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

The subject of the invention is a method for producing coated products for use in window panes or in any other suitable applications, such as furniture glass or glass used in picture frames. For example, in one embodiment, the present invention includes a method of making window panes (e.g., vehicle windows such as windshields, rear windows, roof windows or side windows, or insulating glass for windows or shower doors) including the step of heating a coated glass substrate at least a layer containing diamond-like carbon (DLC). According to one example embodiment, DLC can be used to generate energy during heat treatment (HT) to transform at least another layer into a new layer as heat treated layers that was not before heat treatment. Certain other exemplary embodiments of the invention include such coated or untreated heat treated products that can be used as window glass or in many other suitable applications such as furniture glass and the like.

Car windows (for example, windshields, rear windows, roof windows and side windows) are products known in the art. For example, car windshields typically contain two bent glass substrates connected by a polymeric inner layer such as polyvinyl butyral dehydrogen (PVB). It is known that one of the two glass substrates can be coated (for example, by low-E coating) to reduce sunlight, such as IR (infrared) and / or UV (UV) reflection, so that the interior of the vehicle was more friendly in certain weather conditions. Conventionally, vehicle windshields are made as follows. The first and second flat, glass substrates are prepared, one of them optionally having a low-E spray coating. A pair of glass substrates are washed and folded together (e.g. by applying one on top of the other), then after folding the substrate is heated together and bent to the desired shape necessary for the windshield of the vehicle at a high temperature (e.g., for 8 minutes at a temperature of about 600625^aboutC). The two glass curved substrates are then laminated together with a polymer inner layer to obtain a windshield.

Insulated glass (IG) windows are also known in the art. Conventional insulated glass panes contain at least the first and second glass substrates (one of which may contain a coating that protects its internal surface from sunlight) that are bonded to each other by at least one gasket (gaskets) or spacers (spacers). The resulting space or gap between the glass substrates may or may not be filled with gas and / or the pressure may be reduced therein in various cases. In addition, many insulated glass panes require tempering. Thermal tempering of glass substrates for this type of insulated glass panes usually requires heating the glass substrate to a temperature (s) of at least about 600^aboutC in sufficient time to allow thermal tempering.

Other types of coated products also require heat treatment (e.g., tempering, heat binding and / or heat strengthening) in certain applications. For example, without limitation, glass shower doors, glass table tops and the like require heat treatment in some cases.

A diamond-like carbon (DLC) coating is known for its scratch resistance. For example, various DLC coatings are described in US Pat. Ser. Americas with the following numbers: 6 303 226,

303 225; 6 261 693; 6 338 901; 6 312 808; 6 280 834;

284 377; 6 335 086; 5 858 477; 5 635 245; 5 888 593;

135 808; 5,900,342 and 5,497,661, all of which are incorporated herein by reference.

It may sometimes be desirable to provide a window coating or other glass product with a protective coating containing DLC ​​to protect against scratches and similar damage. Disadvantageously, the DLC layer tends to oxidize and burns at a temperature of about 380 to 400^aboutC or higher, and the effect of temperature is usually carried out in an atmosphere containing oxygen. Thus, it is understood that DLC as a coating protective layer cannot be subjected to heat treatment at the extremely high temperatures described above, which are often required for the production of vehicle windows, insulating glass for windows, glass table tops and / or the like. Accordingly, DLC alone cannot be used as a heat-treated coating, because it will be oxidized during heat treatment and then disappear as a result of this reaction (i.e., it will burn).

Certain other types of scratch-resistant substances also cannot withstand the heat treatment necessary for tempering, thermal strengthening and / or bending of the glass substance under the coating.

Accordingly, it is understood by those skilled in the art that there is a need to develop a method for coating products with a scratch-resistant coating that is able to undergo heat treatment, so that after heat treatment the product coated with the appropriate layer remains a scratch-resistant product. There is also a need to produce coated products, both heat treated and heat treated products.

In certain example embodiments of this invention, its subject is a method of making a coated product (e.g., a window pane, such as a vehicle window, building window or the like) that can be heat treated, which is a coated product with a scratch resistance greater than glass uncoated.

In certain example embodiments of this invention, the coated product includes hydrogenation of appropriate layers comprising DLC ​​and zirconium nitride prior to subjecting the product to heat treatment. The DLC layer may be located below and / or above the layer containing zirconium nitride. During heat treatment, the hydrogenated DLC layer reacts as a fuel that produces carbon dioxide and / or water when burned with oxygen. Such an exothermic reaction, associated with the combustion of hydrogenated carbon with DLC, causes spontaneous propagation of the combustion wave along the layers of the starting reagents. The high temperature developed during this combustion reaction heats the layer containing zirconium nitride to a temperature (temperatures) well above the temperature used during the heat treatment process, thereby causing a transformation in the layer containing zirconium nitride into a new layer after heat treatment containing zirconium oxide. In certain example embodiments of this invention, the new heat treated layer comprising zirconia may also contain nitrogen.

The new heat treated layer containing zirconia is surprisingly highly scratch resistant. Thus, it can be said that a method has been proposed which allows the production of a heat treated, scratch resistant product; and the coated product may also have good permeability properties. In certain example embodiments, coated heat treated products exhibit a higher scratch resistance than the DLC containing non-heat treated products.

