Articles including anticondensation and/or low-e coatings and/or methods of making the same

SUMMARY OF EXEMPLARY EMBODIMENTS

It is known that moisture condenses on skylights, refrigerator / freezer doors, vehicle windows, and other glass products. Increasing the condensation on skylights deteriorates the aesthetics of the glazing. Similarly, the accumulation of condensation on the door of a fridge / freezer in supermarkets or similar sometimes makes it difficult for buyers to quickly and easily find the products they are looking for. And increasing the condensation in vehicles is often annoying in the morning, because the driver must sometimes scrape the frost or ice and / or start defrosting the vehicle and / or wipers to be able to drive safely. Moisture and fog on the windshield often also cause nervousness, although they can also potentially pose a greater safety risk when the driver travels through hill areas where sudden temperature drops occur, etc.

Over the years, various anti-condensation products have been developed to solve these and / or other problems in many applications. See, e.g., U.S. Patent Nos. 6,818,309; 6,606,833; 6,144,017; 6,052,965; 4,910,088. As mentioned above, some approaches use active heating elements to reduce condensation build-up, for example, as in vehicle de-icers, actively heated fridge / freezer doors, etc. These active solutions, unfortunately, need time to work in the context of vehicles and thus solve the problem when it occurs appear. In the case of refrigerator / freezer doors, such active solutions can be expensive and / or energy ineffective.

Some approaches include a thin film anti-condensation coating on the window. These tests generally involve the pyrolytic deposition of a fluorine-doped tin oxide coating (FTO) with a thickness of 4,000-6,000 angstroms on the outer surface (e.g., surface 1) of a window such as, for example, a skylight. Although pyrolytic deposition techniques are known to provide "hard coatings," unfortunately the FTO is quite easy to shape, changes color over time, and has other disadvantages.

Thus, it will be appreciated that there is a need in the art for articles comprising improved thin film, anti-condensation and / or low E coatings, and methods for making them.

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One aspect of some embodiments relates to anti-condensation and / or low-E coatings that are suitable for exposure to the external environment, and / or methods for their production. The external environment may in some cases mean the exterior and / or interior of the vehicle or house (as opposed to, for example, a more protected area between neighboring substrates).

Another aspect of some embodiments relates to anti-condensation and / or low E coatings that have low sheet resistance and low hemispheric emissivity so that the glass surface is more likely to retain heat from the interior area, thereby reducing (and sometimes even eliminating completely). presence of condensation on it.

Yet another aspect of some embodiments relates to coated articles having a depressurization and / or low E coating formed on the outer surface and one or more low E coatings formed on one or more of the respective interior surfaces of the article. In certain embodiments, the anti-condensation coating may be thermally tempered (e.g., at a temperature of at least 580 degrees C for at least about 2 minutes, more preferably at least about 5 minutes) or annealed (e.g., at a temperature lower than that required for quenching) ).

The products of some embodiments may be, for example, skylights, windows or vehicle windows, IG units, VIG units, refrigerator / freezer doors, and / or the like.

Some examples relate to a coated article comprising: a coating supported by a substrate, wherein the coating is a deposition coating comprising the following layers arranged in a direction from the first substrate: a layer comprising silicon nitride and / or silicon oxides, a layer comprising transparent conductive oxide (TCO), a layer comprising silicon nitride , and a layer comprising one or more of zirconium oxide, zirconium nitride, aluminum oxide, and aluminum nitride, wherein the anti-condensation coating is on the outer surface of the substrate, so that the anticonductor coating is exposed to the external environment, and the anti-condensation coating has a hemispherical emissivity lower than 0.23. and sheet resistance less than 30 ohms / square.

Some examples relate to a coated article comprising a coating supported by a substrate. The coating is a deposition coating comprising the following thin film layers arranged in the following order from the first substrate: a silicon barrier layer, a first silicon-containing contact layer, a transparent conductive oxide (TCO) layer, a second silicon-containing contact layer, and a zirconium oxide layer. The anti-condensation coating is located on the outer surface of the substrate so that the anti-condensation coating is exposed to the external environment. The anti-condensation coating has a hemispherical emissivity of less than 0.23 and a sheet resistance of less than 30 ohms / square.

According to certain embodiments, the external environment is the interior of a home or a vehicle. According to some embodiments, the external environment is an external environment. According to some embodiments, the low E coating is on a substrate opposite the anti-condensation coating.

In certain embodiments, the coated article may be incorporated into a skylight, a window, a IG unit, a vacuum glazing unit (VIG), a fridge / freezer door, and / or a window or vehicle glass. The anti-condensation coating can be, for example, on the surface one and / or the surface of four IG or VIG units.

In certain embodiments, a method for manufacturing a glazing unit (IGU) is provided. The first glass substrate is provided. A plurality of layers are applied, directly or indirectly, on the first major surface of the first glass substrate, the plural layers comprising, first of all, the first glass substrate: a first layer comprising silicon oxides having refractive index 1.5-2.1, an ITO containing layer having a refractive index

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1.7-2.1, and a second layer containing silicon oxides having a refractive index of 1.5-2.1. The first glass substrate is thermally treated with many layers on itself. The second glass substrate is substantially parallel, spaced apart from the first glass substrate such that the first major surface of the first glass substrate is away from the second glass substrate. The first and second glass substrates are sealed together.

According to some embodiments, the first and second layers comprising silicon oxides have refractive indexes 1.7-1.8 and / or the ITO inclusive layer has a refractive index of 1.8-1.93.

According to certain embodiments, said thermal treatments include laser annealing, exposure to NIR-SWIR radiation, and / or heating in an oven.

In certain embodiments, a method for manufacturing a glazing unit (IGU) is provided. The first glass substrate is provided. A plurality of layers are applied, directly or indirectly, on the first major surface of the first glass substrate, the plurality of layers successively from the first glass substrate: a first layer comprising silicon oxides, an ITO containing layer, and a second layer comprising silicon oxynitrides. The first glass substrate is thermally treated with many layers on itself. The second glass substrate is substantially parallel, spaced apart from the first glass substrate such that the first major surface of the first glass substrate is away from the second glass substrate.

