Method of making heat treated coated article using diamond-like carbon (dlc) coating and protective film on acid-etched surface.
Abstract
There is provided a method of making a heat treated (HT) coated article to be used in shower door applications, window applications, or any other suitable applications where transparent coated articles are desired. For example, certain embodiments of this invention relate to a method of making a coated article including a step of heat treating a glass substrate coated with at least a layer of or including diamond-like carbon (DLC) and an overlying protective film thereon. In certain example embodiments, the protective film may be of or include both (a) an oxygen blocking or barrier layer, and (b) a release layer. Following and/or during heat treatment (e.g., thermal tempering, or the like) the protective film may be removed. Other embodiments of this invention relate to the pre-HT coated article, or the post- HT coated article.

Term
5.7 yearsleft in the term
Expires 20 June 2032.
- Priority
- Filed
- Granted
- Today
- Expires
20 claims: 13 independent, 7 dependent
- 1CLAIMS REIVINDICACIONES 1. Un método para hacer un artículo revestido, el método está caracterizado porque comprende:proporcionar un substrato de vidrio que incluye una primera superficie principal y una segunda superficie principal, la primera superficie principal es atacada con ácido con un mordiente ácido blando y la segunda superficie principal es opuesta a la primera superficie principal;disponer una capa que comprende carbón tipo diamante (DLC), sobre la primera superficie principal;y disponer una película protectora sobre el substrato de vidrio encima de por lo menos la capa que comprende DLC, la película protectora incluye por lo menos capas de desprendimiento y barrera de oxígeno, las capas de desprendimiento y barrera de oxígeno son materiales diferentes y/o tienen diferentes estequiometrías en comparación unas con otras, en donde el substrato de vidrio con la capa que comprende DLC y la película protectora sobre el mismo se pueden tratar térmicamente a una temperatura suficiente para la templadura térmica, fortalecimiento térmico y/o doblamiento térmico con el fin de causar la remoción de la película protectora sin causar una calcinación significativa de la capa que comprende DLC. one. A method for making a coated article, the method is characterized in that it comprises: providing a glass substrate that includes a first main surface and a second main surface, the first main surface is acid-attacked with a soft acid mordant and the second main surface it is opposite the first main surface;disposing a layer comprising diamond type carbon (DLC), on the first main surface;and disposing a protective film on the glass substrate above at least the layer comprising DLC, the protective film includes at least layers of shedding and oxygen barrier, layers of shedding and oxygen barrier are different materials and / or they have different stoichiometries compared to each other , whereas the glass substrate with the layer including DLC and the protective film thereon can be heat treated at a temperature sufficient for thermal tempering, thermal strengthening and / or thermal bending in order to cause the removal of the protective film without causing significant calcination of the layer comprising DLC.
- 5The method according to any of the preceding claims, characterized in that the release layer comprises zinc oxide. 5. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque la capa de desprendimiento comprende óxido de zinc.
- 6The method according to any of the preceding claims, characterized in that the oxygen barrier layer comprises aluminum nitride. 6. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque la capa barrera de oxígeno comprende nitruro de aluminio.
- 7The method according to any of the preceding claims, characterized in that it further comprises applying a temporary protective sheet in liquid or solid form on top of the protective film. 7. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque comprende además aplicar una lámina protectora temporal en forma líquida o sólida encima de la película protectora.
- 8The method according to any of the preceding claims, characterized in that it further comprises the heat treatment of the glass substrate with the layer comprising DLC and the protective film thereon. 8. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque comprende además el tratamiento térmico del substrato de vidrio con la capa que comprende DLC y la película protectora sobre el mismo.
- 10The method according to any of the preceding claims, characterized in that at least part of the layer comprising DLC is set forth in order to be the outer layer of the coated article as a result of the heat treatment. 10. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque por lo menos parte de la capa que comprende DLC se expone con el fin de que sea la capa exterior del artículo revestido como resultado del tratamiento térmico.
- 11El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque la capa barrera de oxígeno comprende nitruro de aluminio y la capa de desprendimiento comprende oxinitruro de zinc. raise. The method according to any of the preceding claims, characterized in that the oxygen barrier layer comprises aluminum nitride and the release layer comprises zinc oxynitride.
- 12The method according to any of the preceding claims, characterized in that before the heat treatment the dielectric layer or barrier is 15-150 nm thick, the inclusive DLC layer is 3-10 nm thick, the detachment layer is 100 -300 nm thick and the oxygen barrier layer is 35-75 nm thick. 12. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque antes del tratamiento térmico la capa dieléctrica o barrea es de 15-150 nm de espesor, la capa inclusiva de DLC es de 3-10 nm de espesor, la capa de desprendimiento es de 100-300 nm de espesor y la capa barrera de oxígeno es de 35-75 nm de espesor.
- 13The method according to any of the preceding claims, characterized in that the second main surface is exposed to a tin bath during the manufacture of the glass substrate. 13. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque la segunda superficie principal se expone a un baño de estaño durante la fabricación del substrato de vidrio.
- 14A method for making a heat treated coated article, the method is characterized in that it comprises:providing a glass substrate that includes a first main surface and a second main surface, the first main surface has been acid-attacked with at least one acid mordant Soft, the second main surface is opposite the first main surface, the first main surface supports, in order moving away from the substrate: a layer comprising diamond type carbon (DLC) on the first main surface and a protective film that includes at least layers of detachment and oxygen barrier, the layers of detachment and oxygen barrier are different materials and / or have different stoichiometry in comparison with each other;and heat treating the glass substrate with the layer comprising DLC and the protective film thereon, in order to remove the layers of detachment and oxygen barrier and cause at least a portion of the layer comprising DLC to be exposed as an outer layer of the heat treated coated article. 14. Un método para hacer un artículo revestido tratado térmicamente, el método está caracterizado porque comprende: proporcionar un substrato de vidrio que incluye una primera superficie principal y una segunda superficie principal, la primera superficie principal ha sido atacada con ácido con por lo menos un mordiente ácido blando, la segunda superficie principal es opuesta a la primera superficie principal, la primera superficie principal soporta, en orden alejándose del substrato: una capa que comprende carbón tipo diamante (DLC) sobre la primera superficie principal y una película protectora que incluye por lo menos capas de desprendimiento y barrera de oxígeno, las capas de desprendimiento y barrera de oxígeno son diferentes materiales y/o tienen diferentes estequiometrías en comparación unas con otras;y tratar térmicamente el substrato de vidrio con la capa que comprende DLC y la película protectora sobre el mismo, con el fin de eliminar las capas de desprendimiento y barrera de oxígeno y causar que por lo menos una porción de la capa que comprende DLC sea expuesta como una capa exterior del artículo revestido tratado térmicamente.
- 17The method according to any of claims 14-16, characterized in that the release layer comprises zinc oxide and / or zinc oxynitride and mainly the oxygen barrier layer comprises aluminum nitride. 17. El método de conformidad con cualquiera de las reivindicaciones 14-16, caracterizado porque la capa de desprendimiento comprende óxido de zinc y/u oxinitruro de zinc y en donde la capa barrera de oxígeno comprende nitruro de aluminio.
- 18The method according to any of claims 14-17, characterized in that the release layer consists essentially of zinc oxide and / or zinc oxynitride and the oxygen barrier layer consists essentially of aluminum nitride. 18. El método de conformidad con cualquiera de las reivindicaciones 14-17, caracterizado porque la capa de desprendimiento consiste esencialmente de óxido de zinc y/u oxinitruro de zinc y la capa barrea de oxígeno consiste esencialmente de nitruro de aluminio.
- 19A heat treatable coated article, characterized in that it comprises:a glass substrate having a first main surface and a second main surface, the first main surface is attacked with acid with two passes of a soft acid mordant;Meanwhile the first main surface supports at least temporarily, in order away from the substrate: a layer comprising silicon;a layer comprising diamond type carbon (DLC);even zinc shedding layer;and a layer comprising aluminum nitride, whereas the glass substrate can be heat treated in order to cause the removal of the inclusive zinc release layer and the layer comprising aluminum nitride, leaving the layer comprising DLC as an outer layer and where the coated article has a higher scratch resistance than it would otherwise have if the first main surface were corroded with a hard acid mordant. 19. Un artículo revestido tratable térmicamente, caracterizado porque comprende: un substrato de vidrio que tiene una primera superficie principal y una segunda superficie principal, la primera superficie principal es atacada con ácido con dos pasadas de un mordiente ácido blando;en donde la primera superficie principal soporta por lo menos temporalmente, en orden alejándose del substrato: una capa que comprende silicio;una capa que comprende carbón tipo diamante (DLC);una capa de desprendimiento inclusiva de zinc;y una capa que comprende nitruro de aluminio, en donde el substrato de vidrio se puede tratar térmicamente con el fin de causar la remoción de la capa de desprendimiento inclusiva de zinc y la capa que comprende nitruro de aluminio, dejando la capa que comprende DLC como una capa exterior y en donde el artículo revestido tiene una resistencia a arañazos más alta que aquella que tendría de otra manera si la primera superficie principal fuera corroída con un mordiente ácido duro.
Independent claims13
129 paragraphs in 6 sections, as filed
The reference patent is granted based on articles 1<sup>to</sup>. 2<sup>to</sup> fraction V, 6<sup>to</sup> Section III, and 59 of the Industrial Property Law.
