Untitled record

ES 2 343 335 T3

DESCRIPTION

Manufacturing process of an article coated with a highly transparent protective hard layer.

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 unit IG window, or shower screen) including a stage of heat treatment of a glass substrate coated with at least one layer comprising diamond-like carbon (DLC). The DLC is used to generate energy during heat treatment (HT) to transform at least one other layer in the coating to form a new post-HT layer (s) that was not present before heat treatment.

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) on ​​it for solar control purposes such as reflecting IR and / or UV radiation, so that the interior of the glass 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 put together (i.e. stacked one on top of the other), and then, while in place, they are bent together into the desired shape for the windshield at high temperature (s) (for example, 8 minutes at approximately 600-625 degrees C). The two curved glass substrates are subsequently 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 (s) of at least about 600 degrees C for a period of time sufficient to enable thermal tempering.

Other types of coated articles also require heat treatment (HT) (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 HT in certain cases.

Diamond-like carbon (DLC) is sometimes known for its scratch-resistant properties. For example, different types of DLC 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.

Sometimes it is desirable to provide a window unit or other glass article with a protective coating that includes DLC to protect it from scratches and the like. Unfortunately, DLC tends to oxidize and calcine at temperatures of about 380 to 400 degrees C or higher, since the heat treatment is typically carried out in an atmosphere that includes oxygen. In this way, it will be understood that DLC as a protective coating cannot withstand the heat treatments (HT) 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, DLC 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 not capable of withstanding 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 (HT) such that after heat treatment the coated article remains scratch resistant. . There is also a need for corresponding coated articles, both heat treated and pre-HT.

Brief Summary of Invention Examples

In accordance with the present invention, there is provided a method of manufacturing a coated article (eg, a window unit such as for a vehicle, building or the like) that can be heat treated.

ES 2 343 335 T3 so that after heat treatment (HT) the coated article is scratch resistant to a greater degree relative to uncoated glass.

In certain example embodiments, a coated article includes respective layers comprising hydrogenated diamond-like carbon (DLC) and zirconium nitride prior to heat treatment (HT). The DLC can be located below and / or above the layer comprising zirconium nitride. During HT, the hydrogenated DLC acts as a fuel that after combustion with oxygen produces carbon dioxide and / or water. This exothermic reaction, caused by the combustion of the hydrogenated carbon in the DLC, 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-HT layer. comprising zirconium oxide. The new post-HT layer comprising zirconium oxide may also include nitrogen in certain example embodiments of this invention.

The new post-HT layer comprising zirconium oxide is surprisingly scratch resistant. Thus, it can be seen that a technique has been provided which allows for the existence of a heat treatable scratch resistant product; and the coated article may also have good transmission properties. In certain example embodiments, the scratch resistance of the post-HT coated article can be even better than that of non-HT DLC.

In certain example embodiments, a method of manufacturing 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 hydrogenated diamond-like carbon (DLC) 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 DLC is burned or calcined generating sufficient heat to cause the layer comprising zirconium nitride to transform into a heat treated layer comprising zirconium oxide in the coated article. heat treated.

In other exemplary embodiments of this invention, a method of manufacturing 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 (DLC) 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 DLC ​​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 crystalline 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 (DLC). Other layers can also be provided at any suitable location. Such a coated article, in certain example 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 (DLC) and a layer that will phase transform during heat treatment; heating the layer comprising DLC ​​and the layer to be phase transformed to cause combustion of the layer comprising DLC ​​thereby causing the layer comprising DLC ​​to generate heat upon combustion thereof; and using the heat generated by combustion of the layer comprising DLC ​​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.

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.

ES 2 343 335 T3

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

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

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

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

As the layer (s) comprising zirconium nitride are heated to said high temperature due to the combustion of the DLC during HT, at least the layer (s) comprising zirconium nitride are transformed due to the High temperature (s) in a new post-HT layer (s) comprising zirconium oxide. The new post-HT layer (s) comprising zirconium oxide may also include nitrogen in certain example embodiments of this invention (eg, 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-HT 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 example embodiments, the scratch resistance of the post-HT coated article can be even greater than that of DLC without HT.

In certain example embodiments of this invention, the post-HT layer (s) comprising zirconium oxide include a cubic nanocrystalline crystal structure. The entire layer (s) may be of a nanocrystalline cubic crystal structure type, or alternatively only part of the layer (s) may include nanocrystalline cubic crystal structure. Zirconium nitride typically does not grow in the cubic phase, unless at a temperature of at least about 2,000 degrees Celsius. Pre-HT ZrN is not typically found in cubic crystalline form. Since HT is only at a temperature no greater than about 900 degrees C (more preferably no greater than about 800 degrees C), it would be expected that the pre-HT non-cubic zirconium nitride would not grow in cubic phase during HT. However, it has surprisingly been found that the combustion generated by DLC during HT causes at least part of the layer comprising zirconium nitride to heat up sufficiently to cause it to transform into a post-HT layer (s). comprising zirconium oxide including a cubic nanocrystalline crystal structure (with or without nitrogen) that is highly scratch resistant.

