Method of making a coated article coated with a hard protective highly transparent layer

ES 2 297 486 T3

DESCRIPTION

Heat-treatable coated article with carbon-like diamond (CTD) and / or zirconium in the coating.

This application is the partial continuation (CP) of United States Patent Application Serial No. 10 / 700,359, filed November 4, 2003, the full disclosure of which is incorporated herein by reference.

This invention relates to a method of manufacturing a coated article for use in a window unit or any other suitable application such as glass for furniture or glass for framing pictures. For example, certain embodiments of this invention relate to a method of manufacturing a window unit (for example, a vehicle window such as a vehicle windshield, rear window, sunroof, or side window, or a window unit). IG window, or shower screen) including a heat treatment step of a glass substrate coated with at least one layer comprising diamond-like carbon (CTD). In certain exemplary embodiments, CTD can be used to generate energy during heat treatment (TT) to transform at least one other layer of the coating to form a new post-TT layer or layers that were not present prior to heat treatment. Other certain exemplary embodiments of this invention relate to said coated article, heat treated or not, which can be used in window applications, or any other suitable application such as glass for furniture or the like.

Background of the invention

Vehicle windows (eg, windshields, rear windows, sunroofs, and side windows) are known in the art. For purposes of example, vehicle windshields typically include a pair of curved glass substrates laminated together by a polymeric interlayer such as polyvinyl butyral (PVB). It is known that one of the two glass substrates may have a coating (e.g. low-E coating - low E) on it for solar control purposes such as reflecting IR and / or UV radiation, so that the interior of the vehicle may be more comfortable in certain weather conditions. Conventional vehicle windshields are manufactured as follows. First and second flat glass substrates are provided, one optionally having a low E coating sprayed thereon. The pair of glass substrates are washed and stored together (i.e. stacked on top of each other), and then while in storage they are curved together into the desired shape for the windshield at high temperature (s) (for example, 8 minutes at about 600-625 ° C). Subsequently, the two curved glass substrates are laminated together by the polymeric interlayer to form the vehicle windshield.

Insulating glass (IG) window units are also known in the art. Conventional IG window units include at least first and second glass substrates (one of which may have a solar control coating on an interior surface thereof) that are coupled together by at least one seal (s) or spacer (s). The resulting space or gap between the glass substrates may or may not be filled with gas and / or evacuated at a low pressure in different cases. However, many IG units are required to be tempered. Thermal tempering of glass substrates for such IG units typically requires heating the glass substrates to a temperature or temperatures of at least about 600 ° C for a period of time sufficient to enable thermal tempering.

Other types of coated articles also require heat treatment (TT) (eg, tempering, heat bending, and / or heat setting) in certain applications. For example and without limitation, glass shower enclosures, table top glass, and the like require TT in certain cases.

Diamond-like carbon (CTD) is sometimes known for its scratch resistant properties. For example, different types of CTD are discussed in the following US Patents: 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 herein by reference.

Sometimes it is desirable to provide a window unit or other glass article with a protective coating that includes CTD to protect it from scratches and the like. Unfortunately, CTD tends to oxidize and calcine at temperatures of about 380 to 400 ° C or higher, since the heat treatment typically takes place in an atmosphere that includes oxygen. In this way, it will be understood that CTD as a protective coating cannot withstand the heat treatments (TT) at the extremely high temperatures described above that are often required in the manufacture of vehicle windows, IG window units, dash glass table, and / or the like. Accordingly, CTD cannot be used alone as a coating to be heat treated, because it oxidizes during heat treatment and substantially disappears as a result of heat treatment (ie calcines).

Certain other types of scratch resistant materials are also unable to withstand sufficient heat treatment for tempering, heat setting and / or bending of an underlying glass substrate.

Accordingly, those skilled in the art will understand that there is a need in the art for a method of manufacturing a scratch resistant coated article that can be heat treated (TT) such that

ES 2 297 486 T3 after heat treatment the coated article remains scratch resistant. There is also a need for corresponding coated articles, both heat treated and pre-TT.

Brief summary of the examples of the invention

In certain exemplary embodiments of this invention, a method of manufacturing a coated article (e.g., a window unit such as for a vehicle, building, or the like) that can be heat treated is provided such that after heat treatment (TT ) the coated article is scratch resistant to a greater degree than uncoated glass.

In certain exemplary embodiments, a coated article includes respective layers comprising hydrogenated diamond-like carbon (CTD) and zirconium nitride prior to heat treatment (TT). The CTD can be located below and / or above the layer comprising zirconium nitride. During TT, the hydrogenated CTD acts as a fuel which after combustion with oxygen produces carbon dioxide and / or water. This exothermic reaction, caused by the combustion of the hydrogenated carbon in the CTD, causes the spontaneous propagation of a combustion wave through the initial reactants. The high temperature developed during this combustion heats the layer comprising zirconium nitride to a temperature (s) well above the heat treatment temperature, thus causing the layer comprising zirconium nitride to transform into a new post-TT layer. comprising zirconium oxide. The new post-TT layer comprising zirconium oxide may also include nitrogen in certain exemplary embodiments of this invention.

The new post-TT layer comprising zirconium oxide is surprisingly scratch resistant. Thus, it can be seen that a technique has been provided which allows a heat treatable scratch resistant product to exist; and the coated article may also have good transmission properties. In certain exemplary embodiments, the scratch resistance of the post-TT coated article can be even better than CTD without TT.