In certain embodiments, a glazing unit (IGU) is provided. IGU contains the first glass substrate. The plurality of layers are sputtered, directly or indirectly, onto the first major surface of the first glass substrate, the plural layers comprising sequentially from the first glass substrate: a first layer comprising silicon oxides having refractive index 1.5-2.1, an ITO containing layer having a refractive index of 1.7-2.1, and a second layer containing silicon oxides having a refractive index of 1.5-2.1. The second glass substrate is substantially parallel, spaced apart from the first glass substrate, with the first major surface of the first glass substrate facing away from the second glass substrate at assembly. The edge seal seals together the first and second glass substrates. The first glass substrate is thermally treated with many layers on itself. The first substrate with multiple layers on the first major surface of the first glass substrate has a hemispherical emissivity of less than or equal to about 0.20 and a sheet resistance less than or equal to about 20 ohms / square after said heat treatment.

The features, aspects, advantages, and embodiments described herein may be combined to implement still further embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features and advantages can be better and more fully understood by referring to the following detailed description of illustrative embodiments in conjunction with drawings in which:

FIGURE 1 is an exemplary coated article comprising an anti-condensation coating;

FIGURE 2 is an exemplary unit of an IG unit comprising an anti-condensation coating placed on the outermost surface exposed to the outside atmosphere;

FIGURE 3 is an example unit of a glazing unit comprising an anti-condensation coating placed on the innermost surface exposed to the internal environment;

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FIGURE 4 is an exemplary unit of an IG unit comprising anti-condensation coatings disposed on the outermost and innermost surface of an IG unit;

FIGURE 5 is a graph illustrating the operation of an embodiment, the current anti-condensation product, and a naked glass substrate at a change in temperature, humidity, and dew point over a period of 18 hours;

FIGURE 6 is an exemplary coated article comprising a countercondensation coating;

FIGURE 7 is a coated article comprising an anti-condensation coating in accordance with an embodiment; and

FIGURE 8 is a schematic view of a system comprising an IR heater in accordance with certain embodiments.

DETAILED DESCRIPTION OF EMBODIMENTS OF AN INVENTION

Referring now more specifically to the attached drawings, on which similar numerals indicate similar parts on several views.

Certain embodiments of the present invention relate to thin film anti-condensation coatings that are exposed to the environment. Such coatings have low hemispherical emissivity in certain embodiments, which aids the glass surface to keep the heat supplied from the inside. For example, in a skylight and / or other exemplary applications in building windows, the glass surface retains more heat from inside the buildings. In vehicle applications, the windshield retains more heat from inside the vehicle. This helps to reduce (and sometimes even prevent) the initial formation of condensation. As indicated above, such anti-condensation coatings may be on the surface (or many surfaces) exposed to the environment in some cases. As such,

Fig. 1 is a coated article comprising an exemplary anti-condensation coating. The example of Fig. 1 includes a glass substrate 1 supporting a multi-layer thin film anti-condensation coating 3. The anti-condensation coating 3 has low hemispheric emissivity. In certain examples, the hemispherical emissivity is less than 0.25, more preferably less than 0.23, further more preferably less than 0.2, and sometimes even less than 1.0-1.5. This is achieved by providing a thin layer of transparent conductive oxide (TCO) such that a sufficiently low sheet resistance is obtained. In the example of Fig. 1, TCO 5 is indium tin oxide (ITO). A sheet resistance of 10-30 ohms / square will generally be sufficient to obtain the desired hemispherical emissivity values. Some examples described herein provide a sheet resistance of 1327 ohms / square, with the example provided below for sheet resistance of 17 ohms / square. In some examples, it is possible to select TCO 5 so that the sheet resistance drops down to about 5 ohms / square, although this low value is not needed in all examples. Fig. 6 illustrates a coated article comprising similar layers, but in Fig. 6 layers 11 and 13 are absent. In Fig. 6, the layer comprising silicon oxides 9b can be both a silicon-containing barrier layer and a lower contact layer, and be made from a combination of layers 9b and 11 of Fig. 1. In Fig. 1 and Fig. 6, the top layer 7 can be with or include zirconium oxide, aluminum oxide, aluminum nitride, and / or aluminum oxazides in certain example embodiments of this invention. Layers 9a,

Referring to Figures 1 and 6, TCO 5 is protected from the environment by the zirconia layer 7. A barrier layer containing silicon 11 may be between TCO 5 and a substrate.

-5EP 2 539 291 also for the protection of TCO 5, e.g., by sodium migration. In the example of Fig. 1, the barrier layer comprising silicon 11 is silicon nitride, and the silicon nitride barrier layer 11 is next to the titanium oxide layer 13. The silicon nitride barrier layer 11 and the titanium oxide layer 13 assist the optics of the entire article. It will be appreciated that the low / high / low layer system can also be used to improve the optics of the final product in certain examples. In certain examples, the silicon nitride barrier layer 11 may be oxidized, e.g., such that it is a silicon oxynitride layer. In other words, layer 11 may be of or include silicon oxynitrides, for example. In certain instances, a barrier layer comprising silicon nitride (e.g.

Additional silicon-containing layers 9a and 9b may sandwich TCO 5. As shown in the example of Fig. 1, the upper layer comprising silicon 9a is a silicon nitride layer, while the lower layer comprising silicon 9b is a silicon oxynitride layer. It will be appreciated that any suitable combination of silicon with oxygen and / or nitrogen may be used.

The table below provides exemplary physical thicknesses and thickness ranges for the example of Fig.

1:

<td></td><td>Sample thickness range (nm)</td><td>Sample thicknesses (nm)</td>

<td>ZrOx (7)</td><td>2-15</td><td>7</td>

<td>SiNx (9a)</td><td>10-50</td><td>thirty</td>

<td>ITO (5)</td><td>75-175</td><td>130</td>

<td>SiOxNy (9b)</td><td>10-50</td><td>35</td>

<td>TiOx (13)</td><td>2-10</td><td>3.5</td>

<td>SiNx (11)</td><td>10-20</td><td>13</td>

The thicknesses for layers 9b, 5, 9a and 7 for the example of Fig. 6 are similar and the above table also applies to these layers. However, in Fig. 6, the layer based on silicon nitride and / or silicon oxynitride 9b may be a pear, e.g., from about 10-200 nm, more preferably from about 10-100 nm. As indicated above, other TCOs may be used instead of, or in addition to, ITOs. For example, some examples may include the ITO / Ag / ITO sandwich system. Some examples may include zinc oxide, aluminum zinc oxide (AZO), p-type aluminum oxide, doped or undoped Ag, FTO, and / or the like. When Ag is included in the layer system as TCO, layers containing Ni and / or Cr may be located directly at (contact with) Ag. In certain examples, each layer in the stack of layers may be sputter-deposited. In some examples, one or more layers can be deposited using various techniques. For example, when the FTO is incorporated as TCO 5, it can be pyrolytically deposited (e.g., using combustion deposition or CVD).