Thus, it can be seen that in certain example embodiments of this invention the layer including pre-HT zirconium nitride is transformed during HT into a new post-HT layer comprising zirconium oxide that includes a cubic crystal structure. nanocrystalline, although the temperatures used in the furnace

ES 2 343 335 T3 during HT are considerably less than those normally required to allow cubic growth. It is the combustion of the DLC during HT 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 nanocrystalline crystal structure after HT. .

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

Fig. 1 is a schematic diagram illustrating how a coated article can be manufactured in accordance with an example 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 of or including DLC ​​5, a first layer of or including zirconium nitride 7 (eg, ZrN, or any other suitable stoichiometry), and a top layer of or including DLC ​​9. The glass substrate 1 is typically of or includes sodium-calcium silica glass, although other types of glass can be used in certain cases.

Dielectric layer (s) 3 are provided to prevent diffusion of sodium into the DLC during HT (ie, a barrier to diffusion). This layer (s) 3 also allows thermal imbalance to occur seamlessly between the DLC 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 barrier 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 example embodiments. of this invention. Any of the barrier layer materials 3 mentioned above can be doped (eg 0.5 to 15%) with A1, stainless steel, or any other metal (s) in certain embodiments of this invention. The barrier layer (s) 3 are formed on the glass substrate 1 by sputtering, or by any other suitable technique.

Layers 5 and 9 comprising DLC ​​can be of any suitable type of DLC, including but not limited to any of the types of DLC described in any of US Patent Nos.^s 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.

For purposes of example only, each of the layer (s) 5 and / or 9 including DLC ​​is about 5 to 1,000 angstroms (A) thick in certain example embodiments of this invention, more preferably 10-300 A thick, and even more preferably 45-65 A thick. In certain example embodiments of this invention, the DLC layer (s) 5 and / or 9 may have an average hardness of at least about 10 GPa, more preferably at least about 20 GPa, and even more preferably 20-90 GPa approximately. Said hardness makes layers 5 and 9 resistant to scratching, certain solvents and / or the like. Layer (s) 5 and / or 9, in certain example embodiments, may be of or include a special type of DLC known as highly tetrahedral amorphous carbon (t-aC), and may be hydrogenated (t -aC: H) in certain embodiments. In certain hydrogenated embodiments, the t-aC: H type of DLC 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 DLC 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 example embodiments, at least about 50% of the carbon-carbon bonds in DLC layer (s) 5 and / or 9 may be carbon-carbon (C - - C) bonds of the type sp³, 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 example embodiments of this invention, the DLC 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.

Examples of linear ion beam sources that can be used to deposit layers 5 and 9 that include DLC on substrate 1 include any of those listed in US Pat.^s 6,261,693, 6,002,208, 6,335,086, or 6,303,225 (all incorporated by reference herein). When using an ion beam source to deposit layer (s) 5 and / or 9, a hydrocarbon feedstock gas (e.g. C2H2), HMDSO, or any other suitable gas can be used. used in the ion beam source to cause the source to emit an ion beam towards substrate 1 to form layer (s) 5 and / or 9. It is noted that the hardness and / or density of the layer (s) 5 and / or 9 can be adjusted by varying the ionic energy of the deposition apparatus. In certain example embodiments, at least about 2,000 V (anode to cathode volts) may be used, for example, about 3,000 V,

ES 2 343 335 T3 in the ion source to deposit the layer (s) 5 and / or 9. It is noted that the expression "on the substrate" as used in this document is not limited to being in direct contact with the substrate since other layer (s) can still be provided between them.

Layer 7 including zirconium nitride is provided between DLC layers 5 and 9 in certain example embodiments of this invention. In certain example embodiments, layer 7 including zirconium nitride can be located directly between DLC layers 5 and 9 so that it contacts each other; however in other exemplary embodiments other layer (s) (not shown) may be provided between layer 7 including zirconium nitride and DLC 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 example embodiments of this invention. The 7 pre-HT layer (s) comprising zirconium nitride (and the 7 'discussed below) may include about 10-70% Zr, more preferably about 30-65% Zr, even more preferably about 40-60% 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 example embodiments of this invention, layer 7 including zirconium nitride (and layer 7 'to be discussed below) can have a density of at least 6 g / cm³, more preferably at least 7 g / cm³. Furthermore, in certain example embodiments, the zirconium nitride layer 7 (y 7 ') may have an average hardness of at least 650 kgf / mm, more preferably at least 700 kgf / mm, and / or may have a bond overlap ratio of at least 0.25 (more preferably at least about 0.30) for the purpose of strength. In certain example 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 the purpose of strength. It is also noted that in certain example embodiments of this invention, the ZrN in layer 7 (and 7 ') can have a melting point of at least 2,500 degrees C, and can be about 2,980 degrees C in certain cases. example. In certain example embodiments of this invention, zirconium nitride layer 7 (y 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 example embodiments.