In certain example embodiments, a method of making a coated heat treated product has been proposed, comprising: applying a coating layer to a glass substrate, coating with a layer comprising zirconium nitride and a layer comprising hydrogenated DLC applied to the layer containing zirconium nitride; performing a heat treatment of the glass substrate and coating layer in a manner sufficient for thermal tempering, thermal strengthening and / or thermal binding of the glass substrate; and wherein during said heat treatment, with respect to the layer containing hydrogenated DLC, it burns or burns it, which produces sufficient heat to cause the transformation of the zirconium nitride-containing layer to the heat-treated layer containing zirconium oxide in the heat-treated product.

In certain example embodiments of this invention, there is provided a method of making a heat-treated coated product, comprising: applying a coating layer to a glass substrate, coating with a metal nitride-containing layer and a DLC-containing layer applied to the metal nitride-containing layer; heat treatment of the glass substrate and coating layer; and wherein said heat treatment of the DLC-containing layer that is subjected to firing or burning, which produces a sufficient amount of heat to cause the metal nitride-containing layer to be converted into a heat-treated layer containing metal oxide in the heat-treated coated article. The metal may be zirconium or any suitable metal or metal alloy.

In yet other example embodiments of this invention, its subject is a coated and heat treated product comprising a coating applied to a glass substrate, the coating of which includes: the outermost layer containing nanocrystalline zirconia with a regular spatial crystalline structure; and wherein the zirconia-containing layer further contains from 0.25 to 20% carbon.

In other example embodiments of this invention, its subject is a coated product comprising a coating applied to a glass substrate, the outer coating of which, relative to the glass substrate, is a zirconium nitride layer; and a layer comprising hydrogenated

DLC. The product may also have other layers in any appropriate arrangements. Such coated products, in accordance with certain example embodiments, may be adapted to the heat treatment process to effect at least partial conversion of nitride to oxide.

In other example embodiments of this invention, its subject is a method of making a coated product, comprising: applying coatings to a substrate, a layer comprising DLC, and a layer that undergoes heat treatment; heating the DLC-containing layer and the transforming layer as a result of burning the DLC-containing layer to generate heat in the DLC-containing layer during its combustion; and utilizing the heat generated as a result of the combustion of the layer comprising DLC ​​to allow for phase transformation of the layer undergoing this transformation such that after heating a new phase-transformed layer is formed.

Figure 1 is a schematic diagram illustrating a coated product consistent with the embodiment of the present invention before and after heat treatment.

Figure 2 is a schematic diagram illustrating a coated product compatible with another embodiment of the present invention before and after heat treatment.

Figure 3 is an XPS chart illustrating the chemical element contents of the coated product prior to heat treatment, in accordance with an example of the present invention.

Fig. 4 is an XPS chart illustrating the chemical element contents of the product of Fig. 3 after heat treatment of the coated product according to Fig. 3.

Figure 5 is a schematic diagram illustrating a coated product according to an embodiment of the present invention, before and after heat treatment.

Figure 6 is a schematic diagram illustrating a coated product according to another embodiment of the present invention, before and after heat treatment.

Figure 7 is a schematic diagram illustrating a coated product according to yet another embodiment of the present invention, before and after heat treatment.

The attached drawings are now more detailed in which similar reference numbers point to similar parts or layers and allow for a broad overview.

Certain exemplary embodiments of the present invention show methods for producing coated products that can be heat treated in which coated products contain coatings (one or more layers) containing DLC ​​and / or zirconium. In some cases, the heat treatment involves heating a load-bearing glass substrate, with a DLC and / or zirconium layer including the layer (s) applied to the substrate, to a temperature of 550 to 800^aboutC, more preferably from 580 to 800^aboutC (i.e. to a temperature much higher than the burning temperature for DLC). In particular, the object of certain example embodiments of this invention is a manufacturing method that provides heat treated coated products that are more scratch resistant than uncoated glass.

In certain example embodiments of this invention, coated products are prepared by an original process (e.g., prior to heat treatment or are subjected to heat treatment) and include appropriate alternative layers containing hydrogenated DLC and zirconium nitride. DLC can be located below and / or above zirconium nitride. During heat treatment (for example, using temperatures or temperatures from 550 to 800^aboutC, more preferably from 580 to 800^aboutC), hydrogenated DLC acts as a fuel that produces carbon dioxide and water when burned with oxygen from the atmosphere. This exothermic reaction of hydrogenated carbon combustion with DLC causes spontaneous expansion of the combustion wave in the initial reactants. The high temperature created during the combustion of DLC, as a result of the separated heat energy, heats the layer (layers) containing zirconium nitride to a temperature (temperatures) much higher than the temperature used during heat treatment. For example, DLC combustion can heat part of the layer (s) containing zirconium nitride to a temperature of at least about 1200^aboutC, more specifically to at least about 1500^aboutC and most preferably to a temperature of at least about 2000^aboutC.

Since the layer (s) containing zirconium nitride is heated to such a high temperature as a result of DLC combustion during heat treatment, at least the layer (s) containing zirconium nitride are transformed as a result of this high temperature (temperatures) into a new layer (s) after heat treatment containing zirconia. The new layers (layer) after heat treatment containing zirconia may also contain nitrogen compounds, in accordance with certain example embodiments of this invention (for example, ZrO: N; ZrO2: N, ZrOx: N (in which x is a number from 1 to 3, more preferably from 1.5 to 2.5) and / or any other suitable stoichiometric ratio). The new layer (s) after heat treatment, containing zirconium oxide (possibly together with nitrogen compounds) is unexpectedly highly scratch resistant. Thus, it was found that a method based on heat treatment and allowing to obtain a scratch resistant product could be proposed; and the resulting coated products may have good light transmission properties. In accordance with certain example embodiments, the scratch resistance of heat treated coated products may also be better than non heat treated DLC products.