In certain examples, a diamond-like carbon (DLC) layer may be directly above and contact with zirconium oxide. This may help to create a more durable, hydrophilic-like coating in certain examples. Hydrophilic coatings generally have a contact angle lower than or equal to 10 degrees. The zirconium oxide deposited by sputtering usually has a contact angle of less than about 20 degrees. However, the formation of DLC on top of DLC on top of zirconium oxide promotes wettability and creates a harder layer. In hardening, for example, the zirconium oxide / DLC stack has a contact angle of less than or equal to about 15 degrees. Thus, a durable hydrophilic-like coating can be obtained. It is noted that this layer can be formed by providing a zirconium nitride layer, and then a DLC layer, which, after hardening, will give a layer

-6EP 2 539 291 zirconium oxide and a DLC layer. See, for example, application No. 12 / 320,664 which describes a thermally treated coated article comprising DLC ​​and / or zirconium in its coating.

Additionally or alternatively, a thin hydrophilic / or photocatalytic coating may be above the zirconia. Such a layer may contain TiO2, BiO, BiZr, BiSn, SnO anatase and / or any other suitable material. Such a layer may also aid wettability and / or provide self-cleaning properties of the article.

In certain examples, the zirconium oxide protective layer 7 may be replaced with aluminum oxide and / or aluminum oxazide. Additionally, in certain instances, the layer 7 may be initially deposited in a multilayer form so as to comprise a first layer with or comprising zirconium nitride directly on the layer comprising silicon nitride 9a, and a second layer with or containing diamond-like carbon (DLC). Then, when a thermal treatment is desired (e.g., thermal toughening comprising a temperature (y) of at least about 580 degrees C), the coated article is thermally treated and the above-containing DLC ​​inclusive layer is fired during thermal treatment and the layer comprises zirconium nitride transformed into zirconium oxide thereby resulting in a thermally treated coated article having a stack of thermally treated layers,

Although not shown in the examples of Fig. 1 or Fig. 6, a silver-low low E coating may be on a glass substrate opposite the anti-condensation coating 3. For example, the low silver-based coating E may be any of the low E coatings described with applications No. 12 / 385,234; 12 / 385.802; 12 / 461.792; 12 / 591.611; and 12 / 654,594. Of course, other low E coatings commercially available from the subject of the present invention and / or other low E coatings may also be used in connection with various embodiments of the present invention. When the coated article is hardened, it can be passed through a "face down" hardening furnace. In other words, when the coated article is hardened, the anti-condensation coating may lie on the rolls.

In some embodiments, the transmission of visible light may be high when a counter-condensation coating is used. For example, in certain embodiments, the transmission of visible light is preferably at least about 50%, more preferably at least about 60%, even more preferably at least about 65%. In certain embodiments, the transmission of visible light may be 70%, 80%, or even more.

The coated article shown in Fig. 1 or Fig. 6 can be incorporated into a glazing unit (IG). For example, Fig. 2 is a unit of a glazing unit comprising an anti-condensation coating placed on the outermost surface exposed to the outside atmosphere. The IG unit in the example of Fig. 2 includes first and second substantially parallel and spaced apart glass substrates 1 and 21. These substrates define the space or gap 22 between them. The first and second glass substrates 1 and 21 are sealed using edge seal 23, and a plurality of posts help to maintain the distance between the first and second substrates 1 and 21. The first substrate 1 supports the anti-condensation coating 3. As will be appreciated from the example of Fig. 2, the anti-condensation coating 3 is exposed to the external environment. It is a departure from common practice, where low E coatings are generally protected from the outside environment. The arrangement of Fig. 2 is possible due to the strength of the anti-condensation coating 3.

Although not shown in Fig. 2, as described above, a low E coating (e.g., a silver E low coating) may be on the inner surface of one of the first and second substrates 1 and 21. In other words, although not shown in Fig. 2, the low E coating may be on surface 2 or surface 3 of the IG unit shown in Fig. 2.

When the example of Fig. 2 is provided from a skylight connection, for example, the outer substrate 1 may be hardened and the inner substrate 21 may be laminated, e.g. for safety reasons. This may be true for other IG unit products as well, depending on

-7EP 2 539 291 of the desired application. In addition, it will be appreciated that the structure of the IG unit shown in the example of Fig. 2 can be used in combination with generally vertical and generally horizontal applications. In other words, the structure of the IG unit shown in the example of Fig. 2 can be used in fridge / freezer doors that are generally vertical or generally horizontal.

In some examples, the space or gap 22 between the first and second substrates 1 and 21 can be emptied and / or filled with an inert gas (such as argon, for example), and the edge seal 23 can be a hermetic seal, e.g. when forming a vacuum glazing unit ( VIG).

Fig. 2 shows an IG unit having two glass substrates. However, the exemplary anti-condensation coatings described herein can be used in connection with products that include first, second, and third substantially parallel and spaced apart glass substrates (sometimes also referred to as "three-bit" products). The anti-condensation coating may be on surface 1 (the outermost surface exposed to the environment), and low E coatings may be on one or more inner surfaces (surfaces other than surface 1 and surface 6). For example, the anti-condensation coating may be on surface 1, and low E coatings may be on surfaces 2 and 5, 3 and 5, etc., in various embodiments of the invention.

As indicated above, some embodiments may be used in connection with automotive windscreens, windows, mirrors, and / or the like. The hemispherical emissivity of the external glass surfaces of the vehicle is typically greater than approximately .84. however, by reducing the hemispheric emissivity to the above-identified (and / or other) ranges, the glass surface can retain more heat provided by the interior of the vehicle. This in turn may result in the reduction or elimination of condensation formation on the surface through which the vehicle passes from a cooler to a warmer climate (e.g., hilly areas), reduction or elimination of condensation and / or frost formation on the surface through which the light passes when parking and leaving for the night, etc.

The zirconium oxide top coating is advantageous for vehicle windows because it has a comparatively low coefficient of friction. More specifically, this lower coefficient of friction facilitates window movement up and down.