In certain exemplary embodiments, a method of preparing a heat-treated coated article is provided, the method comprising: providing a coating supported by a glass substrate, the coating comprising a layer comprising zirconium nitride and a layer comprising carbon of the type hydrogenated diamond (CTD) provided on at least the layer comprising zirconium nitride; heat treating the glass substrate and coating in a manner sufficient for heat tempering, heat setting and / or heat bending of the glass substrate; and wherein during said heat treatment the layer comprising hydrogenated CTD is combusted or calcined generating sufficient heat to cause the layer comprising zirconium nitride to transform into a heat treated layer comprising zirconium oxide in the article. heat treated coated.

In other exemplary embodiments of this invention, a method of preparing a heat-treated coated article is provided, the method comprising: providing a coating supported by a glass substrate, the coating comprising a layer comprising a metal nitride and a layer comprising diamond-like carbon (CTD) provided on at least the layer comprising the metal nitride; heat treating the glass substrate and coating; and wherein, during heat treatment, the layer comprising CTD is burned or calcined causing the layer comprising the metal nitride to transform into a heat treated layer comprising an oxide of the metal in the heat treated coated article. . The metal can be Zr, or any other suitable metal or metal alloy.

In still other exemplary embodiments of this invention, there is provided a heat-treated coated article that includes a coating supported by a glass substrate, the coating comprising: an outermost layer comprising nanocrystalline zirconium oxide comprising a cubic lattice structure; and wherein the layer comprising zirconium oxide additionally comprises 0.25 to 20% carbon.

In other exemplary embodiments of this invention, a coated article is provided that includes a coating supported by a glass substrate, the coating from the glass substrate outwardly comprising: a layer comprising zirconium nitride; and a layer comprising hydrogenated diamond-like carbon (CTD). Other layers can also be provided at any suitable location. Such a coated article, in certain exemplary embodiments, can be adapted to be heat treated to cause the nitride to at least partially transform into an oxide.

In other exemplary embodiments of this invention, a method of manufacturing a coated article is provided, the method comprising: providing a coating supported by a substrate, the coating comprising a layer comprising diamond-like carbon (CTD) and a layer that is will phase transform during heat treatment; heating the layer comprising CTD and the layer to be phase transformed to cause combustion of the layer comprising CTD thereby causing the layer comprising CTD to generate heat after combustion thereof; and using the heat generated by the combustion of the layer comprising CTD to assist in the phase transformation of the layer to be phase transformed such that a new layer is formed which has been phase transformed after heating.

ES 2 297 486 T3

Brief description of the drawings

Figure 1 is a schematic diagram illustrating coated articles in accordance with one embodiment of this invention before and after heat treatment.

Figure 2 is a schematic diagram illustrating coated articles in accordance with another embodiment of this invention before and after heat treatment.

Figure 3 is an XPS chart illustrating chemical elements in a pre-TT coated article in accordance with an example of the present invention.

Figure 4 is an XPS graph illustrating chemical elements in the coated article of Figure 3, after the coated article of Figure 3 has been subjected to TT.

Figure 5 is a schematic diagram illustrating coated articles in accordance with one embodiment of this invention before and after heat treatment.

Figure 6 is a schematic diagram illustrating coated articles in accordance with another embodiment of this invention before and after heat treatment.

Figure 7 is a schematic diagram illustrating coated articles in accordance with yet another embodiment of this invention before and after heat treatment.

Detailed Description of Exemplary Embodiments of the Invention

Reference is now made more particularly to the accompanying drawings in which like reference numerals indicate like parts or layers throughout the various views.

Certain exemplary embodiments of this invention relate to processes for preparing coated articles that may use heat treatment (TT), wherein the coated article includes a coating (one or more layers) that includes diamond-like carbon (CTD) and / or or zirconium. In certain cases, TT may involve heating a glass support substrate, with the layer or layers including CTD and / or zirconium on it, to a temperature or temperatures of 550 to 800 ° C, more preferably 580 to 800 ° C (which is well above the calcination temperature of the CTD). In particular, certain exemplary embodiments of this invention relate to a technique for allowing the post-TT coated article to be more scratch resistant than uncoated glass.

In certain exemplary embodiments, the coated article as originally formed (ie, before TT, or pre-TT) includes respective alternating layers comprising hydrogenated diamond-like carbon (CTD) and zirconium nitride. The CTD can be located below and / or above the zirconium nitride. During TT (for example, using a temperature (s) of 550 to 800 ° C, more preferably 580 to 800 ° C), the hydrogenated CTD acts as a fuel that upon combustion with oxygen in the atmosphere produces carbon dioxide and water. This exothermic reaction, caused by the combustion of the hydrogenated carbon in the CTD, causes the spontaneous propagation of a combustion wave through the initial reactants. The high temperature developed during this combustion of the CTD heats the layer or layers comprising zirconium nitride to a temperature well above the temperature used for heat treatment. For example, combustion of the CTD may heat part or all of the layer (s) comprising zirconium nitride to a temperature of at least about 1200 ° C, more preferably at least about 1500 ° C, and more. preferably still at least about 2,000 ° C.