In accordance with certain example embodiments of this invention, the heat treated layers (layer) containing zirconia exhibit a nanocrystalline regular spatial crystal structure. Undamaged layers (layer) may exhibit a type of nanocrystalline regular spatial crystalline structure, or alternatively only part of the layer (layers) may be characterized by a nanocrystalline regular spatial structure. Zirconium nitride usually does not increase spatially if the temperature is not at least around 2000^aboutC. Zirconium nitride before heat treatment usually does not occur in the form of a regular spatial network. Because the heat treatment only takes place at a temperature of no more than about 900^aboutC (more preferably not more than about 800^aboutC), it is obvious that zirconium nitride with irregular structure prior to heat treatment cannot grow into a regular form during heat treatment. However, it has surprisingly been found that the combustion of DLC during heat treatment causes that at least part of the layer containing zirconium nitride is heated high enough to induce transformation into a layer (s) after heat treatment, containing zirconia in nanocrystalline regular spatial form (with or without compounds) nitrogen), which has a very high scratch resistance.

Thus, it has been found that in accordance with certain example embodiments of this invention, the zirconium nitride layer prior to heat treatment is transformed during the heat treatment into a new heat treated layer containing zirconium oxide with a nanocrystalline regular spatial structure, even when the temperatures used in the oven during heat treatments are much lower than required for typical spatial crystal growth. This combustion of the DLC during heat treatment generates the amount of energy / heat that is sufficient to allow the zirconium layer to undergo phase change and regular growth, or at least such that the final phase after heat treatment produces a product with a nanocrystalline regular spatial structure.

As a result of the heat treatment, the amount of oxygen after heat treatment in the zirconium-containing layer (s) is much greater than the amount of oxygen in the zirconium-containing layer (s) prior to heat treatment. For example, in certain example embodiments of this invention, the zirconia layer (s) after heat treatment contain at least 5 times more oxygen compared to the zirconium nitride layer (s) prior to heat treatment, more preferably at least 10 times more and most preferably at least 20 times more oxygen compared to the layer (s) prior to heat treatment. According to certain example embodiments of this invention, the zirconium nitride layer (s) prior to heat treatment contain from about 0-10% oxygen, more preferably from about 0-5% oxygen, and most preferably from about 0-2% (mol%) oxygen . Meanwhile, in certain example embodiments of this invention, after the heat treatment and transformation phase induced by the combustion of DLC, the heat treatment layer (s) comprising zirconia contains much more oxygen, as will be outlined below.

Figure 1 schematically illustrates how, in accordance with an exemplary embodiment of the present invention, a coated product can be produced. Initially, the coated product is made using a glass substrate

1. The coated product comprises, applied to the glass substrate 1, at least one optional dielectric layer 3 with or containing silicon nitride, silicon oxo-nitride, silicon oxide or the like; a first layer 5 with DLC or containing DLC, a first layer 7 with zirconium nitride or containing zirconium nitride (e.g., ZrN or any other compound having a suitable stoichiometric ratio), and a top layer 9 with DLC or containing DLC. The glass substrate 1 is usually made of or contains soda-lime-quartz glass, although other types of glass may be used in some cases.

The dielectric layer (s) 3 is introduced to prevent sodium diffusion into the DLC layer during heat treatment (i.e. a diffusion barrier is placed). Such layer (s) 3 also allows for thermal adjustment14 which does not occur without problems between the DLC layer and the glass substrate, which greatly simplifies thermal bending and similar processes. Surprisingly, it has been found that the use of silicon oxide as barrier 3 (compared to silicon nitride) often results in improved optical properties of the final product after heat treatment, such as increased light transmission in certain example embodiments of this invention. The above-mentioned barrier layer materials 3 can be supplemented (e.g., 0.5 to 15%) with aluminum, stainless steel or any metal (s) in certain example embodiments of this invention. The barrier layer (s) 3 is produced on a glass substrate 1, by cathodic sputtering, or by any other method.

Layers 5 and 9 containing DLC ​​may be any type of diamond-like carbon, such as, but not limited to, any of the diamond-like carbon described in any of the following US Pat. Ser. Americas with the following numbers: 6 592 993; 6,592,992; 6,531,182;

461 731; 6 447 891; 6 303 226; 6 303 225; 6 261 693;

338 901; 6 312 808; 6 280 834; 6 284 377; 6 335 086;

858 477; 5,635,245; 5,888,593; 5,135,808; 5,900 342 and / or

470 661, all of which are incorporated herein by reference.

For example, for illustrative purposes only, in certain example embodiments of this invention, the layer (s) containing DLC ​​5 and / or 9, each of which may have a thickness of about 5 to 1,000 Angstroms (A), more preferably 10 to 300 A thick and most preferably from 45 to 65 A thick. In accordance with certain example embodiments of this invention, layer (s) 5 and / or 9 comprising DLC ​​may have an average hardness of at least about 10 GPa, more preferably at least about 20 GPa, and most preferably from about 20 to about 90 GPa. These hardness layers 5 and 9 are scratch-resistant, some solvents and / or have similar characteristics. Layer (s) 5 and / or 9, in certain example embodiments, may be constructed or may contain a particular type of DLC known as highly tetrahedral amorphous carbon (t-aC) and in some embodiments hydrogenated carbon (t-aC: H). In certain embodiments, t-aC: H hydrogenated carbon of the diamond-like carbon type contains 4 to 39% hydrogen, more preferably 5 to 30% hydrogen, and most preferably 10 to 20% hydrogen.