In accordance with article 23 of the Industrial Property Law, the present patent is valid for twenty non-extendable years, counted from the date of submission of the international application and will be subject to the payment of the fee to keep the rights in force .
Who subscribes to this title does so based on the provisions of articles 6<sup>to</sup> fraction III, 7<sup>to</sup> BIS 2 and 59 of the Industrial Property Law; articles 1<sup>to</sup>, 3<sup>to</sup> fraction V subsection a), sub subsection ¡i), 4<sup>to</sup> and 12<sup>to</sup> sections I and III of the Regulations of the Mexican Institute of Industrial Property; articles 1<sup>to</sup>, 3<sup>to</sup>, 4<sup>to</sup>, 5<sup>to</sup> fraction V subsection a), subparagraph ii), 16 fractions I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property; one<sup>to</sup>, 3<sup>to</sup> and 5<sup>to</sup> subsection a) and the second to last paragraph of the Agreement that delegates powers to the Deputy Directors General, Coordinator, Divisional Directors, Regional Office Holders, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property.
This document is signed with an advanced electronic signature (FAITHFUL), based on Articles 7 BIS 2 of the Industrial Property Law; 3rd of its Regulations, and 1 section III, 2 section V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Electronic Payment and Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.
DIVISIONAL SUB-DIRECTOR OF PATENT FUND EXAMINATION BIOTECHNOLOGICAL, PHARMACEUTICAL AND CHEMICAL AREAS
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EMELIA HERNÁNDEZ PRIEGO
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EMELIA HERNANDEZ PRIEGO | 00001000000405397295 | Administration Service
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MX 2019'61273
<td></td><td>«; Continuation of Classification Symbols</td>
<td>Classification:</td><td>CPC: C03C2217 / 282; C03C2218 / 15; C03C2218 / 31; C03C2218 / 33; C03C2218 / 36; C03C2218 / 322; C03C2218 / 328; C03C2218 / 355; Y10T156 / 1163</td>
METHOD FOR MAKING A TREATED ARTICLE
THERMALLY USING A DIAMOND TYPE CARBON COATING (DLC) AND A PROTECTIVE FILM ON A SURFACE ATTACKED WITH ACID
FIELD OF THE INVENTION
Certain embodiments of this invention refer to a method for making a heat treated coated article (HT) that is used in shower door applications, window applications, table top applications or any other application. adequate. For example, certain embodiments of this invention relate to a method for making a coated article that includes a step that consists of thermally treating a glass substrate coated with at least one layer comprising diamond-type carbon (DLC). English) and an overlying protective film on it. In certain exemplary embodiments, the protective film may be of or may include both (a) an oxygen barrier or blocking layer and (b) a release layer. After and / or during heat treatment (for example, thermal tempering or the like) the protective film can be completely or partially removed. Other embodiments of this invention relate to the coated article before HT or to the coated article after HT.
BACKGROUND AND SUMMARY OF THE EXEMPLARY MODES OF THE INVENTION
Coated items such as transparent shower doors and IG window units are frequently heat treated (HT), such as being thermally tempered, for security and / or strengthening purposes. For example, coated glass substrates for use in shower door units and / or windows are often heat treated at a high temperature (s) (for example, at least about 580 ° C , more typically about 600-650 ° C) for tempering purposes.
Diamond type carbon (DLC) is sometimes known for its scratch resistance properties. For example, different types of DLC are raised in the following United States Patents Nos. 6,303,226; 6,303,225; 6,261,693; 6,338,901; 6,312,808; 6,280,834; 6,284,377; 6,335,086; 5,858,477; 5,635,245; 5,888,593; 5,135,808; 5,900,342; and 5,470,661, all of which are incorporated by this act in this document by reference.
Sometimes it would be desirable to provide a window unit or other glass article with a protective coating that includes DLC for the purpose of protecting it from scratches and the like. Unfortunately, DLC tends to oxidize and calcine at temperatures of approximately 380 to 400 ° C, since heat treatment is typically conducted in an atmosphere that includes oxygen. Thus, it will be appreciated that the DLC as a protective outer coating cannot withstand the heat treatments (HT) at the extremely high temperatures described above which are frequently required in the manufacture of vehicle windows, IG window units, upper parts of glass tables and / or similar.
Therefore, those skilled in the field will appreciate that there is a need in the field for a method of providing heat treated (HT) coated articles with a protective coating (one or more layers) comprising DLC. There is also a need for corresponding coated articles, both heat treated and before HT.
Certain exemplary embodiments of this invention refer to a method for making a heat treated (HT) coated article that is used in shower door applications, window applications, table top applications or any other suitable application. For example, certain embodiments of this invention relate to a method for making a coated article that includes a step that consists of thermally treating a glass substrate coated with at least one layer comprising diamond-type carbon (DLC) and a protective film. overlying on it. In certain exemplary embodiments, the protective film may be of or may include both (a) an oxygen barrier or blocking layer and (b) a release layer. After and / or during heat treatment (for example, thermal tempering or the like) the protective film can be completely or partially removed. Other embodiments of this invention relate to the coated article before HT or to the coated article after HT.
An exemplary advantage of the use of different and different oxygen blocking and shedding layers in the protective film is that each layer of the protective film can be optimized for its intended function. Consequently, the optimized performance of the protective film can be improved and made thinner if desired.
In certain exemplary embodiments of this invention, a method for making a heat treated coated article is provided, the method comprises: providing a glass substrate; forming at least one layer comprising diamond carbon (DLC) on the glass substrate; forming a protective film on the glass substrate above at least the layer comprising DLC, the protective film includes a release layer and an oxygen barrier layer, the release layer and the oxygen barrier layer are of different material and / or different stoichiometry in mutual relationship; thermally treating the glass substrate with the layer comprising DLC and the protective film thereon so that during the heat treatment the protective film prevents significant calcination of the layer comprising DLC, wherein the heat treatment comprises heating the substrate of glass at sufficient temperature (s) for thermal tempering, thermal strengthening and / or thermal bending; and exposing the protective film to a release liquid and removing at least part of the protective film during and / or after heat treatment.
In certain exemplary embodiments of this invention, a method is provided for making a heat treated coated article, the method comprises: heat treating a coated glass substrate, the coated glass substrate comprises, before heat treatment, a glass substrate, a layer comprising diamond type carbon (DLC) on the glass substrate; and a protective film on the glass substrate above at least the layer comprising DLC, wherein the protective film includes a detachment layer and an oxygen barrier layer and the detachment layer and the oxygen barrier layer are of different material and / or different stoichiometry in mutual relationship; during the heat treatment of the glass substrate coated with the layer comprising DLC and the protective film thereon, the protective film prevents significant calcination of the layer comprising DLC and where the heat treatment comprises heating the glass substrate at temperature (s) sufficient for thermal tempering, thermal strengthening and / or thermal bending; and exposing the protective film to a release liquid and removing at least part of the protective film during and / or after heat treatment.
In certain exemplary embodiments of this invention, a method of making a coated article is provided, the method comprises: providing a glass substrate that includes a first main surface and a second main surface, the first main surface is exposed to a tin bath during the manufacture of the glass substrate and the second main surface is opposite to the first main surface and is attacked with acid; ion beam treating the first main surface of the substrate in order to remove a portion of the surface of the substrate, the surface portion comprises tin, tin oxide and / or surface contaminants; disposing an inclusive layer of zirconium on the first main surface after ion beam treatment; and disposing a layer comprising diamond type carbon (DLC), directly or indirectly, on the inclusive zirconium layer. The glass substrate with the inclusive zirconium layer and the layer comprising DLC can be heat treated at a temperature sufficient for thermal tempering, thermal strengthening and / or thermal bending in order to cause calcination of the layer comprising DLC but without also causing significant calcination of the zirconium inclusive layer.
In certain exemplary embodiments of this invention, a method for making a heat treated coated article is provided, the method comprises: providing a glass substrate that includes a first main surface and a second main surface, wherein the first main surface has been exposed to a tin bath during the manufacture of the glass substrate and has been treated with ion beam for the purpose of remove a portion of the surface thereof that comprises tin, tin oxide, and / or surface contaminants, where the second main surface is opposite to the first main surface and has been attacked with acid, and where the first main surface supports, in order away from the substrate, an inclusive layer of zirconium and a layer comprising diamond type carbon (DLC ); and heat treating the glass substrate with the inclusive zirconium layer and the layer comprising DLC thereon, in order to remove the layer comprising DLC and cause at least a portion of the inclusive zirconium layer to be exposed as an outer layer of the heat treated coated article.
In certain exemplary embodiments of this invention, a heat treatable coated article is provided, comprising: a glass substrate having a first main surface and a second main surface, where the first main surface is a tin side of the substrate and is corroded with ion beam or finely milled in order to remove tin, tin oxide and / or surface contaminants of a portion of the surface thereof, the second main surface is attacked with acid. The first main surface supports at least temporarily, in order away from the substrate: a layer comprising zirconium nitride and a layer comprising diamond type carbon (DLC). The glass substrate can be heat treated in order to (a) cause the removal of the layer comprising DLC and (b) convert the layer comprising zirconium nitride to a layer comprising zirconium oxide. The first main surface corroded with an ion beam or finely milled causes the fogging to be lower after treatment than would be otherwise if the first main surface were not corroded with an ion beam or finely milled.