Since the layer or layers comprising zirconium nitride are heated to said high temperature due to the combustion of the CTD during TT, at least the layer or layers comprising zirconium nitride are transformed due to the high temperature (s) into a new one. post-TT layer or layers comprising zirconium oxide. The new postTT layer (s) comprising zirconium oxide may also include nitrogen in certain exemplary embodiments of this invention (e.g., ZrO: N; ZrO₂: N, ZrO_x: N (where x is 1 to 3, more preferably 1.5 to 2.5), and / or any other suitable stoichiometry). The new post-TT layer (s) comprising zirconium oxide (optionally with nitrogen) is surprisingly scratch resistant. Thus, it can be seen that a technique has been provided which enables a heat treatable scratch resistant product to be manufactured; and the coated article may also have good transmission properties. In certain exemplary embodiments, the scratch resistance of the post-TT coated article can be even greater than that of CTD without TT.

In certain exemplary embodiments of this invention, the post-TT layer (s) comprising zirconium oxide include a cubic lattice nanocrystalline structure. The entire layer (s) may be of a cubic lattice type nanocrystalline structure, or alternatively only part of the layer (s) may include cubic lattice nanocrystalline structure. Zirconium nitride typically does not grow in the cubic phase, at least at a temperature of at least about 2,000 ° C. Pre-TT ZrN is not typically found in cubic lattice form. Since the TT is only at a temperature no greater than about 900 ° C (more preferably no greater than about 800 ° C), it would be expected that the pre-TT non-cubic zirconium nitride would not grow in cubic phase during the TT. However, it has surprisingly been found that the combustion generated by CTD during TT causes at least part of the layer comprising zirconium nitride to heat sufficiently to cause it to become a post-TT layer or layers.

ES 2 297 486 T3 comprising zirconium oxide including a cubic lattice nanocrystalline structure (with or without nitrogen) that is highly scratch resistant.

Thus, it can be seen that in certain exemplary embodiments of this invention the layer including pre-TT zirconium nitride is transformed during TT into a new post-TT layer comprising zirconium oxide that includes a cubic lattice nanocrystalline structure, although the temperatures used in the furnace during the TT are considerably lower than those normally required to allow for cubic growth. It is the combustion of the CTD during TT that causes sufficient energy / heat to be generated in the layer including zirconium to allow it to change phase and grow in at least a cubic manner to finally comprise a cubic lattice nanocrystalline structure after TT.

As a result of TT, the amount of oxygen in the layer (s) that include post-TT zirconia is much greater than the amount of oxygen in the layer (s) that include pre-TT zirconia. For example, in certain exemplary embodiments of this invention, the post-TT layer (s) comprising zirconium oxide includes at least 5 times more oxygen than the pre-TT layer (s) comprising zirconium nitride, more preferably at least 10 times more and more preferably at least 20 times more than the pre-TT layer (s). In certain exemplary embodiments of this invention, the pre-TT layer (s) comprising zirconium nitride include about 0-10% oxygen, more preferably about 0-5% oxygen, and even more preferably about 0- 2% (atomic%) oxygen. While, in certain exemplary embodiments of this invention, after TT and phase transformation due to CTD combustion, the post-TT layer (s) comprising zirconium oxide include much more oxygen as will be explained below.

Figure 1 is a schematic diagram illustrating how a coated article can be manufactured in accordance with an exemplary embodiment of this invention. Initially, a coated article is formed using a glass substrate 1. The coated article includes, supported by the glass substrate 1, at least one optional dielectric layer 3 of or including silicon nitride, silicon oxynitride, silicon oxide, or the like; a first layer 5 of or including CTD, a first layer 7 of or including zirconium nitride (eg ZrN, or any other suitable stoichiometry), and a top layer 9 of or including CTD. The glass substrate 1 is typically of or includes soda-lime-silica glass, although other types of glass can be used in certain cases.

Dielectric layer (s) 3 is provided to prevent diffusion of sodium into the CTD during TT (ie, a barrier to diffusion). This layer (s) 3 also allows thermal imbalance to occur seamlessly between the CTD and the glass substrate to more easily allow thermal bending and the like. Unexpectedly, it has been discovered that the use of silicon oxide as a protective layer 3 (compared to silicon nitride) often leads to improved optical results of the final product after heat treatment such as higher visible transmission in certain exemplary embodiments of this invention. Any of the materials for the protective layer 3 mentioned above can be doped (eg, 0.5 to 15%) with Al, stainless steel, or any other metal in certain embodiments of this invention. The protective layer (s) 3 is formed on the glass substrate 1 by sputtering, or by any other suitable technique.

Layers 5 and 9 comprising CTDs can be any suitable type of CTD, including but not limited to any of the types of CTD described in any of US Patent 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; and / or 5,470,661, all of which are incorporated herein by reference.

For purposes of example only, each of the layers including CTD 5 and / or 9 are about 5 to 1,000 angstroms (A) thick in certain exemplary embodiments of this invention, more preferably 10-300 A thick, and even more preferably 45 to 65 A thick. In certain exemplary embodiments of this invention, the CTD layer (s) 5 and / or 9 may have a mean hardness of at least about 10 GPa, more preferably at least about 20 GPa, and even more preferably about 20-90 GPa. . Said hardness makes layers 5 and 9 resistant to scratching, to certain solvents and / or the like. Layer (s) 5 and / or 9, in certain exemplary embodiments, may be of or include a special type of CTD known as highly tetrahedral amorphous carbon (t-aC), and may be hydrogenated (t-aC: H) in certain embodiments. In certain hydrogenated embodiments, the taC: H type of CTD may include 4 to 39% hydrogen, more preferably 5-30% H, and more preferably still 10-20% H.