This type of t-aC or t-aC carbon: H used as DLC in layer 5 (s) and / or 9 may contain more sp bonds³ carbon - carbon (C - - C) than bonding sp² carbon - coal (C - - C). In certain example embodiments, at least about 50% of the carbon-carbon bonds in layer 5 (s) and / or 9 containing DLC ​​may be carbon-carbon (C-C) sp-type bonds³, more preferably at least about 60% of the carbon-carbon (C-C) bonds in the layer (s) may be of the sp type³, most preferably at least about 70% of the carbon-carbon (C-C) bonds in the layer (s) may be of the sp type³. In certain example embodiments of this invention, DLC in Layer (s) 5 and / or 9 may exhibit an average density of at least about 2.4 g / cm³, more preferably at least about 2.7 g / cm³.

For applying DLC-containing layers 5 and 9 to substrate 1, exemplary ion beam linear sources may be used in accordance with any of the following US Patent Ser. United States Numbers 6,261 693, 6 002 208, 6 335 086 or 6 303 225 (all references herein). If ion beam sources are used to apply layer (s) 5 and / or 9, a stream of hydrocarbon gas (e.g., C2H2), HMDSO or any other suitable gas is fed to the ion beam source, it can be used in the ion beam source developing in the emission source an ion beam directed towards the substrate 1 to form layer (s) 5 and / or 9. It has been found that the hardness and / or density of the layer (s) 5 and / or 9 can be corrected by changing the ionic energy in the layer application device. In accordance with certain example embodiments, at least about 2000 V (voltage, anode to cathode) may be used, e.g., about 3000 V may be used in the ion source to apply layer (s) 5 and / or 9. It should be noted that the term "on a substrate" as used herein is not limited to direct contact with the substrate, as other layers (layers) may occur between them.

In certain example embodiments of this invention, layer 7 containing zirconium nitride is introduced between layers 5 and 9, containing DLC. In certain example embodiments, layer 7 comprising zirconium nitride is placed directly between layers 5 and 9 containing DLC ​​so that they contact each other, however, according to other example embodiments, another layer (s) (not shown) may be introduced between layer 7 containing nitride zirconium and layer (s) 5 and / or 9 containing DLC. Layer 7 containing zirconium nitride may contain zirconium and nitride or alternatively may contain other substances including but not limited to oxygen or other dopants such as aluminum and the like. The zirconium nitride-containing layer 7 may be produced by sputtering or the like in accordance with certain example embodiments of this invention. Layer (s) 7 (and layer 7 'discussed below) containing zirconium nitride prior to heat treatment may contain from about 10 to 70% zirconium, more preferably from about 30 to 65% zirconium, even more preferably from about 40 to 60% zirconium , and most preferably from about 45 to 55% zirconium (% values ​​are atomic% values); and from about 20 to 60% nitrogen, more preferably from about 30 to 50% nitrogen (% values ​​are mol%).

In certain example embodiments of this invention, layer (s) 7 (and layer 7 'discussed below) containing zirconium nitride may have a density of at least 6 g / cm³, more preferably at least 7 g / cm³. Additionally, in certain example embodiments, the layer 7 (and 7 ') comprising zirconium nitride may have an average hardness of at least 650 kgf / mm, more preferably at least 700 kgf / mm and / or may be overlapped at least 0.25 (more preferably at least 0.30) to increase strength. In some exemplary cases, many of the Zr - N bonds in layer 7 (and 7 ') may be covalent bonds that are stronger than ionic bonds, for example, increase strength. It has also been found that in certain example embodiments of this invention, layer 7 containing ZrN (and 7 ') may have a melting point of at least 2500^aboutC, and in certain example cases it may be about

2980^aboutC. In certain example embodiments of this invention, the zirconium nitride in layer 7 (and 7 ') can be represented by the formula ZrxNy, in which the ratio x: y ranges from 0.8 to 1.2, in certain example embodiments it is preferably about 1.0.

For the purpose of example only, some examples of the thickness of the layer prior to heat treatment are shown below on the left of Figure 1. The layers are listed in order of placing them from the glass substrate to the outer layer.

Coating example (Fig. 1) - Layer thickness (before heat treatment)

<td>Layer</td><td>Generally</td><td>More favorably</td><td>Most preferably,</td>

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

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

The coated product formed prior to heat treatment is shown on the left of Figure 1, optionally it may be heat treated sufficient to at least achieve thermal bonding, bonding at the appropriate temperature and / or thermal strength increase.

Referring to Fig. 1, during heat treatment (e.g., in an oven at a temperature (temperatures) from 550 to 800^aboutC, more preferably from 580 to 800^aboutC), the higher or lower layer 9 containing DLC ​​is burned at high temperature during heat treatment. In particular, layer 9 containing hydrogenated DLC acts as a fuel that burns with atmospheric oxygen during heat treatment to give carbon dioxide and water. Such an exothermic reaction caused by the combustion of hydrogenated carbon in at least layer 9 containing hydrogenated DLC, causes a spontaneous expansion of the combustion wave starting from the initial reactants. The high temperature that develops during such combustion heats the layer 7 containing zirconium nitride to a temperature (s) well above the temperature of the heat treatment used in the furnace. For example, burning the DLC in layer 9 may heat a portion of layer 7 containing zirconium nitride to a temperature of at least about 1200^aboutC, more preferably at least about 1500^aboutC, and most preferably at least about 2000^aboutC.