Certain embodiments may be used in connection with any suitable vehicle including, for example, cars; trucks; trains; boats; ships and other units; aircraft; tractors and other work equipment; etc. In vehicle mirrors, the coating optics can be set so that there is no "double reflection".

The present inventors have also realized that the anti-condensation coating of some examples may also help to meet the so-called "standard .30 / .30." Briefly, the .30 / .30 standard refers to a U value less than or equal to 0.30 and a solar heat gain coefficient (SHGC) less than or equal to 0.30. Current legislation in the US will provide tax relief for investing in windows, skylights, doors, etc. that meet these criteria.

Fig. 3 is an exemplary unit of an IG unit comprising a countercondensation coating (e.g., see the coating of Fig. 1 and / or Fig. 6) placed on the innermost surface exposed to the internal environment. The example of Fig. 3 is similar to the example of Fig. 2, except that the example of Fig. 3 has a counter-condensation coating 3 lying on the surface 4, which is the outer surface of the inner glass substrate 1 exposed to the interior of the building rather than the external environment. .

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In some examples, the internal substrate 1 can be annealed (rather than tempered). The anti-condensation coating may remain the same or substantially the same as between the examples of Fig. 2 and Fig. 3, although the modifications described above with reference to Figs. 1, 2 and / or 6 may also be made in connection with the example of Fig. 3. One the change that can be made is to increase the ITO thickness to achieve the desired U-value. In those cases where the thickness of the ITO is increased, the thickness of the other layers can also be adjusted so that the desired optical properties are obtained. Additional layers may also be added to obtain the desired optical properties. Other structural elements remain the same as between Figures 2 and 3, and similar modifications can be made therein.

When the anti-condensation coating 3 is on the surface 4 as shown in Fig. 3, as determined, the U-value is 0.29. When an additional coating with a low E is on the surface of the 2 IG unit, it has been detected that the U value drops to 0.23. Some examples may also provide SHGCs less than or equal to 0.30, thus helping to meet the .30 / .30 standard.

In products with low U-values ​​(e.g., IG units or VIGs with surface condensation coating 4, bi-metal or VIG, three or three-ton VIG units, etc.), condensation can become a problem, e.g. when the glass is not heated because of low-temperature coatings emissivity. One solution to this problem is shown in Fig. 4, which shows an exemplary unit of an IG unit comprising anti-condensation coatings lying on the outermost and innermost surface of an IGU unit. In the example of Fig. 4, there are first and second substrates 1a and 1b. The first and second anti-condensation coatings 3a and 3b are on the surfaces 1 and 4, respectively. In some examples, additional low E coatings may also be on one or both of the inner surfaces (surfaces 2 and / or 3).

Fig. 5 is a graph illustrating the operation of an embodiment, the present anti-condensation product, and a naked glass substrate at a change in temperature, humidity, and dew point over a period of 18 hours. The images of Fig. 5 have a "checkered" pattern printed on it to help show the presence or absence of condensation. As can be seen in Fig. 5, there is no condensation formed on those samples that were made in accordance with the embodiment. Conversely, a comparative example that contains a pyrolytically deposited FTO shows some of the condensation formed in the first observed period, with a condensation level significantly increasing in the second and third observed period, and slightly falling over the fourth observed period. In fact, the "cross" pattern it is significantly blurred in the second period observed and barely visible in the third. The uncoated glass sample shows significant condensation in all observed periods. The "cross" pattern in the second and third observed period is not visible. The example of Fig. 5 thus shows that the examples described herein provide a higher performance compared to the current comparative and uncoated glass examples.

Fig. 7 is a coated article comprising a countercondensation coating in accordance with an embodiment. The stack of layers of the example of Fig. 7 is similar to the previously described stacks of layers in that it comprises a TCO layer sandwiched by the first and second layers comprising silicon 9a and 9b. In the embodiment of Fig. 7, the first and second layers comprising silicon 9a and 9b comprise silicon oxynitride. The first and second layers containing silicon oxides of the silicon 9a and 9b sandwich the TCO5 layer containing ITO. Examples of thicknesses and refractive indices for each layer can be found in the table below:

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<td></td><td>Sample thickness range (Nm)</td><td>Example thickness (nm)</td><td>Exemplary range factor refraction</td><td>Preferred range factor refraction</td><td>Exemplary coefficient refraction</td>

<td>SiOxNx</td><td>30-100</td><td>60</td><td>1.5-2.1</td><td>1.7-1.8</td><td>1.75</td>

<td>ITO</td><td>95-160</td><td>105</td><td>1.7-2.1</td><td>1.8-1.93</td><td>1.88</td>

<td>SiOxNy</td><td>30-100</td><td>65</td><td>1.5-2.1</td><td>1.7-1.8</td><td>1.75</td>

<td>Glass</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>

Other variants of this stack of layers are possible in various embodiments of the present invention. Such variants may include, for example, adding a protective overcoat comprising ZrOx, adding one or more layers to match the ratio (e.g., containing TiOx) between the glass substrate and the second layer comprising silicon, etc. For example, some embodiments may include modifying the stack of layers from the example of Fig. 7 to add a layer comprising ZrOx (e.g., for potential increase in strength), etc. Thus, it will be appreciated that the possible modifications mentioned herein can be used in any combination or subcombination.

It is also possible to make modifications to meet the so-called "window R5" rating (total U value of the window &lt;0.225) with low emissivity (e.g., &lt;0.20). To meet such standards, the thickness of the TCO layer can be increased. The proposed ITO thickness increases and measures of operation are presented in the table below. It will be appreciated that the silicon-containing layers may also be adjusted to maintain an acceptable optics, and / or that dielectric layers such as titanium oxide-containing layers may be added. It is noted that the glass substrates are 3 mm clear glass substrates that the low E coating is on the surface 2, and that the V3 'gap filled with about 90% Ar and 10% air is found in the IGU embodiments.

<td></td><td colspan="2">monolithic</td><td colspan="2">IGU</td><td colspan="3"></td>

<td># 4 Emissivity</td><td>Tvis</td><td>Rvis</td><td>Tvis</td><td>Rvis, in</td><td>The value of U COG</td><td>Thickness of ITO</td><td>% improvement U values</td>

<td>0.84 (no shell)</td><td>on</td><td>on</td><td>69.3</td><td>12.6</td><td>0.247</td><td>0</td><td>on</td>

<td>0.20</td><td>87.5</td><td>8.5</td><td>67.4</td><td>12.4</td><td>0.205</td><td>130</td><td>17.0%</td>

<td>0.15</td><td>86.2</td><td>8.5</td><td>66.4</td><td>12.4</td><td>0.200</td><td>195</td><td>19.0%</td>

<td>0.10</td><td>85.0</td><td>8.5</td><td>65.5</td><td>12.4</td><td>0.194</td><td>260</td><td>21.5%</td>

<td>0.05</td><td>80.0</td><td>8.5</td><td>61.6</td><td>12.0</td><td>0.188</td><td>520</td><td>23.9%</td>

The embodiment of Fig. 7 is preferably very robust, e.g., after heat treatment, even if it does not include a top layer comprising ZrOx. It was therefore found that it is suitable for use as a so-called surface coating 4. As is known, the fourth IGU surface, for example, is the surface furthest from the sun (and thus typically facing the interior of the building). Thus, the stack of layers of Fig. 7 is particularly well suited for use in an assembly similar to that shown in Fig. 3. It will also be appreciated that the embodiment of Fig. 7 is suitable for use in conjunction with other glazings where it is located. the most internal surface facing the interior of the building (e.g., on the surface of the 6 three-pane IGU, etc.).

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As mentioned above, the stack of layers of Fig. 7 is thermally treated in certain embodiments. This thermal treatment can be achieved by using an infrared (IR) heater, a box or other furnace, a laser annealing process, etc. Further details of the thermal treatment example are given below. The two tables below include performance data for IR heat treatment of the monolithic stack of layers of Fig. 7 and heat treatment on a strip furnace (e.g., at 650 degrees C), respectively.

Activity data (IR treatment) of monolithic annealed

<td>Glass thickness (mm)</td><td>2.8 mm</td>

<td></td><td></td>

<td>T</td><td>88.49</td>

<td>a *, Transmission</td><td>-0.56</td>

<td>b *, Transmission</td><td>0.22</td>

<td>L *, Transmission</td><td>95.36</td>

<td>rg</td><td>9.11</td>

<td>a *, Glass side</td><td>-0.4</td>

<td>b *, Glass side</td><td>-1.13</td>

<td>L *, Glass side</td><td>36.20</td>

<td>rf</td><td>9.10</td>

<td>a *, Movie page</td><td>-0.72</td>

<td>b *, Movie page</td><td>-1.13</td>

<td>L *, Movie page</td><td>36.17</td>

<td>Rendered color rendering ratio (CRI)</td><td>97.91</td>

<td>T-Mist</td><td>0.12</td>

<td>Surface roughness</td><td>1.8</td>

<td></td><td></td>

<td>Sheet resistance</td><td>17-19</td>

<td>Hemispheric emissance</td><td>0.20 or 0.21</td>

Activity data (belt kiln 650) monolithic tempered

<td>T</td><td>88.10</td>

<td>ΔE (Annealed to Hardened)</td><td>0.37</td>

<td>a *, Transmission</td><td>-0.60</td>

<td>b *, Transmission</td><td>0.54</td>

<td>L *, Transmission</td><td>95.20</td>

<td>rg</td><td>9.08</td>

<td>ΔE (Annealed to hardened)</td><td>1.04</td>

<td>a *, Glass side</td><td>-0.26</td>

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<td>b *, Glass side</td><td>-2.16</td>

<td>L *, Glass side</td><td>36.14</td>

<td>rf</td><td>9.06</td>

<td>ΔΕ (Annealed to hardened)</td><td>1.16</td>

<td>a *, Movie page</td><td>-0.69</td>

<td>b *, Movie page</td><td>-2.28</td>

<td>L *, Movie page</td><td>36.10</td>

<td>Rendered color rendering ratio (CRI)</td><td>97.91</td>

<td>T-Mist</td><td>0.12</td>

<td></td><td></td>

<td>Surface roughness</td><td>1.8</td>

<td></td><td></td>

<td>Sheet resistance (NAGY)</td><td>17-19</td>

<td>Hemispheric emissance</td><td>0.19 or 0.20</td>

As indicated above, the embodiment of Fig. 7 can be heat treated using, for example, an infrared heater (IR), box furnace or other, laser annealing process etc. The post-deposition heat treatment step can be beneficial to assist in recrystallization of the ITO layer and support for obtaining the desired emissivity and optics (e.g., including those described above). In this exemplary process, the glass can be heated to about 400 degrees C to help achieve these goals. In certain embodiments, the temperature of the glass will not exceed 470 degrees C to help reduce the likelihood of permanent (or at least timeless) changes in stress introduced into the glass.

Certain embodiments may use a laser diode array in combination with a laser annealing process. It has been found that a laser diode system with the following parameters advantageously helps reduce the sheet resistance to about 20 ohms / square (from, for example, about 65 ohms / square in the state as embedded), helps to achieve a substantially uniform appearance of the coating, and helps to meet the aforementioned measures :

• Laser power - 1 kW • Emission wavelength - 975 nm • Scanning speed - 75 mm / sec.

• Dot size - nominally 12.5 mm x 2 mm

A multi-zone oven can also be used for heat treatment in certain embodiments. Zone temperature, line speed, temperature deviation (e.g., up / down), suction, trim of the element (e.g., in the furnace), cooling air settings (e.g., pressure and flow deviations), and / or other factors can be set to help in obtaining the desired features of action. In certain embodiments, a 10-zone furnace may be used to achieve thermal treatment. A partial subset of zones may assist the ITO recrystallization process, while other zones may assist in slowly cooling the substrate before it exits the furnace. In one example where a 10-zone furnace was used, zones 1-3 as detected were active in the ITO recrystallization process, heating the coating to a temperature close to 400 degrees C, while the rest of the furnace helped in slowly cooling the glass before leaving the cooling air section. Will be appreciated that

In certain instances, it will be desirable to maintain a low starting temperature to assist in reducing the likelihood of rupture. In fact, the glass is very sensitive to thermally cracking in the temperature range of the re-annealing process, especially at temperatures above 200 degrees C.

Further parameters affecting thermal cracking include temperature differences through the thickness of the glass, as well as differences on its surface. The first one has been found to have a large impact on thermal cracking with respect to coated substrates. The temperatures of the bottom and top surfaces of the uncoated glass leaving the oven were almost identical, and the vast majority of transparent glass withstood the annealing process after the initial profile was set (linear velocity, zone temperature, cooling air, no deflection). However, the upper surface of the coated product was measured at 139 degrees C (250 degrees F) higher at the exit of the oven. This is because the heat is lost faster by conductively transferring to the rollers than by radially transferring from the coated upper surface.

However, by identifying and understanding this differential and deflected heating and cooling, it is possible to reduce this difference and, in turn, help reduce the likelihood of rupture. Exemplary furnace profiles for 3.2 mm and 2.3 mm glass are given in the tables below, respectively.

3.2 mm oven profile

<td colspan="2"></td><td colspan="10">Zone</td>

<td>Bake</td><td>Temp. in ° C (Temp in ° F)</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td>

<td>top</td><td>setup</td><td>771</td><td>771</td><td>771</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td></td><td></td><td>(1420)</td><td>(1420)</td><td>(1420)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>The actual</td><td>772</td><td>772</td><td>773</td><td>503</td><td>396</td><td>367</td><td>296</td><td>288</td><td>307</td><td>305</td>

<td></td><td></td><td>(1422)</td><td>(1442)</td><td>(1423)</td><td>(937)</td><td>(745)</td><td>(693)</td><td>(565)</td><td>(551)</td><td>(585)</td><td>(581)</td>

<td>bottom</td><td>setup</td><td>771</td><td>771</td><td>771</td><td>0</td><td>371</td><td>371</td><td>371</td><td>371</td><td>371</td><td>371</td>

<td></td><td></td><td>(1420)</td><td>(1420)</td><td>(1420)</td><td></td><td>(700)</td><td>(700)</td><td>(700)</td><td>(700)</td><td>(700)</td><td>(700)</td>

<td></td><td>The actual</td><td>782</td><td>781</td><td>777</td><td>441</td><td>416</td><td>395</td><td>388</td><td>243</td><td>366</td><td>374</td>

<td></td><td></td><td>(1440)</td><td>(1438)</td><td>(1431)</td><td>(825)</td><td>(780)</td><td>(743)</td><td>(730)</td><td>(453)</td><td>(690)</td><td>(705)</td>

The following parameters were used for this heating profile:

o Linear speed: 18.3 m / min (60 ft / min) o Suction: 0 o Cuts (Zones 1-3): 5-10 (50%) - middle, all others 100% o Main extinguishing: Setting = 0 and silencer closed with Medium-term cooling: 1 "H2O, setting = 0 and silencer open o After cooling: 1" H2O, setting = 0 and open silencer

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Profile of the furnace 2.3 mm

<td colspan="2"></td><td colspan="10">Zone</td>

<td>Bake</td><td>Temp. in ° C (Temp in ° F)</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td>

<td>top</td><td>setup</td><td>771</td><td>771</td><td>771</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td></td><td></td><td>(1420)</td><td>(1420)</td><td>(1420)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>The actual</td><td>772</td><td>772</td><td>773</td><td>503</td><td>378</td><td>339</td><td>284</td><td>274</td><td>283</td><td>299</td>

<td></td><td></td><td>(1422)</td><td>(1442)</td><td>(1423)</td><td>(937)</td><td>(712)</td><td>(643)</td><td>(544)</td><td>(525)</td><td>(542)</td><td>(570)</td>

<td>bottom</td><td>setup</td><td>771</td><td>771</td><td>771</td><td>0</td><td>316</td><td>316</td><td>316</td><td>316</td><td>316</td><td>316</td>

<td></td><td></td><td>(1420)</td><td>(1420)</td><td>(1420)</td><td></td><td>(600)</td><td>(600)</td><td>(600)</td><td>(600)</td><td>(600)</td><td>(600)</td>

<td></td><td>The actual</td><td>782</td><td>781</td><td>777</td><td>441</td><td>340</td><td>321</td><td>322</td><td>197</td><td>317</td><td>316</td>

<td></td><td></td><td>(1440)</td><td>(1438)</td><td>(1431)</td><td>(825)</td><td>(644)</td><td>(609)</td><td>(612)</td><td>(386)</td><td>(602)</td><td>(601)</td>

The following parameters were used for this heating profile:

• Linear speed: 21.3 m / min (70 ft / min) • Suction: 0 • Trimming (Zones 1-3): 5-10 (50%) - middle, all others 100% • Main quenching: 1 "H2O, only up, setting = 0 and silencer open • Medium-term cooling: setting = 0 and silencer closed • After cooling: 1 "H2O, setting = 0 and silencer open

As a further option, the wavelength IR radiation can be used for heat treatment in certain embodiments. Exemplary techniques are provided in US Patent Application No. 12 / 923,082, issued August 31, 2010, the contents of which are incorporated herein by reference. The TCO layer can be advantageously and selectively treated thermally using the specifically tuned radiation of a near infrared-shortwave infrared (NIR-SWIR), for example. Selective heating of the coating may in certain embodiments be obtained using IR emitters with peak results in spectral wavelengths where ITO significantly absorbs but where the substrate (e.g., glass) has reduced or minimal absorption. In certain embodiments,

By advantageously heating the coating using high intensity IR and wavelength techniques described herein, thermal processing of the ITO layer is possible at lower substrate temperatures and / or shorter heating times than would be required in conventional methods. Favorable heating is achieved by using IR wavelengths that are absorbed much more strongly by the coating than the substrate. High intensity IR radiation can be provided, for example, by quartz lamps or laser emitters.

In the case of laser emitters, the laser diode system may be advantageous, e.g., considering the low cost of their purchase compared to other common types of laser (and the availability of a wavelength around 800-1050 nm (e.g., 940 nm) well suits the spectral characteristics of the coating ). However, excimeric, CO2, YAG, quartz, and / or other types of lasers and / or lamps may also be used in various embodiments. For example, it is noted that a wavelength of 810 nm is common to some diode lasers (and in general may be used in connection with low E coatings, for example), and that a wavelength of 1032 nm is common for some YAG lasers. Further, some embodiments may use other lasers (e.g., CO2 lasers

-14EP 2 539 291 or others) for very fast glass heating and thus indirect heating of the coating. In some embodiments, the electromagnetic radiation may be clustered into a rectangular bundle having a very high aspect ratio including the width of the glass. The glass can be transferred on the conveyor in a direction perpendicular to the long axis of the rectangle. In certain embodiments, a "step and repetition" process may be used, e.g. to irradiate smaller sections in a controlled manner such that the entire substrate is finally irradiated. In addition, other sizes and / or shapes may be used including, for example, substantially square shapes, round shapes, etc.