This t-aC or t-aC: H type CTD for layer (s) 5 and / or 9 may include more carbon-carbon sp bonds³ (C - - C) than carbon-carbon sp bonds² (C - - C). In certain exemplary embodiments, at least about 50% of the carbon-carbon bonds in CTD layer (s) 5 and / or 9 may be sp-type carbon-carbon (C - - C) bonds.³, more preferably at least about 60% of the carbon-carbon bonds in the layer (s) may be carbon-carbon (C - - C) sp bonds³, and more preferably still at least about 70% of the carbon-carbon bonds in the layer (s) may be carbon-carbon (C - - C) sp bonds³. In certain exemplary embodiments of this invention, the CTD in layer (s) 5 and / or 9 can have an average density of at least 2.4 g / cm³ about, more preferably at least 2.7 g / cm³ about.

ES 2 297 486 T3

Examples of linear ion jet sources that can be used to deposit layers 5 and 9 that include CTD on substrate 1 include any of those listed in US Patent Nos. 6,261,693, 6,002,208, 6,335 .086, or 6,303,225 (all incorporated by reference into this document). When using an ion jet source to deposit layer (s) 5 and / or 9, a supply of gaseous hydrocarbons (e.g., C₂H₂), HMDSO, or any other suitable gas, can be used in the ion jet source to cause the source to jet ions towards substrate 1 to form layer (s) 5 and / or 9. It is observed that the Hardness and / or density of layer (s) 5 and / or 9 can be adjusted by varying the ionic energy of the deposition apparatus. In certain exemplary embodiments, at least about 2,000 V (anode to cathode volts), eg, about 3,000 V, may be used in the ion source to deposit layer (s) 5 and / or 9. It is noted that the expression "On the substrate" as used herein is not limited to being in direct contact with the substrate since other layer (s) may still be provided between them.

Layer 7 including zirconium nitride is provided between CTD layers 5 and 9 in certain exemplary embodiments of this invention. In certain exemplary embodiments, layer 7 including zirconium nitride can be located directly between CTD layers 5 and 9 so that it contacts each other; however in other exemplary embodiments another layer (s) (not shown) may be provided between layer 7 including zirconium nitride and CTD layer (s) 5 and / or 9. Layer 7 including zirconium nitride may be essentially composed of zirconium and nitride, or alternatively may include other materials including, but not limited to, oxygen, or other dopants such as Al or the like. Layer 7 including zirconium nitride can be formed by sputtering or the like in certain exemplary embodiments of this invention. The preTT layer (s) 7 comprising zirconium nitride (and 7 'discussed below) may include about 10-70% Zr, more preferably about 30-65% Zr, even more preferably 40-60 about% Zr, and more preferably still about 45-55% Zr in terms of atomic%; and about 20-60% N, more preferably about 30-50% N in terms of atomic%.

In certain exemplary embodiments of this invention, layer 7 including zirconium nitride (and 7 'discussed below) can have a density of at least 6 g / cm³, more preferably at least 7 g / cm³. Furthermore, in certain exemplary embodiments, zirconium nitride layer 7 (and 7 ') may have an average hardness of at least 650 kgf / mm, more preferably at least 700 kgf / mm, and / or may have a ratio bond overlap of at least 0.25 (more preferably at least about 0.30) for strength purposes. In certain exemplary cases, many of the Zr-N bonds in layer 7 (and 7 ') may be of the covalent type, which are stronger than ionic bonds, for strength purposes. It is also noted that in certain exemplary embodiments of this invention, the ZrN in layer 7 (and 7 ') can have a melting point of at least 2,500 ° C, which can be about 2,980 ° C in certain exemplary cases. In certain exemplary embodiments of this invention, zirconium nitride layer 7 (and 7 ') can be represented by Zr_xN_Y, where the x: y ratio is 0.8 to 1.2, and is preferably about 1.0 in certain exemplary embodiments.

For example purposes only, certain exemplary thicknesses for the pre-TT layers shown on the left side of Figure 1 are shown below, the layers being shown in order from the glass substrate outward.

Coating Example (Figure 1) Layer Thickness (Pre-TT)

<td>Cap</td><td>general</td><td>Most Preferred</td><td>Even more preferred</td>

<td>Dielectric (layer 3)</td><td>50-500 A</td><td>100-300 A</td><td>180-220 A</td>

<td>CTD (layer 5)</td><td>10-300 A</td><td>15-100 A</td><td>20-45 A</td>

<td>ZrN (layer 7)</td><td>40-500 A</td><td>50-400 A</td><td>90-220 A</td>

<td>CTD (layer 9)</td><td>20-300 A</td><td>30-100 A</td><td>40-65 A</td>

Once the pre-TT coated article shown on the left side of Figure 1 is formed, it may or may not undergo sufficient heat treatment for at least one of heat bending, heat bending, and / or heat setting.

Referring to Figure 1, when subjected to TT (for example, in an oven using a temperature (s) of 550 to 800 ° C, more preferably 580 to 800 ° C), layer 9 including upper CTD or External calcines due to combustion due to the high temperatures used during the TT. In particular, at least layer 9 of hydrogenated CTD acts as a fuel which after combustion with oxygen from the atmosphere during TT produces carbon dioxide and water. This exothermic reaction, caused by the combustion of hydrogenated carbon from at least layer 9 of CTD, causes the spontaneous propagation of a combustion wave through the initial reactants. The high temperature developed during this combustion heats the layer 7 comprising zirconium nitride to a temperature (s) well above the heat treatment temperature used in the furnace. For example, the

ES 2 297 486 T3 combustion of the CTD 9 can heat part or all of the layer 7 comprising zirconium nitride to a temperature of at least about 1200 ° C, more preferably at least about 1500 ° C, and even more preferably at least about 2000 ° C.

Since layer 7 comprising zirconium nitride is heated to said high temperature due to CTD combustion during TT, layer 7 comprising zirconium nitride is transformed during TT into a new post-TT layer 11 comprising zirconium oxide. The new post-TT layer 11 comprising zirconium oxide may also include nitrogen (and / or other dopants) in certain exemplary embodiments of this invention (eg, ZrO: N; ZrO₂: N; or any other suitable stoichiometry). The new post-TT layer 11 comprising zirconium oxide (optionally with nitrogen) is surprisingly scratch resistant thus providing a scratch resistant heat treated coated article. The term "zirconium oxide" as used herein is noted to include ZrO2 and / or any other stoichiometry where the Zr is at least partially oxidized. In this document, any description of layer 11 can also be applied to layer 11 '; and likewise, any description of layer 7 can be applied to layer 7 '.

The post-TT layer 11 comprising zirconium oxide may include 0- + 30% nitrogen in certain exemplary embodiments of this invention, more preferably 0-20% nitrogen, even more preferably 0-10% nitrogen, and still more preferably about 1-5% nitrogen in certain exemplary embodiments of this invention. The post-TT layer 11 comprising zirconium oxide may include about 10-70% Zr, more preferably about 20-60% Zr, still more preferably about 30-55% Zr, and still more preferably the About 30-45% Zr in terms of atomic%. In addition, the post-TT layer (s) 11 comprising zirconium oxide in certain exemplary embodiments of this invention may include about 10-85% oxygen, more preferably about 30-80% oxygen, still more preferably 40% oxygen. -70% oxygen, and still more preferably about 50 to 70% oxygen.

In certain exemplary embodiments of this invention, the post-TT layer 11 comprising zirconium oxide includes a cubic lattice nanocrystalline structure (although the pre-TT layer comprising zirconium nitride does not, in certain cases). As explained above, zirconium nitride typically does not grow in the cubic phase at least at a temperature of at least about 2,000 ° C. Surprisingly it has been found that the combustion generated by the CTD during TT causes at least part of the pre-TT layer comprising zirconium nitride 7 to heat up sufficiently to cause it to grow in the cubic phase and become a post-layer. TT 11 comprising a cubic lattice nanocrystalline structure including zirconium oxide (with or without nitrogen) that is highly resistant to scratching in certain exemplary embodiments of this invention.

Surprisingly it has been found that the use of zirconium nitride (e.g. ZrN) in the pre-TT layer 7 is especially beneficial with respect to allowing a phase transformed post-TT layer 11 including Zr to be formed which is very strong. to scratched.

The final coated article TT (or even no TT) of Figure 1 is scratch resistant and can be used in various applications including, but not limited to, IG window units, laminated vehicle windshields, other types of vehicle windows , applications in furniture, and / or the like.

For the purpose of example only, certain examples of thicknesses are shown below for the post-TT coated article shown on the right hand side of Figure 1, the layers being presented in order from the glass substrate outward.

Coating Example (Figure 1) Layer Thickness (Post-TT)

<td>Cap</td><td>general</td><td>Most Preferred</td><td>Even more preferred</td>

<td>Dielectric (layer 3)</td><td>50-500 A</td><td>100-300 A</td><td>180-220 A</td>

<td>CTD (layer 5)</td><td>0-300 A</td><td>15-100 A</td><td>20-45 A</td>

<td>ZrO: N (layer 11)</td><td>50-800 A</td><td>70-600 A</td><td>100-350 A</td>

It can be seen from the above that the post-TT layer 11 that includes Zr is typically thicker than the pre-TT layer 7 that includes Zr. In other words, the thickness of the layer including Zr increases during TT. In certain exemplary embodiments of this invention, the thickness of the Zr-including layer (eg, from layer 7 to layer 11) may increase by at least about 5% during or due to TT, more preferably at least 10%. about, and still more preferably at least about 40%. This increase in thickness is caused by the transformation of layer 7 into layer 11, where oxygen migrates towards the post-TT layer 11 (that is, more oxygen migrates towards the post-TT layer 11 than nitrogen leaves, in terms of of atomic% and / or size).

ES 2 297 486 T3

Although the CTD layer 5 is shown to be present in the post-TT coated article in Figure 1, it is not required to be present in the post-TT coated article in alternative embodiments of this invention. If the pre-TT CTD layer 5 reaches a sufficient temperature and / or is exposed to enough oxygen during the TT, it may undergo combustion causing it to thin or even disappear due to the TT in certain cases. In such cases, the pre-TT layers 5, 7 and / or 9 can be efficiently transformed during the TT into the post-TT layer 11 including zirconium oxide (it is similar to the embodiment of Figure 5 in this regard).

In certain exemplary embodiments of this invention, the heat-treated layer 11 comprising zirconium oxide includes Zr_xOR_Y, where y / x is from about 1.2 to 2.5, more preferably from about 1.4 to 2.1.

Figure 2 illustrates another exemplary embodiment in accordance with this invention. The embodiment of Figure 2 is similar to the embodiment of Figure 1, except that an additional layer (s) 7 'including ZrN and an additional layer (s) 5' including CTD are provided pre-TT. In other words, the embodiment of Figure 2 includes several sets of alternating layers comprising CTD and pre-TT ZrN. In this way, after TT, an additional layer (s) 11 'including zirconium oxide and an additional 5' layer including CTD can be provided as shown on the right hand side of Figure 2. Layers 5 ', 7 ', and 11' are similar to layers 5, 7, and 11, respectively, discussed above, in certain exemplary embodiments of this invention. However, it is possible that one or both layers of hydrogenated CTD 5, 5 'may be subjected to combustion and substantially disappear or substantially decrease in thickness due to TT in certain exemplary embodiments of this invention when high temperatures and / or long dwell times are used. heating so that only a layer of ZrO remains (for example, see Figure 5), although some CTD may remain as shown in Figure 2. However, as shown in the embodiment of Figure 2, at least the outer layer 9 of hydrogenated CTD typically calcines due to combustion and generates the energy / heat necessary to cause one of more of the layer (s) 7 , 7 'of ZrN is transformed into layer (s) 11, 11' including ZrO as explained above.

Still referring to the embodiment of Figure 2, in certain non-limiting exemplary embodiments of this invention, oxygen from the atmosphere diffuses inwardly through the layer (s) to assist the pre-TT layers 7 and 7 ' of zirconium nitride to be transformed, aided by the heat generated by the combustion discussed above, towards the post-TT layers 11 and 11 'comprising zirconium oxide. However, in other exemplary embodiments of this invention, the zirconium nitride 7 'pre-TT layer does not need to phase transform during TT; In such embodiments, the post-TT layer 11 'would be similar to the pre-TT layer 7' and is essentially composed of zirconium nitride. In still other embodiments of this invention, layer 11 'can be partially transformed and thus include a mixture of zirconium nitride and zirconium oxide.

Figures 3-5 illustrate another exemplary embodiment of this invention. The pre-TT coated article of this embodiment is the same as that of the embodiment of Figure 2 described above. Figure 3 is an XPS chart illustrating the chemical composition of an exemplary pre-TT coated article according to the embodiment of Figure

5. However, in contrast to the embodiment illustrated in Figure 2, in the embodiment of Figure 5 during TT all the CTD layers are burned and essentially disappear. This in turn creates a significant amount of heat that couples with oxygen diffusing into the coating from the surrounding atmosphere causing each of the zirconium nitride pre-TT layers to phase transform during the TT forming at least one post-TT layer 11 comprising zirconium oxide (which may or may not be doped with N). In the embodiment of Figure 5, the pre-TT layers 5, 7 ', 5', 7 and 9 are bonded or ultimately result in a fairly thick post-TT layer 11 comprising zirconium oxide. Figure 4 is an XPS chart illustrating the chemical composition of an exemplary post-TT coated article according to the embodiment of Figure 5.

In the embodiment of Figures 3-5, it can be seen from Figure 4 that residual carbon remains in the zirconium oxide layer 11 after TT due to the presence of the CTD pre-TT layer (s). In certain exemplary embodiments of this invention, the zirconium oxide layer 11 includes 0.25 to 20% C, more preferably 0.25 to 10% C, and still more preferably 0.25 to 5% C C.

Figure 6 is a cross-sectional view of another exemplary embodiment of this invention. In the embodiment of Figure 6, the layer 5 comprising CTD is located directly on the glass substrate 1. Certain carbon atoms can be sub-implanted in the substrate in certain exemplary cases to improve bonding. Layer 7 including zirconium nitride is located between and in contact with CTD layers 5 and 9 in this exemplary embodiment. During heat treatment, at least the outer layer 9 including CTD acts as a fuel to cause at least layer 7 to transform into a new post-TT layer 11 comprising zirconium oxide as shown in Figure 6 and has been previously described. CTD layer 5, during TT, can act as fuel and / or can melt into glass and / or layer 7,11 during TT as a result of combustion.

When layer 5 melts into glass 1 during TT, the result is a transition interface layer close to the substrate surface comprising silicon oxycarbide. In certain embodiments of this invention, the CTD layer 5 can function as a barrier to Na to prevent significant amounts of Na from migrating from the glass to the zirconium-including layer during TT, to reduce the likelihood of damaging the Zr-including layer. .

In certain other cases, it is possible for the CTD layer 5 to contract although not totally disappear during TT in certain exemplary embodiments of this invention.

ES 2 297 486 T3

In the embodiment of Figure 6, the CTD layer 5 may be about 20 to 60 A thick, more preferably 28 to 34 A thick, or it may be any other suitable thickness; Layer 7 including ZrN may be about 100 to 200 A thick, more preferably about 150 to 190 A thick, still more preferably about 160 to 170 A thick, or it may be any other suitable thickness; and CTD layer 9 may be 50 to 200 A thick, more preferably 80 to 120 A thick, still more preferably 90 to 110 A thick, or any other suitable thickness in certain exemplary cases. In certain cases, if the thickness of the lower CTD layer 5 is outside the range of 28 to 34 A, an undesirable haze can increase rapidly, especially on the underside.

Figure 7 is a cross-sectional view of another exemplary embodiment of this invention. The embodiment of Figure 7 is similar to the embodiment of Figure 6, except for the omission of the lower CTD layer 5. Thus, in the embodiment of Figure 7, the layer 7 comprising zirconium nitride is located directly on the glass substrate 1 before the TT.