In certain exemplary embodiments of this invention, a heat treated coated article is provided, comprising: a glass substrate having a first main surface and a second main surface, where the first main surface is a tin side of the substrate and is corroded with ion beam or finely milled in order to remove tin, tin oxide and / or surface contaminants of a portion of the surface thereof and where the second main surface is attacked with acid. The first main surface supports, in order moving away from the substrate, a layer comprising zirconium nitride and a layer comprising diamond type carbon (DLC). The first main surface corroded with an ion beam or finely milled causes the fogging to be lower after treatment than would be otherwise if the first main surface were not corroded with an ion beam or finely milled.
In certain exemplary embodiments of this invention, a method of making a coated article is provided, the method comprises: providing a glass substrate that includes a first main surface and a second main surface, the first main surface is exposed to a tin bath during the manufacture of the glass substrate and the second main surface is opposite to the first main surface and is attacked with acid; ion beam treating the first main surface of the substrate in order to remove a portion of the surface of the substrate, the surface portion comprises tin, tin oxide and / or surface contaminants; arranging a layer comprising diamond type carbon (DLC) on the first main surface after ion beam treatment; and disposing a protective film on the glass substrate above at least the layer comprising DLC, the protective layer that includes at least layers of detachment and oxygen barrier, the layers of detachment and oxygen barrier are of different materials and / or have different stoichiometries compared to each other. The glass substrate with the layer comprising DLC and the protective film thereon can be heat treated at a temperature sufficient for thermal tempering, thermal strengthening and / or thermal bending in order to cause the removal of the protective film without causing a significant calcination of the layer comprising DLC.
In certain exemplary embodiments of this invention, a method of making a coated article is provided, the method comprises: to provide a glass substrate that includes a first main surface and a second main surface, the first main surface has been exposed to a tin bath during the manufacture of the glass substrate and has been treated with an ion beam in order to remove a portion of the surface thereof comprising tin, tin oxide and / or surface contaminants, the second main surface is opposite the first main surface and has been attacked with acid with a soft or hard acid mordant, the first main surface supports, in order moving away from the substrate, a layer comprising diamond-type carbon (DLC), a layer detachment and an oxygen barrier layer; and heat treating the glass substrate with the layer comprising DLC, the shedding layer and the oxygen barrier layer thereon, in order to remove the shedding and oxygen barrier layers and cause at least a portion of The layer comprising DLC is exposed as an outer layer of the heat treated coated article.
In certain exemplary embodiments of this invention, a heat treatable coated article is provided, comprising: a glass substrate having a first main surface and a second main surface, the first main surface is a tin side of the substrate and is corroded with an ion beam or finely milled in order to remove tin, tin oxide and / or surface contaminants of a portion of the surface thereof, the second main surface is attacked with acid. The first main surface supports at least temporarily, in order away from the substrate: a layer comprising diamond type carbon (DLC); an inclusive zinc shedding layer; and a layer comprising aluminum nitride. The glass substrate can be heat treated in order to remove the inclusive zinc release layer and the aluminum nitride layer, leaving the DLC layer as an outer layer. The first main surface corroded with an ion beam or finely milled causes the fogging to be lower after treatment than would be otherwise if the first main surface were not corroded with an ion beam or finely milled.
In certain exemplary embodiments of this invention, a heat treated coated article is provided, comprising a glass substrate having a first main surface and a second main surface, the first main surface is a tin side of the substrate and is corroded with a beam. of ions or is finely milled in order to remove tin, tin oxide and / or surface contaminants from a portion of the surface thereof, The second main surface is attacked with acid with a soft or hard acid mordant. The first main surface supports a layer comprising diamond type carbon (DLC). The first main surface corroded with an ion beam or finely milled causes the fogging to be lower after treatment than would be otherwise if the first main surface were not corroded with an ion beam or finely milled.
In certain exemplary embodiments of this invention, a method of making a coated article is provided, the method comprises: providing a glass substrate that includes a first main surface and a second main surface, the first main surface is acid-attacked with a mordant soft acid and the second main surface is opposite the first main surface; disposing a layer comprising diamond type carbon (DLC) on the first main surface; and disposing a protective film on the glass substrate above at least the layer comprising DLC, the protective film includes at least layers of shedding and oxygen barrier, layers of shedding and oxygen barrier are different materials and / or They have different stoichiometries compared to each other. The glass substrate with the layer comprising DLC and the protective film thereon can be heat treated at a temperature sufficient for thermal tempering, thermal strengthening and / or thermal bending in order to cause the removal of the protective film without causing a significant calcination of the layer comprising DLC.
In certain exemplary embodiments of this invention, a method of making a heat treated coated article is provided, the method comprises: providing a glass substrate that includes a first main surface and a second main surface, the first main surface has been acid-attacked With a soft acid mordant, the second main surface is opposite the first main surface. The first main surface supports, in order moving away from the substrate: a layer comprising diamond carbon (DLC) on the first main surface and a protective film that includes at least layers of detachment and oxygen barrier, the layers of detachment and barrier of oxygen are of different materials and / or have different stoichiometries compared to each other. The glass substrate with the layer comprising DLC and the protective film thereon is heat treated, in order to remove the shedding and oxygen barrier layers and cause at least a portion of the layer comprising DLC to be exposed as an outer layer of the heat treated coated article.
In certain exemplary embodiments of this invention, a heat treatable coated article is provided, comprising: a glass substrate having a first main surface and a second main surface, the first main surface is acid-attacked with two passes of an acid mordant soft. The first main surface supports at least temporarily, in order away from the substrate: a layer comprising silicon; a layer comprising diamond type carbon (DLC); an inclusive zinc shedding layer; and a layer comprising aluminum nitride. The glass substrate can be heat treated in order to cause the removal of the zinc inclusive release layer and the aluminum nitride layer, leaving the layer comprising DLC as an outer layer. The coated article has a higher scratch resistance than it would otherwise have if the first main surface were attacked with a hard acid mordant.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGURE 1 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with an exemplary embodiment of this invention.
FIGURE 2 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 3 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 4 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with an exemplary embodiment of this invention.
The figure. 5 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 6 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 7 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 8 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 9 is a schematic cross-sectional view of a coated article having a silky smooth appearance, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 10 is a schematic view of an ion beam that is used for reconditioning a substrate that has a silky smooth appearance, in accordance with an exemplary embodiment of this invention.
FIGURE 11 is a schematic cross-sectional view of a coated article having a silky smooth appearance and low fogging after heat treatment, in accordance with another exemplary embodiment of this invention.
The figure. 12 is a schematic cross-sectional view of another coated article having a silky smooth appearance and a low fog after the heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 13 compares coated articles that have been corroded with an ion beam according to certain exemplary modalities (left side) with coated articles that have not been corroded with an ion beam (right side).
FIGURE 14 is a schematic cross-sectional view of a coated article having a silky smooth appearance and improved scratch resistance in accordance with certain exemplary embodiments of this invention.
FIGURE 15 is a schematic cross-sectional view of a heat treatable coated article having a silky smooth appearance and improved scratch resistance in accordance with certain exemplary embodiments of this invention.
DETAILED DESCRIPTION OF THE EXEMPLARY MODES OF THE INVENTION
Reference is now made more particularly to the associated drawings in which similar reference numbers indicate similar parts by all the various views.
Certain exemplary embodiments of this invention refer to methods for making coated articles that can use heat treatment (HT), wherein the coated article includes a coating (one or more layers) that includes diamond type carbon (DLC). In certain cases, HT may involve heating a support glass substrate, with the DLC thereon, at a temperature (s) of 550 to 800 ° C, more preferably 580 to 800 ° C (which is very higher than the calcination temperature of the DLC). In particular, certain exemplary embodiments of this invention refer to a technique to allow DLC to resist this HT without significantly calcining during it. In certain embodiments, a sacrificial protective film is formed on the glass substrate above the DLC in order to reduce the probability of calcination of the DLC during HT. In this way, most (if not all) of the DLC remains on the glass substrate and is not calcined, during HT. After HT, the sacrificial protective film (which may include one or more layers) may or may not be removed in different embodiments of this invention.
In certain exemplary embodiments, the sacrificial protective film may be of or may include both (a) an oxygen barrier or blocking layer and (b) a release layer. An exemplary advantage of the use of different and different oxygen blocking and shedding layers in the film 17 is that each layer (17a and 17b) can be optimized for its intended function. Consequently, the optimized performance of the sacrificial film 17 can be improved and made thinner if desired. In certain exemplary embodiments, after HT the inclusive DLC layer protects against abrasion and corrosion and against the adhesion of minerals in hard water (for example, it has good hard water washability).
Figure 1 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with an exemplary embodiment of this invention. Typically, the coated article on the left side of Figure 1 exists during a manufacturing stage before heat treatment (HT), but may also exist after HT in certain cases. The coated article shown in Figure 1 includes the glass substrate 1, the inclusive DLC layer 11 and the sacrificial protective film 17 which may include one or more layers. In certain exemplary embodiments, the protective film 17 includes a first layer 17a and a second layer 17b which may be of the same or different materials.
The glass substrate 1 is typically of or includes soda-lime-silica glass, although in other cases other types of glass may be used.