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

Example Coating (Fig. 1) - Layer Thicknesses (Pre-HT)

<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 Á</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>

Once the pre-HT coated article shown on the left side of Fig. 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 Fig. 1, when subjected to HT (for example, in an oven using a temperature (s) of 550 to 800 degrees C, more preferably 580 to 800 degrees C), layer 9 which includes upper or external DLC calcines due to combustion from the high temperatures used during HT. In particular, at least layer 9 of hydrogenated DLC acts as a fuel which after combustion with oxygen from the atmosphere during HT produces carbon dioxide and water. This exothermic reaction, caused by the combustion of hydrogenated carbon from at least layer 9 of DLC, 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 combustion of the DLC 9 can heat part or all of the layer 7 comprising zirconium nitride to a temperature of at least about 1200 degrees C, more preferably at least about 1500 degrees C and even more preferably at least about 2000 degrees C .

Since layer 7 comprising zirconium nitride is heated to said high temperature due to the combustion of DLC during HT, layer 7 comprising zirconium nitride is transformed during HT into a new post-HT layer 11 comprising zirconium oxide. The new post-HT layer 11 comprising zirconium oxide may also include nitrogen (and / or other dopants) in certain example embodiments of this invention (eg, ZrO: N; ZrO₂: N or any other suitable stoichiometry). The new post-HT 11 layer comprising zirconium oxide (optionally with nitrogen) is surprisingly scratch resistant thus providing

ES 2 343 335 T3 is a scratch resistant heat treated coated article. It is noted that the term "zirconium oxide" as used herein includes ZrO₂ and / or any other stoichiometry where the Zr is at least partially oxidized. Herein, any description of layer 11 can also be applied to layer 11 '; Likewise, any description of layer 7 can be applied to layer 7 '.

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

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

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

The final HT (or even non-HT) coated article of Fig. 1 is scratch resistant and can be used in a variety of applications including, but not limited to, IG window units, laminated vehicle windshields, other types of car windows. vehicle, .... applications in furniture, and / or the like.

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

Example Coating (Fig. 1) - Layer Thicknesses (Pre-HT)

<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>DLC (layer 5)</td><td>0-300 Á</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-HT layer 11 that includes Zr is typically thicker than the pre-HT layer 7 that includes Zr. In other words, the thickness of the layer including Zr increases during HT. In certain example embodiments of this invention, the thickness of the Zr-including layer (eg, layer 7 to layer 11) may increase by at least about 5% during or due to HT, more preferably at least about 10%, 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-HT layer 11 (that is, more oxygen migrates towards the post-HT layer 11 than nitrogen leaves, in terms of atomic% and / or size).

While the DLC layer 5 is shown to be present in the post-HT coated article in Fig. 1, it need not be present in the post-HT coated article in alternative embodiments of this invention. If the pre-HT DLC layer 5 reaches a sufficient temperature and / or is exposed to sufficient oxygen during HT, it can undergo combustion which would cause it to decrease in thickness or even disappear due to HT in certain cases. In such cases, the pre-HT layers 5, 7 and / or 9 can be efficiently transformed during the HT into the post-HT layer 11 including zirconium oxide (it is similar to the embodiment of Fig. 5 in this regard).

In certain example 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.

ES 2 343 335 T3

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

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

Figs. 3-5 illustrate another exemplary embodiment of this invention. The pre-HT coated article of this embodiment is the same as that of the embodiment of Fig. 2 described above. Fig. 3 is an XPS chart illustrating the chemical composition of an exemplary pre-HT coated article according to the embodiment of Fig. 5. However, in contrast to the embodiment illustrated in Fig. 2, in the embodiment of Fig. 5 during HT all DLC layers burn out 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 pre-HT zirconium nitride layers to phase during HT forming at least one post-HT layer 11 comprising zirconium oxide (which may or may not be doped with N). In the embodiment of Fig. 5, the pre-HT layers 5, 7 ', 5', 7 and 9 are bonded or finally result in a fairly thick post-HT layer 11 comprising zirconium oxide. Fig. 4 is an XPS chart illustrating the chemical composition of an exemplary post-HT coated article according to the embodiment of Fig. 5.

In the embodiment of Figs. 3-5, it can be seen from Fig. 4 that residual carbon remains in the zirconium oxide layer 11 after HT due to the presence of the DLC pre-HT 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% of C.