Each of the aforementioned embodiments provides a heat treatable coated article that is highly resistant to scratching after TT. For example, post-TT coated articles according to certain embodiments of this invention may have a critical scratch load using an alumina sphere of at least about 15 lbs. (6.80 kg), more preferably at least 8.16 kg. (18 lbs.), Still more preferably at least 9.07 kg (20 lbs.), Still more preferably at least 10.21 kg (22.5 lbs.), And still more preferably at least 13.61 kg (30 lbs.) . Furthermore, articles coated in accordance with certain exemplary embodiments of this invention are UV stable, and do not degrade significantly upon UV exposure. In certain exemplary embodiments, the coated articles described herein may have a post-TT contact angle of θ with a sessile drop of water of about 25 to 60 degrees; and sometimes the contact angle is less than 35 degrees.

Furthermore, in certain exemplary embodiments, good optics is provided in that post-TT yellow staining is not present although yellowish CTD may be present at least in the pre-TT version of the product. The resulting heat-treated coated article is surprisingly transmissive to visible light. For example, the heat-treated coated article may have a visible transmission of at least 50%, more preferably at least 60%, even more preferably at least 70%, more preferably at least 75%, and sometimes at least 80% in accordance with certain exemplary embodiments of this invention. According to certain exemplary embodiments of this invention, post-TT coated articles have a transmissive value a * of -5 to +2, more preferably -4 to 0, and still more preferably -3.5 to -1; and a transmissive value b * from -8 to +8, more preferably from -3 to +3, and still more preferably from -2 to +2. In other words, coated articles heat treated in accordance with certain exemplary embodiments of this invention appear visually very similar to clear uncoated glass, although numerous layers are provided thereon for purposes of durability.

Another unique aspect of certain exemplary embodiments of this invention is the enormous increase in visible transmission caused by heat treatment. In certain exemplary embodiments, visible transmission increases by at least about 20% visible transmission due to TT, more preferably at least 30%, and still more preferably at least 40%. For example, in certain examples of this invention that have been made, the pre-TT visible transmission has been about 36-37%. After heat treatment for about 400 seconds at about 640 ° C, the post-TT visible transmission was about 77-81%. In each case, the visible transmission increased by approximately 40-45% due to TT. For the purposes of example and understanding, if a pre-TT coated article had 36% visible transmission and after TT the post-TT coated article had 80% visible transmission, then the visible transmission increased by 44% (i.e. , 80% -36% = 44%) due to TT. The apparent reason for this significant increase in visible transmission due to the TT is the disappearance of at least part of the CTD due to the TT by the combustion of the same mentioned above. The CTD blocks the visible transmission to some extent, and its combustion and disappearance during TT allows the visible transmission of the resulting TT coated article to be significantly increased as shown above. In this way, the combustion of CTD not only acts as a fuel that allows the transformation of the layer that includes Zr, but also allows the visible transmission to increase significantly.

Any suitable type of glass substrate 1 can be used in the different embodiments of this invention. For example, various types of soda-lime-silica glass or borosilicate glass can be used for substrate 1. However, in certain exemplary embodiments of this invention, the coating of any of the aforementioned embodiments can be supported by a special type of glass substrate that has a very high visible transmission and a very transparent color. In particular, in said certain exemplary embodiments of this invention, the glass substrate 1 may be any of the glasses described in co-pending United States Patent Application Serial No. 10 / 667,975, the description of which is incorporated into this document by reference. In certain preferred embodiments, the resulting glass has a visible transmission of at least 85%, more preferably at least 88%, and still more preferably at least 90% (e.g., at a reference thickness of about 0.219 inches or 5.56 mm). The advantage of using such a glass substrate 1 is that the resulting TT product is caused to have a visual appearance similar to that of uncoated clear glass even though the coating is provided on it. In addition to the base glass, examples are shown below

ES 2 297 486 T3 of the batch of glass and / or final glass (in terms of percentage by weight of the total glass composition, unless otherwise shown as ppm):

Example of Colorants and Cerium as an Oxidizer in a Glass Substrate

<td>Ingredient</td><td>general</td><td>Favorite</td><td>Most Preferred</td><td>Best</td>

<td colspan="2">Total iron</td><td></td><td></td><td>from 0.03 to</td>

<td></td><td> 0,01-0,20%</td><td> 0,01-0,15%</td><td> 0,02-0,12%</td><td></td>

<td>(Faith₂OR₃):</td><td></td><td></td><td></td><td> 0,10%</td>

<td>Oxide</td><td>of</td><td>0.1 to 10</td><td></td><td></td>

<td></td><td>0 to 15 ppm</td><td></td><td colspan="2">0.5 to 5 ppm 0.5 to 3 ppm</td>

<td>cobalt:</td><td></td><td>ppm</td><td></td><td></td>

<td></td><td></td><td></td><td></td><td>from 0.05 to</td>

<td colspan="2">Cerium oxide: 0.005-1.0%</td><td> 0,01-1,0%</td><td> 0,01-0,5%</td><td></td>