The inclusive layer of DLC 11 may be approximately 5 to 1,000 angstroms (Á) thick in certain exemplary embodiments of this invention, more preferably 10-300 Á thick and much more preferably 20 to 65 Á thick, possibly of approximately 25-50 Á thick, with an exemplary thickness being approximately 30 angstroms. In certain exemplary embodiments of this invention, a layer of DLC 11 may have an average hardness of at least about 10 GPa, more preferably of at least about 20 GPa and much more preferably of about 20-90 GPa. This hardness returns to the layer (s) 11 resistant to scratches, certain solvents and / or the like. In certain exemplary embodiments, layer 11 may be of or may include a special type of DLC known as highly tetrahedral amorphous carbon (t-aC) and in certain embodiments it may be hydrogenated (t-aC: H). In certain hydrogenated embodiments, the type of t-aC or any other suitable type of DLC may include 1 to 30% hydrogen, more preferably 5-20% H and much more preferably 10-20% H. East. TLC type of DLC includes more carbon-carbon bonds (C - - C) sp<sup>3 </sup>which carbon-carbon bonds (C - - C) sp<sup>2</sup>. In certain exemplary embodiments, at least about 30% or 50% of the carbon-carbon bonds in the DLC layer 11 may be carbon-carbon bonds (C - - C) sp<sup>3</sup>, more preferably at least about 60% of the carbon-carbon bonds in layer 11 may be carbon-carbon (C - - C) sp bonds<sup>3</sup> and much more preferably at least about 70% of the carbon-carbon bonds in layer 11 may be carbon-carbon (C - - C) sp bonds<sup>3</sup>. In certain exemplary embodiments of this invention, the DLC may have an average density of at least about 2.4 gm / cm.<sup>3</sup>, more preferably at least about
2.7 gm / cm<sup>3</sup>. Exemplary linear ion beam sources that can be used to deposit the inclusive layer of DLC 11 on substrate 1 include any of those in any of US Pat. Nos. 6,261,693, 6,002,208, 6,335,086 or 6,303,225 (all incorporated in this document as a reference). When an ion beam source is used to deposit the layer (s) 11, the gas (s) of hydrocarbon feedstock (for example, C<sub>2</sub>H<sub>2</sub>), HMDSO or any
<td>other</td><td>gas</td><td>suitable,</td><td>I know</td><td>they can)</td><td>use in</td><td>the</td><td colspan="2">source of</td>
<td>you do</td><td>from</td><td>ions with</td><td>the</td><td>purpose</td><td>to cause</td><td>what</td><td>the</td><td>source</td>
<td>issue</td><td>a</td><td colspan="2">ion beam</td><td>to him</td><td>substrate</td><td colspan="2">1 for</td><td>to form</td>
the layer (s) 11. It should be noted that the hardness and / or density of the layer (s) 11 can be adjusted by varying the ionic energy of the deposition apparatus.
The DLC layer 11 allows the coated article to be more scratch resistant than in the possible case that the DLC layer 11 was not provided. It should be noted that while the layer 11 is on the glass substrate 1 in certain embodiments of this invention, an additional layer (s) may or may not be under layer 11 between substrate 1 and layer 11 in certain exemplary embodiments of this invention. Thus, the phrase about the substrate as used herein is not limited to being in direct contact with the substrate since yet another layer (s) can be provided between them.
For example and without limitation, layer 11 of or including DLC may be any of the inclusive DLC layers of any of US Pat. Nos. 6,592,993; 6,592,992; 6,531,182; 6,461,731; 6,447,891; 6,303,226; 6,303,225; 6,261,693; 6,338,901; 6,312,808;
6,280,834; 6,284,377; 6,335,086; 5,858,477; 5,635,245; 5,888,593; 5,135,808; 5,900,342; or 5,470,661 (all these patents are hereby incorporated herein by reference), or alternatively it may be any other suitable type of DLC inclusive layer. The inclusive layer of DLC 11 may be hydrophobic (high contact angle), hydrophilic (low contact angle) or none, in different embodiments of this invention. The DLC layer 11 may or may not include about 5-30% Si, more preferably about 5-25% Si and possibly about 10-20% Si in certain exemplary embodiments of this invention. Hydrogen can also be provided in the DLC in certain cases.
The sacrificial protective film 17 is provided for the purpose of protecting the DLC layer 11 during HT. In the event that film 17 was not provided, the DLC layer 11 would oxidize significantly during HT and calcine, thereby rendering the final product defenseless against scratches. However, the presence of the sacrificial protective film 17 prevents or reduces the amount of oxygen that the DLC layer 11 can reach during the HT of the surrounding atmosphere, thereby preventing the DLC from oxidizing significantly during the HT. As a result, after HT, the inclusive layer of DLC 11 remains on the glass substrate 1 for the purpose of providing resistance to scratches and / or the like. In certain exemplary embodiments, the protective film 17 includes both an oxygen barrier or blocking layer 17a and a release layer 17b.
It has surprisingly been discovered that the use of zinc and / or zinc oxide in the sacrificial protective film 17 is especially beneficial with respect to the reduction and / or prevention of oxygen diffusion in the DLC during HT. In the exemplary embodiment of Figure 1 of this invention, the protective film 17 includes a first inclusive layer of zinc 17a and a second inclusive layer of zinc oxide 17b. The first inclusive zinc layer 17a may be metallic zinc oxide, substantially metallic or sub-stoichiometric in different exemplary embodiments of this invention; while the second inclusive zinc oxide layer 17b may be of or may include zinc oxide in certain exemplary embodiments of this invention. In certain exemplary embodiments, layer 17a is more metallic than layer 17b. In other words, layer 17b contains more oxygen than layer 17a. In this way, the layer 17a can function as a detachment layer while the layer 17b can function as an oxygen barrier or blocking layer. An oxygen barrier or blocking layer means that the layer prevents significant amounts of oxygen from reaching DLC during HT.
In certain exemplary embodiments of this invention, layer 17a may be of or include ZnO<sub>Y</sub> and layer 17b may be of or include ZnO<sub>x</sub>, where x> y (that is, layer 17b contains more oxygen than layer 17a). On the other hand, in certain exemplary embodiments of this invention, and is from about 0 to 0.9, more preferably from about 0.1 to 0.9, even more preferably from about 0.1 to 0.8, and possibly from about 0.1 to 0.7. Meanwhile, in certain exemplary embodiments of this invention, x is greater than y, and x is from about 0.3 to 1.0, more preferably from about 0.3 to 0.99, even more preferably from about 0.5 to 0.95 and possibly from about 0.6 to 0.90. In this way, it will be appreciated that in certain exemplary cases, both layers 17a and 17b can be of or include zinc oxide and both layers 17a and 17b can be substemetric.
Advantageously, it has been found that the use of the zinc oxide layer 17a that is more metallic than the zinc oxide layer 17b surprisingly allows the most efficient and easiest removal of the protective film 17 during and / or after heat treatment (HT). In other words, layer 17a is a layer of detachment. The different compositions of the zinc oxide inclusive layers 17a and 17b are used to cause different stresses in the layers 17a and 17b, stresses which are manipulated in order to allow the film 17 to be more easily removed during and / or after of HT. In particular, the more metallic zinc oxide-based layer 17a can be considered as a shedding layer to allow the film 17 to be easily removed from the DLC or the substrate during and / or after the HT due to its reduced or zero content of oxygen, while the less metallic (and more oxidized) zinc oxide-based layer 17b can be considered as an oxygen barrier or blocking layer that reduces or prevents the DLC from calcining and / or oxidizing during HT. It should also be taken into account that any absorption layer can be considered as an oxygen barrier layer in certain exemplary cases. In certain exemplary cases, the more oxidic layer 17b can be considered a blocking / protective layer, to protect the less oxidic, softer absorption / barrier layer 17a during heat treatment and otherwise. Zinc oxide is an extremely advantageous material for film 17 because it can be easily removed (for example, using water and / or vinegar) during and / or after HT in a non-toxic manner.
As mentioned above, one or both layers 17a and 17b when they are of or include zinc and / or zinc oxide may be sub-stoichiometric. This is advantageous for the purpose of oxygen absorption during HT. If the zinc oxide of the entire film 17 is very oxidized (that is, it is completely stoichiometric) before HT, then oxygen can diffuse through the zinc oxide. However, the sub-stoichiometric character of layer (s) 17a and / or 17b allows the zinc in the same (s) to absorb oxygen during HT, so that at least layer 17a (and possibly layer 17b) is not calcined during HT. It should be noted that the top layer based on zinc oxide 17b can be calcined or not (completely or partially) during HT in different exemplary embodiments of this invention. It should be borne in mind that another exemplary advantage of sub-stoichiometric zinc oxide (as compared to completely stoichiometric zinc oxide) is that it can be deposited (for example, by ionic spraying or the like) more quickly. One or both layers 17a, 17b may be deposited by means of ionic spraying in a sub-stoichiometric form, in any suitable manner; for example, by varying the flow of gaseous oxygen in the ionic spray chamber (s). For example, as a non-limiting example, the layer 17a can be deposited by means of ionic spraying using 10 ml / kW (with respect to the content of the gaseous oxygen flow), while the layer 17b can be deposited by means of the ionic spraying using 12 ml / kw (the rest of the gas being Ar or the like) in exemplary cases.
It should be noted that one or both layers of zinc oxide 17a and 17b can be impurified with other materials such as Al, N, Zr, Ni, Fe, Cr, Ti, Mg, mixtures thereof or the like, in certain exemplary embodiments of this invention.