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

When layer 5 melts into glass 1 during HT, the result is a transitional interface layer close to the substrate surface comprising silicon oxycarbide. In certain embodiments of this invention, the DLC 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 HT, to reduce the likelihood of damaging the layer that includes Zr.

In certain other cases, the DLC layer 5 may contract even though it does not completely disappear during HT in certain example embodiments of this invention.

In the embodiment of Fig. 6, the DLC layer 5 can be about 20 to 60 A thick, more preferably 28 to 34 A thick, or it can be any other suitable thickness; Layer 7 including ZrN can 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 can be any other suitable thickness; and the DLC 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 houses. In certain cases, if the thickness of the lower DLC layer 5 is outside the range of 28 to 34 A, an undesirable haze can increase rapidly, especially on the underside.

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

Each of the aforementioned embodiments provides a heat treatable coated article that is highly resistant to scratching after HT. For example, post-HT coated articles according to certain embodiments of this invention can have a critical scratch load using an alumina sphere of at least about 15 pounds, more preferably at least 18 pounds, even more preferably at least 20 pounds, even more preferably at least 22.5 pounds, and still more preferably at least 30 pounds. Furthermore, articles coated according to certain example embodiments of this invention are UV stable, and do not degrade significantly upon UV exposure. In certain example embodiments, the coated articles described herein may have a post-HT 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 example embodiments, good optics is provided in that post-HT yellow staining is not present although yellowish DLC may be present at least in the pre-HT 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 example embodiments of this invention. According to certain example embodiments of this invention, post-HT coated articles have a transmissive value a * from -5 to +2, more preferably from -4 to 0, and still more preferably from -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 example embodiments of this invention appear visually very similar to clear uncoated glass, even though the many layers for durability purposes are provided therein.

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

Any type of suitable glass substrate 1 can be used in different embodiments of this invention. For example, various types of sodium calcium silica glass or borosilicate glass can be used for the substrate.

1. However, in certain example embodiments of this invention, the coating of any of the aforementioned embodiments can be supported by a special type of glass substrate having a very high visible transmission and a very transparent color. In particular, in such certain exemplary embodiments of this invention, the glass substrate 1 can be any of the glasses described in WO2005 / 033030 belonging to the same holder. 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% (for example, 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 HT product is caused to have a visual appearance similar to uncoated clear glass - even though the coating is provided on it. In addition to the base glass, examples of the final glass and / or glass batch (in terms of percent by weight of the total glass composition, unless otherwise shown as ppm) are shown below:

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Sample Dyes and Oxidizing Cerium on Glass Substrate

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

<td>total iron</td><td> 0,01 - 0,20 %</td><td> 0,01 -0,15 %</td><td> 0,02-0,12 %</td><td>0.03 to 0.10%</td>

<td>(Faith₂OR₃): oxide</td><td>0 to 15 ppm</td><td>0.1 to 10 ppm</td><td>0.5 to 5 ppm</td><td>0.5 to 3 ppm</td>

<td>cobalt: 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 to 0.5%</td><td>0 to 0.2%</td><td>0.001 to 0.05%</td><td>0.01 to 0.02%</td>

<td>chromium oxide:</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>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) may be added to the coated articles discussed above, and / or certain layer (s) may be removed.

Example 1

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

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

Fig. 3 is an XPS chart illustrating the pre-HT chemical composition of the coated article according to this Example. As can be seen in Fig. 3, the carbon (C) peaks indicate the 5 and 5 'DLC layers, while the Zr peaks indicate the 7 and 7' ZrN layers. C content is seen to increase at the left edge of the graph in Fig. 3 showing the thin sacrificial layer 9 of DLC in the outermost layer of the preHT 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 silicon nitride barrier layer 3.

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

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

Example 2

Example 2 was prepared according to the embodiment of Fig. 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 Fig. 6. DLC layer 5 was 34 A thick, ZrN layer 7 was 160 A thick, and DLC layer 9 was 100 A thick. The two DLC layers were formed by ion beam 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 the substrate 1 and the zirconium oxide layer 11 which included some nitrogen as shown on the right hand side of Fig. 6.

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After HT, 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 (CSL) of 31 pounds, and a haze value of 1. 6.

Example 3

Example 3 was prepared according to the embodiment of Fig. 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 Fig. 7, ZrN layer 7 was 160 A thick, and DLC 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 the substrate 1 and the zirconium oxide layer 11 which included some nitrogen as shown on the right hand side of Fig. 7.

After HT, based on three different samples from this example, the coated article of this example had an average visible transmission of about 81.35%, a critical scratch load (CSL) of 10.8 pounds, and a haze value of 0.44.

In certain non-limiting exemplary embodiments of this invention, post-HT 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, post-HT 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. .

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

More exemplary embodiments may have the following structures: