td colspan="2">ν'- CM</td><td colspan="2"> 188</td><td colspan="2">CO CO</td>
<td></td><td></td><td></td><td colspan="2">Thickness (TO)</td><td>C * N</td><td> 397</td><td>LO r **. t—</td><td> 447</td><td> 73</td><td> 3</td><td> 155</td><td> 287</td><td>IT</td><td>Or h—</td><td> 138</td><td> 306</td>
<td></td><td></td><td></td><td colspan="2">No. of passes</td><td> -</td><td> ▼—</td><td>V-</td><td> -</td><td>CO</td><td>V "V-</td><td>CO</td><td> -</td><td>CO</td><td> -</td><td>co</td><td>V</td>
<td></td><td></td><td></td><td colspan="2">Energ. Kw</td><td> 5,9</td><td> 5,9</td><td> 5,9</td><td> 5,9</td><td> 3,2</td><td> 5,9</td><td> 3,7</td><td> 5,9</td><td> 3,2</td><td> 5,9</td><td> 3,7</td><td> 5,9</td>
<td></td><td></td><td></td><td rowspan="2">Gas (%)</td><td> 02</td><td> 50</td><td> 20</td><td> 50</td><td> 20</td><td> 50</td><td> 50</td><td>20 I</td><td> 20</td><td> 20</td><td> 50</td><td> 20</td><td> 20</td>
<td></td><td></td><td></td><td>-I know</td><td> 50</td><td> 80</td><td> 50</td><td> 80</td><td> 80</td><td> 50</td><td>Or co</td><td> 80</td><td>Or co</td><td>OR WHAT</td><td> 80</td><td> 80</td>
<td></td><td></td><td></td><td colspan="2">Target material</td><td>i—</td><td></td><td></td><td> 1-</td><td>llv ΓΜ</td><td>P</td><td>OR· IXI</td><td>P</td><td>IXI</td><td>P</td><td>ΓΜ</td><td>P</td>
<td></td><td></td><td></td><td colspan="2">Layers i</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td>CM</td><td> -</td><td>CM</td><td> -</td><td>CM</td><td> -</td><td>CM</td>
<td></td><td></td><td></td><td colspan="2">Sample No.</td><td> 46</td><td> 47</td><td> 48</td><td> 49</td><td colspan="2"> 50</td><td colspan="2">IT</td><td colspan="2"> 52</td><td colspan="2"> 53</td>
ES 2 301 569 T3
The coated substrates were exposed to UV radiation from a UVA-340 light source at an intensity of 24 W / m<sup>2</sup> on the coating surface and the contact angle of a drop of water on the coating was measured over time. The results of this procedure for samples 46-53 are shown in Figs. 4-11, respectively. The numbers in the figure legends indicate the post-heating temperatures (° F) as described above.
From Fig. 4-11, it can be seen that for the zirconium oxide (73 A) / titanium oxide (164 A) coating (sample 50) without preheating (Fig. 8), the coating of the invention significantly reduces the water contact angle for post-heating greater than 470 ° F (243 ° C) compared to a titanium oxide coating (173 A) (sample 46) alone (Fig. 4). For a similar coating of the invention (sample 52) preheated to 370 ° F (188 ° C), the contact angle compared to a similar coating of titanium oxide preheated alone (sample 48) is lower even without post-heating (Compare Fig. 10 and 6).
As shown in Fig. 9, for a zirconium oxide (155 A) / titanium oxide (287 A) coating (sample 51) without preheating, the coating shows a lower contact angle than with a dioxide coating. titanium (397 A) (sample 47) alone (Fig. 5) and the contact angle continues to decrease with post-heating. For a similar coating (sample 53) preheated to 370 ° F (188 ° C), the coating of the invention shows good hydrophilicity even without post-heating. By not requiring post-heating to achieve hydrophilicity or super-hydrophilicity (that is, contact angle less than or equal to 5 °), significant time and energy savings can be achieved by practicing the process of the invention.
Figs. 12 and 13 illustrate the effects of preheat and postheat temperature for a coating repeated to that of sample 52. Fig. 12 is a graph of the contact angle during 60 minutes of UV exposure (340 nm with a intensity of 24 W / m<sup>2</sup> on the surface of the coating) versus the post-heat temperature for substrates preheated to 250 ° F (121 ° C), 300 ° F (149 ° C), and 370 ° F (188 ° C). In Fig. 12 it can be seen that as the preheating temperature increases, the contact angle decreases. It appears that preheating has a greater effect on the resulting contact angle than post-heating for post-heating temperatures up to about 500 ° F (260 ° C). Fig. 13 shows that for post-heating temperatures of 261 ° F (127 ° C), 388 ° F (198 ° C), and 495 ° F (257 ° C), the preheating of the substrate appears to have a greater impact on the contact angle than post-heating.
Feature 3
Chemical durability
Repeat coatings of samples 46-53 were also analyzed according to a conventional Cleveland Condensation Analysis (CCC) apparatus (QCT Condensation Analyzer commercially available from Q-Panel Company of Cleveland, Ohio). The degree of coating degradation was determined by measuring the reflectance (expressed in terms of the stimulus value and designated Y or Y (R1) in Figs.) Of the coating using a BYK-Gardner TCS Meter. The results are shown in Fig. 14-21. As shown in Figs. 14 and 15, samples 46 and 47 (titanium alone; no preheat) showed poor results on CCC. As used herein "poor" means that the coating does not survive the CCC test for more than 400 hours as evidenced by a drop in observed reflectance indicating degradation of the coating. Samples 48 and 49 (titanium oxide alone; preheated) in Figs. 16 and 17 showed somewhat better results. However, samples 50 and 51 (zirconium oxide / titanium oxide; no preheat) in Figs. 18 and 19 showed better results in CCC than titanium oxide coatings without preheat. Surprisingly, samples 52 and 53 zirconium oxide / titanium oxide; with preheating) in Fig. twenty and 21 showed markedly improved CCC results on preheated titanium oxide coatings. For example, sample 53 (Fig. 21) not only provided a coating with photoactive hydrophilicity less than 10 ° after 40 minutes of exposure to UV radiation (340 nm at an intensity of 24 w / m<sup>2</sup>) even without post-heating, but it also had surprisingly good results in the CCC.