In certain exemplary embodiments of this invention, the release layer 17a (for example, of zinc or sub-stoichiometric zinc oxide) can be deposited (for example, by ion spraying) in order to be approximately 50-20,000 Á thick, more preferably about 50-3,000 Á thick, even more preferably about 100-1,000 Á thick, an exemplary thickness being about 100-300 Á. In certain embodiments, the inclusive zinc oxide layer 17b can be deposited (for example, via ionic spraying) in order to be approximately 200-10,000 Á thick, more preferably approximately 500-5,000 Á of thickness, more preferably about 1,000-3,000 Á thick, with an exemplary thickness being about 2,000 Á. The more metallic layer 17a may be thicker than the less metallic layer 17b in certain exemplary embodiments of this invention; layer 17a may be at least twice as thick as layer 17b in certain exemplary cases before HT. A preferred thickness of the total sacrificial film 17 in certain exemplary embodiments is less than about 10,000 Á, more preferably less than about 3,000 Á and much more preferably less than about 1,000 Á.
Figure 2 illustrates another exemplary embodiment of this invention. The modality of Figure 2 is the same as the modality of Figure 1 set forth above, except that in the modality of Figure 2 a barrier layer 6 is provided between the glass substrate 1 and the inclusive DLC layer 11. The layer Barrier 6 may be of a dielectric material in certain exemplary embodiments of this invention. The optional barrier layer 6 is to prevent or reduce the oxygen and / or sodium (Na) that migrates from the glass 1 into the DLC layer 11 during the HT. In this regard, this optional barrier layer 6 can improve the overall optical characteristics of the coated article after HT. The barrier layer 6 may be of or may include silicon oxide, silicon nitride, silicon oxynitride and / or the like, although other barrier materials may also be used. The barrier layer (s) 6 is formed on the glass substrate 1 via ionic spraying or by any other suitable technique. The barrier layer 6 may be approximately 10 to 1,000 Á thick in certain exemplary embodiments, more preferably 50 to 500 Á thick and much more preferably 50 to 200 Á thick. It should be noted that a barrier layer (s) 6 can also be provided in other exemplary embodiments of this invention, for example in any of Figures 4-7 if desired between the DLC layer 11 and the glass substrate
1.
Figure 3 illustrates another exemplary embodiment of this invention. The mode of Figure 3 is the same as the mode of Figure 1 (or even the mode of Figure 2 if the barrier layer 6 is used, which may be the case in the mode of Figure 3), except that instead of two discrete layers 17a and 17b the protective film 17 is made of a layer that has oxidation graduation (continuously or not continuously) throughout its thickness. In the embodiment of Figure 3, the film 17 is provided in such a way that the film 17 includes more oxygen at a location farther from the DLC layer 11 than at another location in the film closer to the DLC layer 11. It should be borne in mind that the film 17 in the modalities of Figures 1-2 can also be considered to have oxidation graduation because the overall film 17 is more oxidized in the farthest layer 17b of the DLC layer 11 than in layer 17a closest to the DLC layer 11. However, in the embodiment of Figure 3, it is also possible for continuous or substantially continuous oxidation graduation to occur for all or substantially all of film 17 in certain exemplary cases.
An exemplary process for the manufacture of a coated article will now be described, with reference to Figures 1-3. Initially, the glass substrate 1 is provided and at least one barrier layer 6 (for example, silicon oxide, silicon nitride, silicon oxynitride or the like) can optionally be ionically sprayed onto a surface thereof. Optionally, a multi-layer solar control coating (which is not shown) can be deposited (for example, via ionic spraying) on the surface of the glass substrate 1 that is opposite the barrier layer 6. Thus at least one layer 11 of or including DLC is deposited (for example, by deposition by means of ion beams) on the glass substrate 1, above at least the optional barrier layer 6 in the event that it is present . Then, the protective film 17, for example that includes layers 17a and 17b, is deposited on the substrate 1 above the inclusive DLC layer 11. The protective film 17 can be deposited via ionic spraying, CVD, deposition by ion beams or any other suitable technique. Optionally, a thin protective layer comprising DLC, silicon nitride, aluminum nitride or silicon aluminum nitride (which is not shown), may be provided on top of the sacrificial film 17 before HT, for durability and / or hydrogen barrier.
As shown in Figures 1-2, the glass substrate 1 with films 6 (optional), 11 and 17 thereon is then heat treated (HT) for the purpose of thermal tempering, thermal bending, thermal strengthening and / or Similar. At least part of this HT can be conducted, for example, in an atmosphere that includes oxygen as is known in the field at a temperature (s) of 550 to 800 ° C, more preferably 580 to 800 ° C (i.e. temperature (s) higher than the calcination temperature of the DLC). The HT may last at least one minute, more preferably 1-10 minutes, in certain exemplary non-limiting embodiments of this invention. During HT, the presence of protective film 17 protects the inclusive DLC layer 11 of HT and prevents layer 11 from oxidizing and / or calcining significantly due to significant oxidation during HT. While in some cases some of the layer 11 can be calcined during the HT, most of it is not that the whole of the inclusive DLC layer remains on the substrate 1 even after the HT due to the presence of the protective film 17 .
A significant advantage that is associated with the use of zinc and / or zinc oxide in film 17 is its ease of removal after HT. Protective layers such as silicon nitride are sometimes undesirable since they require complex corrosion in order to remove them after HT. On the other hand, it has been discovered that when the film 17 is made of zinc and / or zinc oxide, soluble in vinegar and / or water (possibly only water without vinegar being required in certain preferred embodiments), the application of vinegar and / or water allows portions of the film 17 that remain after HT to be easily removed in a non-toxic manner. Again, in certain exemplary embodiments, it is possible to remove zinc oxide only with water (without the need for vinegar) in certain cases, which is advantageous from a cost and processing point of view. In certain exemplary cases, rubbing 25 with these liquids can be especially beneficial in removing film 17 after HT when the coated article is still hot because of it (for example, when film 17 is about 80200 ° C , more preferably about 100-180 ° C; although removal of the film 17 can also take place at room temperature in certain exemplary embodiments).
After the film 17 has been removed, the remaining coated article is shown on the right side of Figures 1-2 and includes an outer layer comprising scratch-resistant DLC. The processes mentioned above are advantageous in that they provide a technique for allowing a coated article that includes an inclusive layer of protective DLC 11 to be heat treated without the DLC layer 11 being calcined during this HT. In other words, it becomes possible to provide an inclusive layer of protective DLC 11 on a heat treated product (eg, thermally tempered) in a commercially acceptable manner.
Figure 4 is a cross-sectional view of an exemplary embodiment of this invention that is similar to Figures 1-2, except that the release layer 17a and the oxygen blocking layer 17b need not be zinc oxide. A barrier layer 6 (raised above) may or may not be provided between the glass and the DLC in the embodiment of Figure 4 (although not shown in the figure).
The oxygen barrier or blocking layer 17b may be of or may include a material selected from the group consisting of: zinc oxide, silicon carbide, aluminum nitride, boron oxide, aluminum oxide, aluminum oxynitride, silicon nitride , silicon oxide, silicon oxynitride and mixtures thereof. Preferred materials for the oxygen barrier or blocking layer 17b are aluminum nitride and silicon carbide in certain exemplary embodiments. In certain exemplary embodiments, layer 17b is designed to be approximately as hard and / or durable as glass.
The release layer 17a can be of any suitable material that dissolves or easily reacts with water, vinegar or bleach. The release layer 17a preferably has a melting point (or dissociation temperature) greater than 580 or 600 ° C in certain exemplary embodiments. The release layer 17a may be of or may include oxides, sub-oxides, nitrides and / or boron subnitrides, titanium boride, magnesium, zinc and mixtures thereof. Preferred materials for the release layer 17a in certain exemplary embodiments are zinc, magnesium and / or titanium boride sub-oxides. It should be noted that the term oxide as used herein is broad enough to include sub-oxides.
In certain exemplary embodiments, the release layer 17a is more soluble than the layer 17b in water, vinegar, bleach and / or the like. On the other hand, in certain exemplary embodiments, the oxygen barrier layer 17b is more of an oxygen barrier and / or is harder than the release layer 17a. Exemplary coatings can produce a high quality DLC after HT and after shedding, with good scratch resistance and good hard water washability. The release layer 17a and / or the oxygen barrier layer 17b can be deposited via ionic spraying, or any other suitable technique, in different exemplary embodiments of this invention.
Figure 5 shows an exemplary embodiment where the release layer 17a is of or includes a magnesium suboxide (MgO<sub>x</sub>) and the oxygen barrier or blocking layer 17b is of or includes silicon carbide. Optionally, a barrier layer 6 can be provided between the DLC layer 11 and the glass substrate 1 in certain cases of this mode, to reduce the migration of sodium during or due to HT. After heat treatment or HT (for example, tempering), the product is exposed to a slightly reactive liquid (for example, water, vinegar, diluted ammonia and / or bleach) and the liquid penetrates through to the release layer 17a by path of small holes or grain boundaries in the overlying layer (s) and causes the detachment layer to disappear from the DLC layer 11. In this way, the release layer 17a and the oxygen barrier layer 17b are removed after HT. Hot water is a particularly good release liquid for use with the materials shown in the embodiment of Figure 5. Exemplary thicknesses are as follows in this exemplary embodiment: barrier layer 6 of silicon nitride or silicon oxynitride formed by means of ionic spraying of approximately 125 or 150 A thick; DLC layer 11 approximately 50A thick; MgOx layer 17a approximately 190A thick and SiC layer 17b approximately 280A thick.
Figure 6 shows an exemplary embodiment where the release layer 17a is of or includes a zinc suboxide (ZnO<sub>x</sub>) and the oxygen barrier or blocking layer 17b is of or includes aluminum nitride (A1N). Optionally, a barrier layer 6 can be provided between the DLC layer 11 and the glass substrate 1 in certain cases of this mode, to reduce the migration of sodium during or due to HT. After heat treatment or HT (for example, tempering), the product is exposed to a slightly reactive liquid (for example, water, vinegar, diluted ammonia and / or bleach) and the liquid penetrates through to the release layer 17a by path of small holes or grain boundaries in the overlying layer (s) and causes the detachment layer to disappear from the DLC layer 11. In this way, the release layer 17a and the oxygen barrier layer 17b are removed after HT. Vinegar is a particularly good release liquid for use with the materials shown in the modality of Figure 6. Exemplary thicknesses are as follows in this exemplary embodiment: silicon nitride barrier layer 6 approximately 150 A thick; DLC layer 11 approximately 50A thick; ZnOx layer 17a approximately 500 Á thick and A1N 17b layer approximately 200 Á thick.
Figure 7 shows an exemplary embodiment where the release layer 17a is of or includes a Mg (MgO) suboxide.<sub>x</sub>) and the oxygen barrier or blocking layer 17b is of or includes aluminum nitride (A1N). Optionally, a barrier layer 6 can be provided between the DLC layer 11 and the glass substrate 1 in certain cases of this mode, to reduce the migration of sodium during or due to HT. After heat treatment or HT (for example, tempering), the product is exposed to a slightly reactive liquid (for example, water, vinegar, diluted ammonia and / or bleach) and the liquid penetrates through to the release layer 17a by path of small holes or grain boundaries in the overlying layer (s) and causes the detachment layer to disappear from the DLC layer 11. In this way, the release layer 17a and the oxygen barrier layer 17b are removed after HT. Hot water is a particularly good release liquid for use with the materials shown in the mode of Figure 7. Exemplary thicknesses are as follows in this exemplary mode: DLC layer 11 approximately 50 A thick; MgOx 17a layer approximately 230 A thick and A1N 17b layer approximately 200 A thick.
Figure 8 is also applicable to any of the modalities outlined above. Figure 8 shows an exemplary embodiment where the release layer 17a is of or includes a zinc suboxide (ΖηΟχ), the oxygen barrier or blocking layer 17b is of or includes aluminum nitride (A1N) and a protective layer of outer coating 17c of or including silicon nitride and / or silicon oxynitride. Optionally, a barrier layer 6 (for example, of or including silicon nitride, silicon oxide and / or silicon oxynitride) can be provided between the DLC layer 11 and the glass substrate 1 in certain cases of this embodiment, to reduce sodium migration during or due to HT. After heat treatment or HT (for example, tempering), the product is exposed to a slightly reactive liquid (for example, water, vinegar, diluted ammonia and / or bleach) and the liquid penetrates through to the release layer 17a by path of small holes or grain boundaries in the overlying layer (s) and causes the detachment layer to disappear from the DLC layer 11. In this way, the release layer 17a, the oxygen barrier layer 17b and the protective layer 17c are removed after HT. Vinegar is a particularly good release liquid for use with the materials shown in the embodiment of Figure 8, although other liquids such as water can also be used instead for the removal of the sacrificial film 17. Brushing (for example, via rotating brushes such as nylon brushes or the like) can be used to remove film 17 when wetted with water or the like in certain exemplary cases. Exemplary thicknesses are as follows in this exemplary embodiment: silicon nitride barrier layer 6 of approximately 100-300 Á thick (for example, approximately 200 Á thick); DLC layer 11 of about 30-60 Á thick (for example, about 30-50 Á thick); ZnOx layer 17a approximately 500-2,000 Á thick, oxygen blocking A1N layer 17b approximately 100-300 Á thick (eg approximately 200 Á thick) and inclusive silicon nitride protective layer 17c approximately 0 -500 Á thick (for example, approximately 200-300 Á thick). The silicon nitride based protective layer 17c is advantageous in that it provides improved mechanical durability of the sacrificial film 17 and prevents or reduces damage to the film coated article during transport and handling (for example, if the film 17 is scratched, it may not adequately protect from calcination to DLC during HT).
In accordance with certain exemplary embodiments of this invention, the articles coated in this document lose no more than about 15% of their transmission in the visible spectrum due to HT, more preferably no more than about 10%. On the other hand, the monolithic coated articles herein preferably have a transmission in the visible spectrum after the HT of at least about 50%, more preferably of at least about 60 or 75%.
As indicated above, the substrate 1 may be a glass of soda-lime-silica. This and other glasses can be made using a waterline, for example, with a tin bath. As is known, a substrate of or including floated virio can have two main surfaces. A first main surface of the substrate may be in contact with the tin bath during the flotation process and the (second) opposite main surface may be exposed to the environment. Thus, in certain exemplary embodiments, a substrate can have two main surfaces, often called a tin side and an air side, for example, because the first main surface makes contact with the tin bath while the surface opposite principal is exposed to the environment or the air.
In certain exemplary embodiments, one or both of the tin side and the air side of a substrate can be coated, for example, using the coatings described herein. Additionally, the coatings described herein can be deposited on one or both main surfaces of the substrate, in different exemplary embodiments.
Decorative glass is known. This glass can be based on soda-lime-silica glass and can be, for example, SatinDeco glass<sup>MR</sup> or SatinDeco Elegance glass<sup>MR </sup>commercially available from Guardian Industries Corp. This type of glass implies a silky smooth appearance, is easy to clean and is resistant to body oils that penetrate the glass (so it is also resistant to stains and fingerprints). It provides privacy while still allowing light to shine through it. The visible and performance properties can be obtained, for example, by attacking the glass with acid, thereby creating a microtextured structure. It should be borne in mind that for SatinDeco glass<sup>MR</sup> 6 mm thick commercially available, for example, the transmission in the visible spectrum is at least 80% from both sides, more preferably it is at least 15% from both sides and in some cases it is 90.5% or higher for the incident light on a satin surface and 88.5% or higher for the incident light on a non-satin surface. The acid attack treatment can be performed on one or both sides of the glass, which can be inked or can be neutral in color. Glass with this kind of silky smooth appearance can be used in a variety of applications including kitchens, bathrooms, offices and other environments; to create partitions, stairs, doors, murals and cabins of 25 showers; to achieve desired effects for windows, floors and walls; etc. SatinDeco glass<sup>MR</sup> and SatinDeco
Elegance * ® commercially available may have the following roughness values:
<td></td><td>Ra</td><td>Rz</td><td>Rq</td><td>RSm</td>
<td>SatinDeco * ®</td><td> 1.92</td><td> 11.11</td><td> 2.02</td><td> 61</td>
<td>SatinDeco Elegance * ®</td><td> 0.74</td><td> 9.53</td><td> 1.87</td><td> 141</td>
Note that commercially available Walkerhas Satin * ® glass is similar to Guardian's SatinDeco Elegance * ® product, while Walkerhas commercially available Velor * ® and Opaque * ® glasses are similar to Guardian's SatinDeco * ® product and that exemplary embodiments of this invention can be used with these and other acid-attacked substrates or otherwise that provide the same or similar silky smooth appearance.
It will be appreciated that when a silky smooth appearance is desired, it may also be desirable to use the DLC inclusive protective coatings described herein. In these cases, the air side of the glass can be attacked with acid to create the desired silky appearance. The inclusive protective coating of DLC, on the other hand, can be applied to the opposite main surface or to the tin side of the glass. Figure 9 is a schematic cross-sectional view of a coated article having a silky smooth appearance, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
The type of acid attack can be a hard acid attack or a soft acid attack. SatinDeco glass<sup>MR</sup> It can be produced using a single pass of a hard acid mordant, while the SatinDeco Elegance glass<sup>MR</sup> It can be produced using two passes of soft acid mordant. The choice of a hard or soft acid mordant can result in different surface textures of the corroded glass surface. For example, a hard acid mordant will tend to produce pronounced peaks and valleys, while a soft acid mordant will tend to produce slightly inclined peaks and valleys that will tend to be less deep than those produced by the hard acid mordant. This will also sometimes result in a difference in the fogging that occurs, such that hard acid mordants will tend to produce glass that has greater fogging than a glass substrate treated with a soft acid mordant.
As shown in Figure 9, the glass substrate 1 has a first main surface attacked with acid which helps to provide a silky smooth appearance of the coated article. The pronounced peaks and deep valleys shown in Figure 9 are similar to those produced using a pass with hard acid mordant (although other exemplary modalities may have pronounced peaks and valleys that occur via other mordants, and although still other exemplary modalities may have slightly more undulating peaks with shallow valleys than those that can occur with two passes of soft acid mordant or via some other suitable means). The second main surface Ib supports the protective coating. For example, prior to heat treatment, the second main surface Ib supports one or more dielectric materials 6, a layer comprising DLC 11, and a protective film 17 (which includes one or more release layers 17a and one or more barrier layers of oxygen 17b). After heat treatment and film removal, the second main surface Ib supports one or more of the dielectric materials 6 and the layer comprising DLC 11.
In certain exemplary embodiments, the first main surface is the air side of the float glass substrate 1, while the second main surface Ib is the tin side of the float glass substrate 1. Naturally, this can be reversed in different modalities. of the invention. It should be taken into account that the surface attacked with acid does not support the protective coating either. This is because the protective film may interfere with at least some of the advantageous properties conferred by the acid attack and / or may not provide a good surface for subsequent deposition of the layer comprising DLC. In order to obtain a good balance of the protective scratch resistance of the DLC together with the smooth, silky, desired appearance and anti-fingerprint properties and of easy cleaning from the acid attack, it may be desirable to provide the DLC on the opposite surface of the surface attacked with acid. Typically, the surface attacked with acid is the air side of the substrate (for example, for ease during manufacturing). Thus, as indicated above, the layer comprising DLC 11 can be provided on the tin side of the float substrate, while the acid attack can be performed on the air side of the float glass substrate.
The inventors of the present application have discovered, however, that the arrangement of the protective coating (which includes the layer comprising DLC) on the tin side of the glass substrate results in aesthetically unpleasant amounts of fogging, especially after heat treatment (for example, thermal strengthening or thermal tempering) and the removal of the sacrificial release layer (s).
The inventors have discovered that this increase in fogging may be due to the fact that tin, tin oxide and / or other contaminants can accumulate on the tin side of the substrate while in the tin bath during the flotation process and / or when it is being carried by transport rollers (for example, throughout the line). In some cases, this accumulation of tin and / or tin oxide may be similar to a thin film comprising tin and / or tin oxide that has been deposited on a substrate. In reality, tin and / or tin oxide deposits can result in a continuous or discontinuous layer that contributes to fogging, especially after heat treatment. It is believed that the accumulation of tin and / or tin oxide is at least partially responsible for fogging, such as the presence of bath contaminants and / or rollers, where the rollers and contaminants potentially cause other surface defects that result in result of fogging after heat treatment.
It will be appreciated that in some situations it would be desirable to reduce fogging after heat treatment.
It has been surprisingly and unexpectedly discovered that the appearance and / or severity of fogging after heat treatment can be reduced by reconditioning the tin side of the substrate before deposition of the layers in the stack of protective layers (which include, for example, one or more of the optional dielectric materials 6, the inclusive layer of DLC 11 and the protective film 17). For example, the inventors have discovered that the appearance and / or severity of fogging after heat treatment can be reduced by corrosion and / or fine milling of the tin side of the substrate with an ion beam. It is believed that corrosion and / or fine milling with ion beam can help the removal of at least a part of tin, tin oxide and / or other contaminant accumulated on that surface, thereby eliminating a potential cause of fogging . Ion beam corrosion can be performed using any suitable ion. For example, it has been surprisingly and effectively discovered that corrosion with suitably pure Ar or N2 on the tin side of a substrate reduces fogging after heat treatment when a protective coating is applied to the air side of the substrate. It is difficult to accurately measure the fogging of the coating on a final product because the acid attack acts as a camouflage. However, an indexing fluid can be used to flatten the surface attacked with acid. When this is done, the fogging for the untreated glass with an ion beam was above 1%, while the fogging for the glass treated with an ion beam was less than 0.5%.
As mentioned above, in certain exemplary embodiments, the tin side of the glass substrate 1 can be finely milled with an ion beam before layers 6, 11 and 17a and 17b are disposed thereon. Fine milling with ion beam of the glass substrate can eliminate or reduce tin, tin oxide and / or other contaminant accumulated on the glass, thus the surface results in a final product with a reduced amount of fogging with the heat treatment. For example, any of the exemplary techniques of fine milling with ion beam described in US Pat. No. 6,368,664 can be used to fine-tune the glass substrate 1 in this regard with ion beam, the description of the '664 patent is incorporated herein by reference. Naturally, other techniques are also possible. For example, ion beams, ion sources, ion beam treatments and the like are disclosed, for example, in US Pat. Nos. 6,808,606; 7,030,390; 7,183,559; 7,198,699; 7,229,533; 7,311,975; 7,405,411; 7,488,951 and 7,563,347, and United States Publications Nos. 2005/0082493; 2008/0017112; 2008/0199702, the complete contents of each of which are incorporated by this act in this document by way of reference. Corrosion or fine milling with ion beam using these and other techniques can advantageously help reduce fogging after heat treatment.
Figure 10 is a schematic view of an ion beam that is used for reconditioning a substrate that has a silky smooth appearance, in accordance with an exemplary embodiment of this invention. The ion beam source 102 provides ions 104 that make contact with the surface of the tin side Ib of the substrate 1. The force with which the ions make contact with the surface of the tin side Ib causes at least a portion of the substrate 1 and / or contaminants thereon to be finely milled or corroded. This leaves the substrate 1 with a finely milled surface with ions 1c as a first main surface on the tin side. The surface attacked with acid Ib opposite to the finely milled or corroded surface with ion beam 1c remains intact.
In certain exemplary embodiments, fine milling or ion beam corrosion can be used to remove at least about 2 Á of glass from the substrate, more preferably at least about 5 Á and possibly at least about 10 Á. Then, one or more layers of thin film in the protective coating can be disposed thereon. For example, one or more of the optional dielectric materials 6 and / or the inclusive DLC layer 11 can be deposited using ionic spraying (for example, using flat and / or magnetron targets) or via beam assisted deposition. of ions (IBAD) in different modalities. The battery configurations can be produced by means of an online deposition of a pass in a properly configured system or in any other suitable way in different exemplary modalities.
In some cases, features related to SatinDeco * ® can be provided on the air side of a glass substrate. Thus, in certain examples, any additional coating will be applied on the tin side as stated above. In some cases, therefore, the inclusive DLC coating can be applied on the tin side of a glass substrate. In other exemplary embodiments, however, the inclusive DLC coating described herein can be applied on the air side of a glass substrate.
In any of the modalities outlined above (for example, see Figures 1-9 above), it is also possible to provide an optional scratch resistant layer (for example, of or including SiC or DLC) on layer 17b.
In certain other exemplary embodiments, it may be advantageous to provide coatings as described herein on a main surface of a glass substrate, while another main surface is treated differently.
Figure 11 is a schematic cross-sectional view of a coated article having a silky smooth appearance and low fogging after heat treatment, in accordance with another exemplary embodiment of this invention. A glass substrate 1 is shown in Figure
eleven. The glass substrate 1 includes a surface of the side of air attacked with acid la, which creates an appearance similar to a smooth, silky matte finish that provides privacy while at the same time also allowing light to pass through the substrate. The tin side of the substrate 1 has been corroded or finely milled with an ion beam. The corroded or finely milled surface with ion beam 1c, prior to heat treatment, supports one or more optional dielectric layers or barrier 6, for example, of or including silicon oxide, silicon nitride, silicon oxynitride, zirconium, oxide of tin, titanium oxide or multiple layers for optical purposes (for example, high / low index layer piles, high / low / medium index layer piles, etc.). One or more of the optional dielectric or barrier layers. A layer comprising DLC 11 is provided on one or more of the optional dielectric or barrier layers 6 and an inclusive zinc release layer 17a is provided on top of the layer comprising DLC 11. The zinc inclusive release layer 17a can be of or may include zinc oxide, zinc oxynitride or zinc nitride in different embodiments of this invention. A layer comprising aluminum nitride 17b can be provided on top of the inclusive zinc release layer 17a. Optionally, in certain exemplary embodiments, a temporary protective layer (TPF) 17c may be arranged as an outer layer. To better protect the coated glass sheets at various processing stages, temporary protective coatings have been developed. See, for example, Publications of the United States Nos. 2010/0178850;
2010/0024953; 2009/0068350; 2009/0044897; 2008/0302462 and 2005/0210921, the complete contents of each of which are incorporated by this act in this document by way of reference. Temporary protective coatings can be applied in solid or liquid forms and are designed in such a way that they can be easily removed, typically by detachment.
TPF 17c can be removed by shedding or by abrasive means before heat treatment in certain exemplary embodiments. However, in certain other exemplary embodiments, TPF 17c can be eliminated by virtue of the high temperatures associated with heat treatment. In any case, the inclusive zinc release layer 17a and the layer comprising aluminum nitride 17b can also be removed after heat treatment. An inclusive zirconium layer can be used as one or more of the optional dielectric or barrier layers 6 in certain exemplary embodiments and this layer can be changed with heat treatment. For example, an inclusive layer of ZrN can become an inclusive layer of ZrOx with heat treatment. In certain exemplary embodiments, the layer may consist essentially of ZrN before heat treatment and may consist essentially of ZrO after heat treatment. It will be appreciated that the conversion of ZrN to ZrOx can be complete or partial. In certain exemplary embodiments, the layer may include more N than O before heat treatment and may include more O than N after heat treatment. After heat treatment, the coated article exhibits good fogging properties. The good fogging observable in the coated article as shown and described herein, for example, in relation to the exemplary embodiment of Figure 11, provides higher fogging values compared to items lacking the finely milled or treated surface. ion beam le on the tin side of the substrate.
It should be noted that the textured surface of the substrate 1 may have a prismatic surface, a matte finish surface or the like in different exemplary embodiments of this invention. The textured surface of the substrate 1 may have peaks and valleys defined therein, with inclined portions that interconnect the peaks and valleys. This surface of the substrate 1 can be corroded (for example, by way of corrosion with HF using mordant of HF or the like) and / or stamped by way of rollers or the like during the manufacture of the glass for the purpose of forming a textured surface ( and / or stamped) the. In some cases, corrosion can be performed using a mordant of single or multiple agents, for example, of or including a weak acid. For example, HC1, H2SO4, formic acid (HCOOH), acetic acid (CH3COOH), trichloroacetic acid (CCI3COOH), hydrofluoric acid (HF), hydrocyanic acid (HCN), hydrogen sulfide (H<sub>2</sub>S), and the like.
Figure 12 is a schematic cross-sectional view of another coated article having a silky smooth appearance and under fogging after heat treatment, in accordance with another exemplary embodiment of this invention. Figure 12 is similar to Figure 11 in the sense that the air side of the substrate 1 has been corroded with a strong acid mordant to produce the pronounced peaks and deep valleys that are schematically shown therein. The tin side reconditioned with ion beam le of the substrate 1 also supports a layer comprising zirconium nitride 6 and an inclusive layer of DLC 11 thereon. However, preferably to provide a separate sacrificial protective film 17 (for example, as in the exemplary embodiment of Figure 11), the DLC inclusive layer 11 itself is used as the sacrificial or protective layer. Thus, as shown in Figure 12, the inclusive layer of DLC 11 is removed as a result of heat treatment and the layer comprising ZrN 6 is converted into a layer comprising ZrOx 6 as a result of heat treatment.
It should be noted that a TPF material similar to that described above in relation to Figure 11 can be provided in relation to the embodiment of Figure 12. As before, the TPF material can be removed (for example, by route from detachment, exposure to a removal liquid and / or abrasive media) before heat treatment, or the TPF material can be removed as a result of heat treatment.
Figure 13 compares coated articles that have been corroded with an ion beam according to certain exemplary modalities (left side) with coated articles that have not been corroded with an ion beam (right side). The images on both the right and left sides share the stack of layers illustrated in Figure
12. However, the example on the left side has a main surface of the textured tin side with ion beam 1c, while the example on the right side does not. As can be seen in Figure 13, the finely milled substrate with ion beam on the left side had less fogging after tempering than the non-finely milled substrate on the right side. Thus, it is clear that corrosion or fine milling with an ion beam on the tin side of the substrate results in a structural difference in the coated article glass that can be observed in the form of a lack of fogging after heat treatment. compared to a situation in which corrosion or fine milling with ion beam is not carried out on the tin side of the substrate.
As explained above, by fine-milling with an ion beam first the tin side of the substrate before having a protective coating on it, the fogging of the final product (for example, after processing and / or heat treatments) can be reduced . This is advantageous because the fogging can be kept low while still providing a scratch resistant article that also has an appearance similar to a silky smooth, silky finish, which provides privacy with light transmission.
As indicated above, it is possible to attack with acid one or both sides with a soft or hard mordant. Also as indicated above, it is possible to provide protective coatings of or comprising DLC on one or both surfaces of a glass substrate. That is, it has been surprisingly and unexpectedly discovered that the arrangement of a layer comprising DLC to a softly corroded glass substrate on the acid-attacked side greatly improves scratch resistance. Part of the reason that this is surprising and unexpected is that the arrangement of a layer comprising DLC on an intensely corroded side of a glass substrate does not result in a significant improvement. It is believed that both the topology of the underlying substrate surface and the hard coating disposed thereon affect scratch resistance. Smoother corroded glass peaks gently help in this way to provide better coating coverage as well as overall scratch resistance.
In certain exemplary embodiments, an optional diffusion or barrier layer may be disposed on the corroded surface. As mentioned above, this optional barrier or diffusion layer can help reduce the likelihood of sodium migration of the glass substrate within the layer comprising DLC. The optional barrier or diffusion layer can also help adhere the layer comprising DLC to the substrate and / or can serve as index matching characteristics.
Figure 14 is a schematic cross-sectional view of a coated article having a silky smooth appearance and improved scratch resistance in accordance with certain exemplary embodiments of this invention. As shown in Figure 14, a glass substrate 1 has a smoothly corroded surface Id. This smoothly corroded surface Id may be the air side of the substrate 1 in certain exemplary embodiments, although the tin side may be additionally or alternatively corroded in different exemplary embodiments. The smoothly corroded surface Id supports one or more optional dielectric materials 6, as well as the protective layer comprising DLC 11. When the coated article of Figure 14 must be used in its annealed state, protective outer coating layers are not necessary. However, in certain exemplary modalities, a TPF may be applied on top of the layer comprising DLC 11 in certain other exemplary modalities.
Figure 15 is similar to Figure 14, except that Figure 15 is a schematic cross-sectional view of a heat treatable coated article having a silky smooth appearance and improved scratch resistance in accordance with certain exemplary embodiments of this invention. The outer, protective, removable coating film 17 may include, for example, the release layer (s) 17a and the oxygen barrier layer (s) 17b as set forth above. For example, in certain exemplary embodiments, the release layer 17a may include an inclusive zinc layer (for example, zinc oxide, zinc nitride or zinc oxynitride) and the oxygen barrier layer 17b may include aluminum (e.g., aluminum oxide, aluminum nitride or aluminum oxynitride).
In certain exemplary embodiments, the optional dielectric layer 6 can help by serving as a barrier (for example, for migration blocking effects), while also improving the optical and / or adhesion characteristics of the coated article. An inclusive layer of silicon or other high index material that is neutral in color (or confers color neutrality to annealed or heat treated items) can be used. Silicon nitride, silicon oxide, silicon oxynitride, hafnium oxide and / or other materials can be used for the optional dielectric layer 6.
In the embodiment of Figure 15, as in the modalities described above, the optional dielectric layer 6 can be, for example, 1-500 nm thick, more preferably 5-3 00 nm thick, and even more preferably of 15-150 nm thick. In the embodiment of Figure 15, as in the modalities described above, the inclusive layer of DLC 11 may be, for example, 1-25 nm thick, more preferably 3-10 nm thick and sometimes about 5 nm thick. In the embodiment of Figure 15, as in the modalities described above, the shedding layer 17a can be, for example, 75-500 nm thick, more preferably 100-300 nm thick and sometimes about 150 nm of thickness. In the embodiment of Figure 15, as in the modalities described above, the oxygen barrier layer 17b may be, for example, 20-100 nm thick, more preferably 35-75 nm thick and sometimes approximately 50 nm thick.
Similarly to the above, a TPF material can be applied and removed before or as a result of heat treatment. Also similarly to the above, the protective film 17 can be removed by virtue of heat treatment, for example, such that at least a portion of the inclusive layer of DLC 11 is exposed as an outer layer of the coated article afterwards. of heat treatment.
It should be noted that the steps described in this document can be performed by one or more different parties. For example, the part that provides a matte finish glass substrate may or may not be the same part as the part that supplies the inclusive DLC protective coating and / or the part that performs the heat treatment. In certain exemplary embodiments, a part can acid attack a substrate, a second part can provide the inclusive protective coating of DLC and a third part can heat treat this intermediate part. Other combinations of actors are also contemplated in this document.
While the invention has been described in relation to what is currently considered to be the most practical and preferred modalities, it should be understood that the invention is not limited to the modalities disclosed, but rather, it is intended to cover several modifications and equivalent arrangements that are included within the spirit and scope of the appended claims.
Contents6
9 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9
83 members in 9 offices
Priority claims5
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| 201113174336 | United States of America | A | |
| 2012043203 | United States of America | W | |
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| WO2012US43203 | – | – | – |
Members83
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| WO2009067133A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP2109592A1 | European Patent Office (EPO) | A1 | |
| EP2146937A1 | European Patent Office (EPO) | A1 | |
| EP2152643A1 | European Patent Office (EPO) | A1 | |
| EP2155623A1 | European Patent Office (EPO) | A1 | |
| WO2010024960A1 | World Intellectual Property Organization (WIPO) | A1 | |
| MX2010005478A | Mexico | A | |
| EP2220007A1 | European Patent Office (EPO) | A1 | |
| US7833574B2 | United States of America | B2 | |
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| EP2726429A1 | European Patent Office (EPO) | A1 | |
| BRPI0808380A2 | Brazil | A2 | |
| BRPI0812117A2 | Brazil | A2 | |
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| EP2726286B1 | European Patent Office (EPO) | B1 | |
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1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 366254
- Publication, DOCDB
- 366254
- Publication, EPODOC
- MX366254
- Application
- 20130015029
- Application, DOCDB
- 2013015029
- Application, EPODOC
- MX20130015029
Titles3
- English
- METHOD FOR MAKING A THERMALLY TREATED COATED ARTICLE USING A DIAMOND TYPE CARBON COATING (DLC) AND A PROTECTIVE FILM ON A SURFACE ATTACKED WITH ACID.
- English
- METHOD OF MAKING HEAT TREATED COATED ARTICLE USING DIAMOND-LIKE CARBON (DLC) COATING AND PROTECTIVE FILM ON ACID-ETCHED SURFACE.
- Spanish
- METODO PARA HACER UN ARTICULO RECUBIERTO TRATADO TERMICAMENTE UTILIZANDO UN RECUBRIMIENTO DE CARBON TIPO DIAMANTE (DLC) Y UNA PELICULA PROTECTORA SOBRE UNA SUPERFICIE ATACADA CON ACIDO.
Classification
- CPC, 21
- C03C17/22
- C03C17/3411
- C03C15/00
- C03C17/27
- C03C17/3441
- C03C2217/22
- C03C2217/282
- C03C2217/77
- C03C2217/78
- C03C2217/91
- C03C2218/15
- C03C2218/31
- C03C2218/322
- C03C2218/328
- C03C2218/33
- C03C2218/355
- C03C2218/36
- Y10T156/1163
- B05D3/104
- C03C17/225
- C03C17/23