Generally, higher power densities are considered to be beneficial because they allow for shorter heating times and higher temperature gradients from the coating to the underlying substrate. With shorter heating times, less heat is transferred from the coating through the glass by conduction and the lower temperature can be maintained.

Fig. 8 is a schematic view of a system comprising an IR heater in accordance with certain embodiments. The system of Fig. 8 includes a coater 102 for physically depositing gaseous one or more thin film layers on a substrate, e.g., by spraying. At the bottom of the coater 102 is an IR heater 104. In certain embodiments, a room temperature sputtering apparatus can be used to deposit ITO on a glass substrate. The conveyor system 106 transfers the substrate through the coater 102, where the layer or stack of layers is applied, and to the IR 104 heater. The IR 104 heater, in turn, is tuned to focus the NIR-SWIR radiation on the substrate with the coating applied thereon. The IR radiation wavelength is selected to preferably heat the coating or a specific layer in the coating, e.g.

Although some embodiments have been described as including an IR heater below the coater, it will be appreciated that various embodiments may be located in the coater of the coater. Additionally, in certain embodiments, the IR thermal treatment may be performed at any time after the deposition of the layer to be thermally treated or activated. For example, some embodiments may perform IR heat treatment just after deposition of the ITO layer, while some embodiments may perform IR heat treatment after depositing all layers in a stack of layers. In certain embodiments, multiple IR thermal treatments may be performed at equal times during the deposition process.

A shortwave infrared (SWIR) furnace containing quartz lamps can be used in certain embodiments. The peak IR wavelength 1.15 μm can be used to heat the coating. This wavelength was determined by analyzing the spectral characteristics of the coating and the glass substrate, although other wavelengths are obviously possible. Indeed, an example wavelength range for heating of 0.8-2.5 μm was determined. More preferably, the IR emission range is 1-2 μm. The techniques described in US Patent Application No. 12 / 923,082, for example, can be used to establish optimal or preferred IR emission ranges for the thermal treatment of other coatings (e.g., other TCO coatings, metallic, etc.) on glass.

The power density of the SWIR furnace is 117.33 kW / m² (10.56 kW / ft²) (the output power of the bulb is 3.15 W / mm (80 W / in), with a 25.4 mm (1 ") mount.) The heating times can be from 12130 sec with 12 sec intervals, for example. Heating elements can be around 101.6 mm (4 ") from the glass surface, although the heating elements may be raised or lowered in various embodiments of the invention.

By targeting the IR wavelengths absorbed by the coating, it is possible to generate a large thermal gradient between the coating and the main substrate. Because the thermal mass of the coating is very small compared to glass, the glass essentially acts as a quenching mechanism.

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Increasing the temperature of the main glass is mainly due to direct heat transfer by IR absorption, rather than by conduction from the coating.

It was found that the final crystallinity of the film is obtained only after 48-60 sec of heating, although of course shorter or longer times are possible.

The initial oxidation level of ITO on the samples used here has been optimized for the low sheet resistance after hardening (which results in additional oxidation of the ITO). It is possible that another optimum exists for thermal ITO processing using NIR radiation. When the initial oxidation level of ITO is optimized for NIR heating, it should be possible to significantly reduce the amount of heating required. Theoretically, this time should be reduced to 4860 sec required for re-crystallization using the same heating process. Further reduction of the heating time can be achieved by optimizing the power density requirements vs. heating time.

IR heating techniques described herein preferably preferentially heat the ITO in the coating so that the glass substrate remains below its transition temperature, which is about 480 degrees C for float glass. Preferably, the glass substrate remains below 450 degrees C, and more preferably below 425 degrees C. In certain embodiments, where a peak emission of 1.15 mm is used for 108 sec, the sheet resistance of the exemplary coating is about 1/3 of its deposit equivalent, and emissivity and absorption falls down to about ½ of their deposited counterpart. Meanwhile, the substrate temperature reaches a maximum of only about 400 degrees C, which is also well below its transition temperature.

NIR generally includes IR with a wavelength of 0.75-1.4 μm, and SWIR generally includes IR with a wavelength of 1.4-3 μm. Certain embodiments may generally operate within these wavelengths. The temperature of the substrate preferably does not exceed 480 degrees C, more preferably 450 degrees C, more preferably 425 degrees C, and sometimes 400 degrees C, as a result of such heating NIR-SWIR.

Although certain embodiments have been described herein as relating to anti-condensation coatings, the coatings described herein may be used in connection with other applications. For example, the exemplary coatings described herein can be used in connection with refrigerator / freezer doors and / or other commercial applications, skylights, etc.

In certain embodiments, after heat treatment or thermal activation by other techniques described herein, the coated article may be sent to a producer or other location, e.g., for further processing such as, for example, cutting, dimensioning, incorporation into another article (e.g. unit of the IG unit, skylight, vehicle, glazing, etc.). Preferably, the cracking or catastrophic flaws of the heat-treated coated article will not appear as a result of changes in the glass due to the thermal treatment process.

The "peripheral" and "edge" seals here do not mean that the gaskets are on the absolute edge or edge of the unit, but mean that the gasket is at least partially at or near (e.g., within about two inches) the edges of at least one edge. the foundation of the unit. Similarly, the "edge" as used herein is not limited to the absolute edge of the glass substrate but may also include an area at or near (e.g., within about two inches) of the absolute edge of the substrate (y).

As used herein, the terms "na," "supported on," and the like should not be construed as meaning that the two elements are directly adjacent to each other unless clearly stated. In other words, the first layer may be "on" or "supported by" the second layer, even if there are one or more layers between them.

It will be appreciated that some embodiments may include one or more additional low-E coatings on the surface of one or more glass substrates facing the air gap therebetween (e.g., surfaces 2 and / or 3 in IGU; surfaces 2, 3, 4, and / or 5 in triple IGU, etc.). Surface 4 of the low E coating lying on a transparent glass, for example,

-16EP 2 539 291 can help to improve the overall U-value of the window, e.g., by reflecting the infrared heat back into the interior of the building. The glass may, in certain embodiments, be 2.3mm to 6mm with clear float glass. In such embodiments, the hemispherical emissivity can be reduced to 0.3 and the sheet resistance to 30 ohms / square. Preferably, the emissivity can be reduced to 0.23-0.30 and the sheet resistance to 30 ohms / square, and sometimes the emissivity can be reduced to less than or equal to about 0.2 and the sheet resistance to less than or equal to about 20 ohms / square.