Figs. 22 - 25 show the results of the CCC test for a repeat coating of sample 52 for post-heat temperatures of 261 ° F (127 ° C), 388 ° F (198 ° C), 495 ° F ( 257 ° C), 561 ° F (294 ° C), and room temperature for preheat temperatures of 250 ° F (121 ° C) (Fig. 22), 300 ° F (149 ° C) (Fig. 23), and 370 ° F (188 ° C) (Fig. 24). From these results, it appears that as the preheat temperature increases, the post-heating has less and less effect on the chemical durability of the coating. Fig. 25 shows that for this coating, if the substrate is heated to approximately 370 ° F (188 ° C), post-heating below approximately 561 ° F (294 ° C) appears to have little or no effect on the chemical durability of the coating.
ES 2 301 569 T3
Feature 4
Photocatalysis
Some of the coatings of the invention were measured for photocatalytic activity according to the standard stearic acid test. Table VI shows the results for those measures that have a statistical value R<sup>2</sup> of more than 0.93. The values of the photocatalytic activity are in units of centimeter<sup>-1</sup>/ min (cm<sup>-1</sup>/ min).
<td colspan="3">TABLE VI</td>
<td>Sample</td><td>Postheating (° C)</td><td>Photocatalytic activity</td>
<td> 49</td><td> 303</td><td> 0,0031</td>
<td> 48</td><td> 303</td><td> 0,0038</td>
<td> 52</td><td> 243</td><td> 0,0024</td>
<td> 52</td><td> 303</td><td> 0,0025</td>
As can be seen in Table VI, the coatings analyzed show photocatalytic activity under the conditions evaluated. For the other samples analyzed for photocatalytic activity, the results showed an R value<sup>2</sup> of less than 0.93, making the results unalterable statistically, and therefore these values are not quoted.
Those skilled in the art will readily appreciate that modifications can be made to the invention without departing from the concepts described in the foregoing description. Accordingly, the particular embodiments described in detail herein are illustrative only and do not limit the scope of the invention, to which the full scope of the appended claims and each and every one of their equivalents is to be given.
Contents27
11 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11
27 members in 12 offices
Priority claims10
| Document | Office | Kind | Date |
|---|---|---|---|
| 20000229449P | United States of America | – | |
| 22944900 | United States of America | P | |
| 22944900 | United States of America | P | |
| 20010943163 | United States of America | – | |
| 94316301 | United States of America | A | |
| 94316301 | United States of America | A | |
| 229449P01986965 | – | – | – |
| 943163 | – | – | – |
| US20000229449P | – | – | – |
| US20010943163 | – | – | – |
Members27
| Document | Office | Kind | |
|---|---|---|---|
| US2002045073A1 | United States of America | A1 | |
| CA2417936A1 | Canada | A1 | |
| WO0240417A2 | World Intellectual Property Organization (WIPO) | A2 | |
| AU3922502A | Australia | A | |
| WO0240417A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO0240417A9 | World Intellectual Property Organization (WIPO) | A9 | |
| EP1315682A2 | European Patent Office (EPO) | A2 | |
| MXPA03001686A | Mexico | A | |
| US2003235720A1 | United States of America | A1 | |
| US6677063B2 | United States of America | B2 | |
| JP2004513864A | Japan | A | |
| WO2004092089A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2002239225B2 | Australia | B2 | |
| CA2417936C | Canada | C | |
| US7323249B2 | United States of America | B2 | |
| EP1315682B1 | European Patent Office (EPO) | B1 | |
| AT387411T | Austria | T | |
| ATE387411T1 | Austria | T1 | |
| DE60133012D1 | Germany | D1 | |
| US2008124460A1 | United States of America | A1 | |
| PT1315682E | Portugal | E | |
| DK1315682T3 | Denmark | T3 | |
| ES2301569T3This record | Spain | T3 | |
| US2008248291A1 | United States of America | A1 | |
| JP4194838B2 | Japan | B2 | |
| DE60133012T2 | Germany | T2 | |
| US7842338B2 | United States of America | B2 |
Numbers
- Publication
- 2301569
- Publication, DOCDB
- 2301569
- Publication, EPODOC
- ES2301569T
- Application
- 1986965
- Application, DOCDB
- 01986965
- Application, EPODOC
- ES20010986965T
Titles2
- Spanish
- PROCEDIMIENTOS PARA OBTENER REVESTIMIENTOS FOTOACTIVOS Y/O FASE ANATASA CRISTALINA DE OXIDOS DE TITANIO Y ARTICULOS REALIZADOS DE ESTA FORMA.
- English
- PROCEDURES TO OBTAIN PHOTOACTIVE COATINGS AND / OR CRYSTAL ANATASE PHASE OF TITANIUM OXIDES AND ARTICLES MADE IN THIS FORM.
Classification
- CPC, 8
- C23C14/5806
- C03C17/3417
- C03C2217/71
- C23C14/024
- C23C14/083
- C23C14/185
- C23C14/5853
- Y02T50/60
- IPC, 12
- C03C17 245
- B01J21 06
- B01J35 00
- B01J37 02
- C03C17 27
- C03C17 34
- C23C14 02
- C23C14 08
- C23C14 18
- C23C14 58
- C30B23 04
- C30B29 16