Since the layer 7 containing zirconium nitride is heated to such a high temperature as a result of DLC combustion during heat treatment, the layer 7 containing zirconium nitride is transformed during heat treatment into a new layer 11 after heat treatment containing zirconium oxide. The new layer 11, formed after heat treatment and containing zirconium oxide, may also contain nitrogen (and / or other admixtures) in certain example embodiments of this invention (for example, ZrO: N; ZrO₂N; or other compounds in appropriate stoichiometric ratios). The new layer 11, after heat treatment containing zirconium oxide (possibly containing nitrogen) surprisingly proved to be scratch resistant, thus, it provided a coated heat treated and scratch resistant product.

As used herein, the term "zirconia" means ZrO₂and / or any other stoichiometric connection in which the zirconium is at least partially oxidized. In the present specification, any description of layer 11 may also be applied to layer 11 '; and likewise any description of layer 7 may be applied to layer 7 '.

Layer 11 obtained after heat treatment and containing zirconia, in certain example embodiments of this invention, contains at least 0 to 30% nitrogen, more preferably 0 to 20% nitrogen, even more preferably 0 to 10% nitrogen, and in certain embodiments exemplary embodiments of the present invention most preferably from about 1 to 5% nitrogen. The layer 11 obtained after heat treatment and containing zirconia may contain from about 10 to 70% zirconium, more preferably from about 20 to 60% zirconium, even more preferably from about 30 to 55% zirconium, and most preferably from about 30 to 45% zirconium , specified in atomic%. In addition, the layer (s) 11 obtained after heat treatment and containing zirconia, in certain example embodiments of this invention may contain from about 10 to 85% oxygen, more preferably from about 30 to 80% oxygen, even more preferably from about 40 to 70 % oxygen, and most preferably from about 50 to 70% oxygen.

In certain example embodiments of this invention, the layer 11 obtained after heat treatment and containing zirconia contains a nanocrystalline regular crystalline structure (although in some instances its layer prior to heat treatment containing zirconium nitride does not have). As mentioned above, zirconium nitride usually does not grow as a regular structure below a temperature of at least about 2000^aboutC. Surprisingly, it was found that combustion in a layer containing DLC ​​during heat treatment causes that at least a portion of layer 7 containing zirconium nitride prior to heat treatment will be efficiently heated to grow in a regular structure and will become layer 11, which after heat treatment contains zirconium oxide (with or without nitrogen) and has a nanocrystalline regular crystal structure, which is very scratch resistant in certain example embodiments of this invention.

It has surprisingly been found that the use of zirconium nitride (e.g., ZrN) in layer 7, prior to heat treatment, is particularly advantageous in that it allows the formation after transformation of zirconium-containing transformed layer 11, with very high scratch resistance.

The final coated heat treated (or non-heat treated) product of Figure 1 exhibits high scratch resistance and can be used for a variety of applications, including but not limited to insulated glass, laminated vehicle windscreens, and other types of glass in vehicles, for furniture and / or similar uses.

For the sake of example only, some examples of layer thicknesses in coated products after heat treatment are shown below to the right of Figure 1. The layers are arranged in order from the glass substrate to the outer layer.

Example of a coating (Fig. 1) - layer thickness (after heat treatment)

<td>Layer</td><td>Generally</td><td>More favorably</td><td>Most preferably,</td>

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

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

<td>Zr0 N (layer 11)</td><td>50-800 A.</td><td>70-600 A.</td><td>100-350 A.</td>

Based on the above data, it can be concluded that the layer 11 obtained after heat treatment and containing zirconium is usually thicker than the zirconium containing layer 7 before heat treatment. In other words, the thickness of the zirconium-containing layer increases during heat treatment. In accordance with certain example embodiments of this invention, the thickness of the zirconium containing layer (e.g., from layer 7 to layer 11) may increase at least about 5% over time or as a result of heat treatment, more preferably at least about 10%, and most preferably at least about 40% . This increase in thickness is caused by the transformation of layer 7 into layer 11 when oxygen migrates to layer 11 after heat treatment (i.e., more oxygen migrates to layer 11 after heat treatment than nitrogen, which is determined in atomic% and / or size) .

While the DLC-containing layer 5 is present as present in the coated heat-treated product in Figure 1, it need not be present in the coated heat-treated product in accordance with alternative embodiments of the present invention. If the layer 5 containing DLC ​​before the heat treatment is subjected to an appropriate temperature and / or exposed to oxygen during the heat treatment, it may be incinerated, which will result in a reduction in thickness or in some cases even its disappearance during the heat treatment. In such cases, the pre-heat treatment layers known as 5, 7 and / or 9 can be effectively converted during heat treatment into the zirconia layer 11 obtained after heat treatment (similar to Figure 5 in this embodiment).

In accordance with certain example embodiments of this invention, the heat treated layer 11 contains zirconia Zr_xABOUT_sin which the value of the y / x ratio ranges from about

1.2 to 2.5, more preferably from about 1.4 to 2.1.

Figure 2 illustrates another embodiment of the present invention. The embodiment illustrated in Figure 2 is similar to the embodiment shown in Figure 1, except that an additional layer (s) 7 'containing zirconium nitride and an additional layer 5' (DLC) containing DLC ​​are introduced prior to heat treatment. In other words, the embodiment shown in Fig. 2 includes a product containing multiple alternative coating applications prior to heat treatment containing DLC ​​and ZrN. Thus, after heat treatment, an additional 11 'layer (s) containing zirconia and an additional 5' layer (s) containing DLC ​​are obtained; the layer 5 'can be seen on the right side of Fig. 2. Layers 5 ', 7' and 11 'in certain example embodiments of this invention are similar to layers 5, 7 and 11, respectively, which are discussed above. However, it is possible that one or both of the 5 and 5 'hydrogenated DLC layers may, in certain example embodiments of this invention, burn and substantially diminish or decrease in thickness as a result of heat treatment if high temperature and / or long heating period is provided so that a single ZrO layer is maintained (for example, see Figure 5), however small amounts of DLC may remain, as shown in Figure 2. However, according to the embodiment of Fig. 2, at least the outer layer 9 containing DLC ​​usually burns and generates the energy / heat necessary to convert one or more layers 7, 7 'containing ZrN into the oxide layer (s) 11, 11' zirconium as outlined above.

Further discussing the embodiment shown in Figure 2, in an exemplary but non-limiting embodiment of the present invention, oxygen from the atmosphere diffuses inward through the layer (s) to allow the transformation of layers 7 and 7 'containing zirconium nitride prior to heat treatment, aided by the heat released as a result of the combustion reaction mentioned above, which transformation leads to heat treatment of layers 11 and 11 'containing zirconia. However, in accordance with other example embodiments of this invention, the zirconium nitride-containing layer 7 'need not undergo phase transformation during the heat treatment prior to heat treatment; according to these embodiments, the layer 11 'obtained after the heat treatment may be similar to the layer 7' before the heat treatment and contain essentially zirconium nitride. In yet other embodiments of the present invention, the layer 11 'can be partially transformed and thereby obtain a mixture of zirconium nitride and zirconia.

Figures 3-5 show another example embodiment of the present invention. The coated product in this embodiment, before being subjected to heat treatment, is the same as that shown in the embodiment illustrated in Figure 2, described above. Figure 3 is an XPS chart illustrating the chemical transformation of an example coated product prior to being subjected to heat treatment as embodied in Figure 5. However, unlike the embodiment shown in Figure 2, in the embodiment shown in Figure 5, during the heat treatment, the layers containing DLC ​​are subjected to combustion and essentially disappear. During this combustion significant amounts of heat are released and the diffusing oxygen binds to the coating from the surrounding atmosphere, which causes each of the layers containing zirconium nitride to be transformed during heat treatment before heat treatment, so that at least one layer forms after heat treatment. 11 containing zirconia (which may or may not contain nitrogen). According to the embodiment shown in Fig. 5, layers 5, 7 ', 5', 7 and 9 before heat treatment combine or eventually form one rather thick layer 11, obtained after heat treatment, containing zirconium oxide. Figure 4 is an XPS chart illustrating the chemical transformation of an example coated product which after heat treatment was obtained in accordance with the embodiment shown in Figure 5.

The embodiment shown in Figs. 3-5 can be illustrated in Fig. 4, where the carbon remaining after heat treatment in the zirconia layer 11 depends on the presence of DLC in the layer (s) prior to heat treatment. In certain example embodiments of this invention, the layer 11 comprising zirconia also contains from 0.25 to 20% carbon, more preferably from 0.25 to 10% carbon, most preferably from 0.25 to 5% carbon.

Figure 6 is a cross-sectional view of another example embodiment of the present invention. In the embodiment shown in Figure 6, the layer 5 comprising DLC ​​is placed directly on the glass substrate 1. In accordance with certain example cases, certain carbon atoms may be incorporated into the substrate to improve binding. In this example embodiment, layer 7 containing zirconium nitride is sandwiched between layers 5 and 9 containing DLC. During heat treatment, at least one DLC-containing outer layer 9 acts as a fuel and causes that at least layer 7, after heat treatment, is transformed into a new layer 11 containing zirconia, as shown in Figure 6 and as described above . During heat treatment as a result of combustion, the DLC-containing layer 5 may act as a fuel and / or may be fused to glass and / or layers 7 and 11.

If layer 5, during heat treatment, blends into the glass layer 1, a transitional layer is obtained between the surfaces near the surface of the substrate layer that contains silicon oxy-carbide. In certain embodiments of the present invention, the DLC-containing layer 5 can act as a barrier to sodium atoms, preventing the migration of significant amounts of sodium during heat treatment, from the glass substrate to the zirconium-containing layer, reducing the likelihood of damage to the zirconium-containing layer.

In some other cases, certain example embodiments of this invention, it is possible that the DLC containing layer 5 may shrink during heat treatment, but does not disappear completely.

In the embodiment shown in Fig. 6, layer 5, containing DLC, may have a thickness of from about 20 to 60 A, more preferably a thickness of 28 to 34 A, or may have any other suitable thickness; the layer 7 containing ZrN may have a thickness of from about 100 to 200 A, more preferably a thickness from about 150 to 190 A, most preferably a thickness from about 160 to 170 A, or may have any other suitable thickness; and the layer 9 comprising DLC ​​may have a thickness of about 50 to 200 A, more preferably a thickness of 80 to 120 A, most preferably a thickness of 90 to 110 A, or may have any other suitable thickness. In some cases, if the thickness of the bottom layer 5 containing DLC ​​falls below the range of 28 to 34 A, unwanted haze increases rapidly, especially in thinner places.

Figure 7 is a cross-sectional view of another example embodiment of the present invention. The embodiment shown in Figure 7 is similar to the embodiment shown in Figure 6, except for the absence of a bottom layer 5 containing DLC. Thus, Fig. 7 shows an embodiment in which the layer 7, containing zirconium nitride prior to heat treatment, was placed directly on the glass substrate 1.

Each of the incarnations listed above provides very high scratch resistance given during heat treatment of coated products undergoing this treatment. For example, heat treated coated products according to certain embodiments of the present invention may have a critical scratch load, tested using an alumina ball of at least about 15 pounds, more preferably at least 18 pounds, even more preferably 20 pounds, even more preferably at least 22.5 pounds and most preferably at least 30 pounds. In addition, coated products according to certain embodiments of the present invention are resistant to UV radiation and do not degrade significantly when exposed to UV rays. In certain example embodiments, coated products may after heat treatment exhibit a grip angle Θ with a drop of water during its dislocation of from about 25 to 60^about; and sometimes the grip angle is less than 35^about.

In addition, in certain example embodiments, good optical properties with little yellow color are obtained in the products after heat treatment, even when yellowish color was present in the products prior to the DLC heat treatment. The coated products obtained after heat treatment are surprisingly transparent to visible light. For example, heat treated coated products, in accordance with certain example embodiments of this invention, may have a light transmittance 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 example embodiments of this invention, coated heat-treated articles exhibit a * transmittance value of -5 to +2, more preferably -4 to 0, and most preferably -3.5 to -1; and a transmissivity b * of from -8 to +8, more preferably from -3 to +3, and most preferably from -2 to +2. In other words, coated heat treated products in accordance with certain example embodiments of this invention visually show significant similarity to pure uncoated glass, even when multiple layers have been applied to increase durability.

Another unique aspect of certain example embodiments of this invention is the extreme increase in light transmission due to heat treatment. In certain example embodiments, the visible radiation transmission increases by at least about 20% visible transmission after heat treatment, more preferably at least 30%, and most preferably by at least 40%. For example, in certain examples of the present invention, visible light transmission of about 36-37% is obtained for products prior to heat treatment. However, after heat treatment for about 400 seconds at a temperature of about 640^aboutC, visible light transmission was around 77-81%. In each case, after heat treatment, visible light transmission increases by about 40-45%. To give an example and explain this phenomenon, if the coated product exhibits a visible transmission of 36% before heat treatment and the coated product has a visible transmission of 80% after heat treatment, thus the visible transmission increases by 44% (i.e., 80 % - 36% = 44%) in the result

36% heat treatment. There is a clear association between such a significant increase in visible light transmission and heat treatment causing at least some of the DLC to disappear during heat treatment as a result of said combustion. DLC blocks visible transmission to a certain extent, while its combustion and disappearance during heat treatment allows for the aforementioned significant increase in heat transmission in the heat treated coated product. Thus, the combustion of DLC not only acts as a fuel that allows the transformation of the zirconium-containing layer, but also significantly increases visible light transmission.

Glass substrate 1 of any suitable type may be used in various embodiments of the present invention. For example, different types of soda - lime - quartz glass or boron - quartz glass can be used to make substrate 1. However, in certain example embodiments of this invention, coatings in any of the above embodiments may be applied to specialty glass substrates that exhibit very high visible light transmission and a very light color. In particular, in such certain example embodiments of this invention, the glass substrate 1 may be any type of glass disclosed in our patent application US Ser. America, filed after serial number 10/667 975, which is incorporated herein by reference. In certain preferred embodiments, the glass obtained has a visible transmission of at least 85%, more preferably at least 88%, and most preferably at least 90% (for example, at a thickness of about 0.219 inches or 5.56 mm). The advantage of using such a glass substrate 1 is that a heat-treated product with a appearance similar to the appearance of uncoated transparent glass even when applied to the coating. In addition to the basic glass product, examples of lots of glass and / or the final glass product are given below (values ​​in percent by weight with respect to the total composition of the composition, unless otherwise stated in ppm):

Examples of dyes and ceric oxidant in a glass substrate

<td>Ingredient</td><td>Generally</td><td>favorably</td><td>More favorably</td><td>Most preferably,</td>

<td>Total that</td><td> 0,01-0,20%</td><td> 0,01-0,15%</td><td> 0,02-0,12%</td><td> 0,03-0,10%</td>

<td>lazo (Fe2O3)</td><td></td><td></td><td></td><td></td>

<td>Cobal oxide</td><td>0 to 15</td><td>0.1 to 10</td><td>0.5 to 5</td><td>0.5 to 3</td>

<td>here</td><td>ppm</td><td>ppm</td><td>ppm</td><td>ppm</td>

<td>Cerium Oxide</td><td> 0,005-1,0%</td><td> 0,01-1,0%</td><td> 0,01-0,5%</td><td> 0,05-0,2%</td>

<td>Erbium oxide</td><td>0 to 1.0%</td><td> 0,01-0, 30%</td><td> 0,02-0,20%</td><td> 0,02-0,15%</td>

<td>Titanium oxide</td><td> 0-0,5%</td><td> 0-0,2%</td><td> 0,001-</td><td> 0,01-0,02%</td>

<td></td><td></td><td></td><td> 0,05%</td><td></td>

<td>Chromium oxide</td><td>0-10 ppm</td><td>0-8 ppm</td><td>0-5 ppm</td><td>1-5 ppm</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>Iron oxide</td><td> 0,0001-</td><td> 0,0001-</td><td> 0,001-</td><td> 0,001-</td>

<td>FeO</td><td> 0,05%</td><td> 0,01%</td><td> 0,008%</td><td> 0, 003%</td>

It has been found that in other embodiments of the present invention, additional layers (not shown) may be incorporated into the coated products described above and / or some layers may be removed.

Example 1

By way of example and without limitation, the following example of a coated product may be prepared and tested in accordance with an exemplary embodiment of the present invention. The product according to example 1 is similar to the product shown in the embodiment in Fig. 5.

The glass substrate 1 is cleaned and washed. It is then subjected to ion beam etching using argon gas to clean its surface. Then, on the glass substrate, a barrier layer 3 containing silicon nitride (complemented with aluminum) about 100 A thick, layer 5 containing DLC ​​(type ta-C: H) about 70 A thick, layer 7 'containing zirconium nitride is applied about 100 A, another layer 5 'containing DLC ​​(type ta-C: H) about 70 A thick, another layer 7 containing zirconium nitride, about 100 A thick, and the outer layer 9 containing DLC ​​(type ta-C: H) ) about 70 A thick (see Figure 5). Zirconium nitride-containing layers 7 and 7 'are applied by sputtering zirconium in an atmosphere containing nitrogen and argon, and DLC-containing layers are applied by means of an ion beam using an anode-cathode voltage of about 3000 V in an acetylene stream.

Figure 3 is an XPS chart illustrating the chemically coated product of this example before heat treatment. As shown in Figure 3, carbon peaks indicate layers 5 and 5 'containing DLC, while zirconium peaks indicate layers 7 and 7' containing zirconium nitride. The carbon content was found to increase at the left end of Figure 3, indicating a thin outer layer 9 containing DLC ​​prior to heat treatment. A high oxygen value on the right side of the graph indicates a glass substrate, while a combination of silicon and nitrogen peaks in the same area indicates the optical barrier of silicon nitride in the layer

3.

The coated product of example 1 is heat treated at a temperature of about 625^aboutC in about four minutes.

Figure 4 is an XPS chart of the coated product as shown in Figure 3 (i.e., from Example 1) after it has been heat treated. Figure 4 proves that the outer layer 9 burns off during heat treatment as a result of combustion and that the pre-heat layers 5, 7 ', 5' and 7 combine or are transformed into a thick layer 11 containing zirconia with high scratch resistance, somewhat complemented nitrogen (see, coated product on the right in Figure 5, which shows a heat treated product). In the drawing 4 it can be said that small amounts of carbon are present in the layer 11 containing zirconia, being residues of previous DLC containing layers in the product prior to heat treatment.

Example 2

Example 2 is made according to the embodiment shown in Fig. 6. On a transparent glass substrate 10 mm thick, and with a composition similar to the one above, layers 5, 7 and 9 are applied as shown in Fig. 6. Layer 5 comprising DLC has a thickness of 34 A, layer 7 containing zirconium nitride has a thickness of 160 A, and layer 9 containing DLC ​​characterizes a thickness of 100 A. Two layers containing DLC ​​are produced by means of an ion beam in an atmosphere of acetylene gas, while layer 7 containing zirconium nitride is prepared by cathodic sputtering at a power of about 3kW. Then, after heat treatment, a coated product is obtained comprising a substrate 1 and a layer 11 containing zirconia with some amounts of nitrogen, as shown in the right side of Fig. 6.

Based on the three different samples obtained by this method, after heat treatment, the coated product exhibits an average visible light transmission value of about 78.61%, a critical scratch value (CSL) of 31 pounds, and a haze value of 1.6.

Example 3

Example 3 is made according to the embodiment shown in Fig. 7. On a transparent glass substrate 1 with a thickness of 10 mm, and with a composition similar to that shown above, layers 7 and 9 are applied as shown in Fig. 7. Layer 7 containing nitride zirconium has a thickness of 160 A, and the layer 9 containing DLC ​​has a thickness of 60-100 A. As in other examples, the layer containing zirconium nitride is produced by sputtering. Then, after heat treatment, a coated product is obtained comprising a substrate 1 and a layer 11 containing zirconia with some amounts of nitrogen, as shown in the right side of Fig. 7.

Based on the three different samples obtained by the method of this example, after heat treatment the coated product exhibits an average visible light transmission value of about

81.35%, a critical scratch value (CSL) of 10.8 pounds and a haze value of 0.44.

In one example non-limiting embodiment of the present invention, the heat treated coated product may have a visible transmission of at least 70%, more preferably at least 75%. In certain example non-limiting embodiments of the present invention, the heat treated coated product may have a haze value of not more than 2.5, more preferably not more than 1.75, and sometimes not more than

1,0.

While the invention is presented in connection with what is currently the most practical and based on preferred embodiments, it is understood that the invention is not limited to the disclosed incarnations, but, on the contrary, includes various modifications and equivalent uses, included in the spirit and scope of the appended claims.