Whereas the invention is described in connection with what is now considered the most practical and preferred embodiment, it is to be understood that the invention should not be limited to the disclosed embodiment, but on the contrary it is intended to include various modifications and equivalent solutions falling within the scope of the appended strzeżeń.

In the following, further embodiments are described to facilitate the understanding of the invention:

1. A method for manufacturing a glazing unit (IGU), the method comprising:

providing the first glass substrate (1);

placing a plurality of layers, directly or indirectly, on the first major surface of the first glass substrate (1), the plurality of layers comprise successively from the first glass substrate:

a first layer (9b) comprising silicon oxynitride having refractive index 1.5-2.1, a layer comprising ITO (5) having a refractive index of 1.7-2.1, and a second layer (9a) containing silicon oxynitride having a refractive index of 1.5-2.1;

thermal treatment of the first glass substrate (1) with multiple layers on itself;

providing a glass substrate (21) which is substantially parallel, away from the first glass substrate, such that the first major surface of the first glass substrate is away from the second glass substrate; and sealing together the first and second glass substrates.

2. The method of example 1, wherein the first (9b) and second (9a) layer containing silicon oxynitride has refractive index 1.7-1.8.

3. The method of example 1, wherein the layer comprising ITO (5) has refractive index 1.8-1.93.

4. The method of example 2, wherein the layer comprising ITO (5) has refractive index 1.8-1.93.

5. The method of example 1, wherein the first substrate (1) with multiple layers on the first major surface of the first glass substrate has a hemispherical emissivity of less than or equal to about 0.23 after said thermal treatment.

6. The method of example 1, wherein the first substrate (1) with multiple layers on the first major surface of the first glass substrate has a hemispherical emissivity of less than or equal to about 0.20 after said thermal treatment.

7. The method of example 1, wherein the first substrate (1) with multiple layers on the first major surface of the first glass substrate has sheet resistance less than or equal to about 20 after said heat treatment.

8. The method of example 1, wherein said thermal treatment includes a laser annealing process.

9. The method of example 8, wherein said laser annealing process comprises a laser diode system operating at about 1 kW and a transmission wavelength of approximately 975 nm.

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10. The method of example 1, wherein said heat treatment uses a furnace having a plurality of zones.

11. The method of example 10, wherein the partial subset of said zones re-crystallizes the layer comprising ITO (5).

12. The method of example 11, wherein the temperature of the first glass substrate (1) remains below 425 degrees C during said heat treatment.

13. The method of example 1, wherein said thermal treatment includes infrared heat treatment.

14. The method of example 13, wherein said infrared heat treatment is performed at a wavelength of about 1-2 microns.

15. The method for manufacturing a glazing unit (IGU), the method comprising:

providing the first glass substrate (1);

placing a plurality of layers, directly or indirectly, on the first major surface of the first glass substrate, the plurality of layers comprise, successively from the first glass substrate:

a first layer comprising silicon oxynitrides (9b), a layer comprising ITO (5), and a second layer comprising silicon oxides (9a);

heat treatment of the first glass substrate (1) with multiple layers on itself; and providing a second glass substrate (21) substantially parallel away from the first glass substrate such that the first major surface of the first glass substrate (1) is away from the second glass substrate (21), wherein the first substrate (1) has plural layers on the first. the main surface of the first glass substrate has a hemispherical emissivity of less than or equal to about 0.20 and sheet resistance less than or equal to about 20 ohms / square after said thermal treatment.

16. The method of example 15, wherein the first (9b) and second layer (9a) containing silicon oxynitride has refractive index 1.7-1.8.

17. The method of example 15, wherein the layer comprising ITO (5) has refractive index 1.8-1.93.

18. The method of example 16, wherein the layer comprising ITO (5) has refractive index 1.8-1.93.

19. The method of example 15, wherein said heat treatment comprises laser annealing, exposure to NIR-SWIR radiation, and / or heating in an oven.

20. A combined glass unit (IGU), containing:

first glass substrate (1);

the plurality of layers deposited by sputtering, directly or indirectly, on the first major surface of the first glass substrate, the plurality of layers comprise, successively from the first glass substrate:

a first layer comprising silicon oxides (9b) having a refractive index of 1.5-2.1, a layer comprising ITO (5) having a refractive index of 1.7-2.1, and a second layer comprising silicon oxynitride (9a) having a refractive index of 1.5-2.1;

-18EP 2 539 291 a second glass substrate (21) substantially parallel and remote from the first glass substrate (1), the first major surface of the first glass substrate (1) facing away from the second glass substrate (21) during assembly; and an edge seal (23) sealing together the first (1) and second (21) glass substrates, where the first glass substrate (1) is heat treated with a plurality of layers on top of each other, and wherein the first substrate (1) with multiple layers on the first main substrate (1) the surface of the first glass substrate has a hemispherical emissivity of less than or equal to about 0.20 and sheet resistance less than or equal to about 20 ohms / square after said thermal treatment.

21. A coated article, containing:

a glass substrate (1) supporting a plurality of deposited sputtering layers, directly or indirectly, on its first major surface, the plurality of layers comprise successively from the glass substrate:

a first layer comprising silicon oxides (9a) having a refractive index of 1.5-2.1, a layer comprising ITO (5) having a refractive index of 1.7-2.1, and a second layer comprising silicon oxynitride (9a) having a refractive index of 1.5-2.1;

wherein the glass substrate (1) is heat treated with a plurality of layers thereon, and wherein the substrate with multiple layers on the first major surface of the first glass substrate (1) has a hemispherical emissivity lower than or equal to about 0.20 and sheet resistance less than or equal to about 20 ohms / square after said heat treatment.

LEGAL PATENT LAW "BELLEPAT"

Izabela Szychuiska-Ha.wrane.k ul Słowackiego 44. 37-700 Przsnł-śl tel (016) 7o2-37-77 fax: (016) 675-02-87 mobile phone (0608) 503-081 e-maii <a href="mailto:bellepat@op.pl">bellepat@op.pl</a> NIP: 795-207-16-72 REGON: 1803505: 6

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<img file="PL2539291T3_D0001.tif" />

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