<td></td><td></td><td></td><td></td><td> 0,2%</td>

<td>Oxide</td><td>of</td><td></td><td></td><td>from 0.02 to</td>

<td></td><td>0 to 1.0%</td><td> 0,01-0,30%</td><td> 0,02-0,20%</td><td></td>

<td>erbium:</td><td></td><td></td><td></td><td> 0,15%</td>

<td>Oxide</td><td>of</td><td></td><td colspan="2">0.001 to 0.01 to</td>

<td></td><td>0 to 0.5%</td><td>0 to 0.2%</td><td></td><td></td>

<td>titanium:</td><td></td><td></td><td> 0,05%</td><td> 0,02%</td>

<td>Oxide</td><td>of</td><td></td><td></td><td></td>

<td></td><td>0 to 10 ppm</td><td>0 to 8 ppm</td><td>0 to 5 ppm</td><td>1 to 5 ppm</td>

<td>chrome:</td><td></td><td></td><td></td><td></td>

<td>Redox glass</td><td> : &lt;=0,20</td><td> &lt;= 0,12</td><td> &lt;= 0,10</td><td> &lt;= 0,08</td>

<td>% Of ugly:</td><td> 0,0001-0,05%</td><td> 0,0001-0,01%</td><td> 0,001-0,008%</td><td> 0,001-0,003%</td>

It is noted that in other embodiments of this invention, additional layers (not shown) can be added to the coated articles discussed above, and / or certain layer (s) can be removed.

Example 1

For purposes of example, and without limitation, the following exemplary coated article was prepared and tested in accordance with an exemplary embodiment of this invention. This Example 1 is similar to the embodiment of Figure 5.

Glass substrate 1 was cleaned / washed. It was then ion blast etched using argon gas to clean the surface thereof. Then a protective layer 3 of silicon nitride (doped with Al) approximately 100 A thick, a layer 5 of CTD (ta-C: H type) approximately 70 A thick, a layer 7 'of nitride zirconium about 100 A thick, another 5 'layer of CTD (ta-C: H type) about 70 A thick, another layer 7 of zirconium nitride about 100 A thick, and a CTD sacrificial outer layer 9 (ta-C: H type) approximately 70 A thick were formed on a glass substrate (see Figure 5). Layers 7 and 7 'of ZrN were formed by sputtering to a Zr target in an atmosphere including N and Ar, and the CTD layers were formed by ion jet deposition using an anode-cathode voltage of approximately 3,000 V and acetylene as the supply gas.

Figure 3 is an XPS chart illustrating the pre-TT chemical composition of the coated article according to this Example. As can be seen in Figure 3, the carbon (C) peaks indicate the 5 and 5 'CTD layers, while the Zr peaks indicate the 7 and 7' ZrN layers. The C content is seen to increase at the left edge of the graph of Figure 3 showing the thin sacrificial layer 9 of CTD in the outermost layer of the pre-TT coating. The high oxygen content on the right hand side of the graph indicates the glass substrate, and the combination of Si and N peaks in the same area indicates the optional protective layer 3 of silicon nitride.

The coated article from Example 1 was then subjected to TT at about 625 ° C for about four minutes.

ES 2 297 486 T3

Figure 4 is an XPS plot of the coated article of Figure 3 (ie, this Example 1) after TT. Figure 4 illustrates that CTD overlay layer 9 was calcined during TT due to combustion, and that pre-TT layers 5, 7 ', 5' and 7 'were fused or transformed into a thick essentially composed layer by scratch resistant zirconium oxide 11 which was lightly doped with nitrogen (see the coated article on the right in Figure 5 which is the post-TT article). It can be seen from Figure 4 that residual carbon is left on the zirconium oxide layer 11 due to the previous CTD layers that were present prior to heat treatment.

Example 2

Example 2 was prepared according to the embodiment of Figure 6. On a 10mm thick transparent glass substrate having a composition similar to that discussed above, layers 5,7 and 9 were formed as shown in Figure 6. CTD layer 5 was 34 A thick, ZrN layer 7 was 160 A thick, and CTD layer 9 was 100 A thick. The two CTD layers were formed by ion jet deposition using acetylene gas, while the zirconium nitride layer 7 was formed by sputtering using a power of about 3 kW. After heat treatment, the coated article included substrate 1 and zirconium oxide layer 11 which included some nitrogen as shown on the right hand side of Figure 6.

After TT, based on three different samples from this example, the coated article of this example had an average visible transmission of approximately 78.61%, a critical scratch load (CAC) of 14.06 kg (31 pounds) and a haze value of 1.6.

Example 3

Example 3 was prepared according to the embodiment of Figure 7. On a 10mm thick transparent glass substrate 1 having a composition similar to that discussed above, layers 7 and 9 were formed as shown in Figure 7, ZrN layer 7 was 160 A thick, and CTD layer 9 was 60-100 A thick. As in the other examples, the zirconium nitride layer was formed by sputtering. After heat treatment, the coated article included substrate 1 and zirconium oxide layer 11 which included some nitrogen as shown on the right hand side of Figure 7.

After TT, based on three different samples from this example, the coated article of this example had an average visible transmission of approximately 81.35%, a critical scratch load (CAC) of 4.90 kg (10.8 lbs. ) and a turbidity value of 0.44.

In certain non-limiting exemplary embodiments of this invention, post-TT coated articles may have a visible transmission of at least 70%, more preferably at least 75%. In certain non-limiting exemplary embodiments of this invention, the post-TT coated articles may have a haze value of no greater than 2.5, more preferably no greater than 1.75, and sometimes no greater than 1.0.

Although the invention has been described in relation to what are presently considered to be the most practical and preferred embodiments, it should be understood that the invention is not limited to the described embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.