Methods of making low-e matchable coated articles

ES 2 296 982 T3

DESCRIPTION

Equivalent Low-E Coated Articles Manufacturing Procedures.

This invention relates to articles with a low E (emissivity) coating that have approximately the same color characteristics to the naked eye both before and after heat treatment (eg, heat tempering), and corresponding processes. In certain embodiments, these articles may combine: (1) high visible transmission characteristics, (2) good durability before and / or after heat treatment, and / or (3) a low AE * value indicating color stability after heat treatment. heat treatment (HT). These coated articles can be used monolithically, in insulating glass (IG) units, laminated window units, vehicle windshields, and / or other vehicle or architectural applications.

Background of the invention

Low emissivity (low E) coating systems are known in the art. For example, co-owned U.S. Patent No. 5,376,455 describes: glass / Si₃N / NiCr / Ag / NiCr / Si₃N₄. Unfortunately, the low-E coating system of the '455 patent does not have a sufficiently comparable color to its counterpart not heat treated after heat treatment (HT).

The need for substantial equivalence (before heat treatment vs. after heat treatment) is known. Glass substrates are often produced in large quantities and cut to size to meet the needs of a particular situation such as a new office building with multiple doors and windows, the needs of vehicle windows, etc. Often in these applications it is desirable that some of the windows and / or doors be heat treated (ie tempered, heat strengthened or heat bent), while in others this is not necessary. Office buildings often employ IG units and / or laminates for security and / or thermal control reasons. It is desirable that units and / or laminates that are heat-treated (HT) substantially resemble their non-heat-treated counterparts (eg, with respect to color, reflectance, and / or the like, at least on the glass side) for purposes architectural and / or aesthetic. Furthermore, in certain exemplary but not limiting situations, good post-HT durability (eg, scratch resistance and / or chemical durability) can reduce the need for edge removal to reduce window manufacturing costs.

Commonly owned US Patent No. 5,688,585 describes a solar control coated article including: glass / SI₃N₄/ NiCr / Si3N₄. One of the objects of the Patent 5,688,585 is to provide a layer system coated by a sputtering process which, after heat treatment (HT), has a color comparable to that of its non-heat treated counterpart. Although the coating systems of the '585 patent are excellent for their intended purposes, they have certain drawbacks. In particular, they tend to have fairly high emissivity and / or sheet resistance values ​​(eg, because a silver (Ag) layer is not disclosed in the '5,688,585 patent).

In the prior art it has been possible to achieve equivalence in systems other than those of the aforementioned patent 5,688,585, but only between two different layer systems of which one is heat treated and the other is not. The need to develop and use two different layer systems to achieve equivalency creates additional manufacturing expense and inventory needs that are undesirable.

US Patent Nos. 6,014,872 and 5,800,933 (see Example B) describe a heat-treatable low-E layer system that includes: glass / TiO₂/Yes₃N₄/ NiCr / Ag / NiCr / Si₃N₄. Unfortunately, when this low E layer system is heat treated, it does not have a color roughly equivalent to its non-heat treated counterpart (when viewed from the glass side). This is because this low-E layer system has an AE * (glass side) value greater than 4.1 (i.e., for example B, Aa *_G is 1.49, Ab *_Gis 3.81 and AL * (glass side) is not measured; using equation (1) below, AE * on the glass side necessarily has to be greater than 4.1 and probably has a value much greater than this).

US Patent No. 5,563,734 describes a low E coating system that includes: substrate / TiO₂/ NiCrN_x/ Ag / NiCrN_x/Yes₃N₄. Unfortunately, it has been discovered that when high flow rates of nitrogen (N) are used when the NiCrN layers are formed_x (see the high N flow rate of 143 sccm in Table 1 of the '734 patent; which translates to approximately 22 sccm / kW), the resulting coated articles do not exhibit a stable color upon heat treatment (i.e. they tend to have high AE * (glass side) values ​​greater than 6.0). In other words, if subjected to HT, the low-E layer system of the '734 patent would not be roughly equivalent in color to its unheated counterpart (viewed from the glass side). Furthermore, the coating systems of the '734 patent tend to lack good durability after HT, as they are susceptible to scratching due to the high flow of nitrogen gas used to make them.

WO 01/40131 relates to insulating and laminated glass units having sputter coated layer systems, which can be heat treated and have a color equivalent to that of the counterpart, not heat treated. The functional part of the described layer system comprises two nickel or nickel alloy layers that are substantially free of a nitride or oxide and interposed with a metallic layer of silver.

ES 2 296 982 T3

In addition, it is sometimes desirable for a coated article to have high visible transmission characteristics and / or good durability (mechanical and / or chemical). Unfortunately, certain known steps that are performed to improve visible transmission characteristics and / or pre-HT durability tend to degrade post-HT durability. In this way, it is often difficult to obtain a combination of high visible transmission and good durability.

In view of the foregoing, it will be apparent to those skilled in the art that there is a need for a low E coating or layering system that, after HT, is substantially equivalent in color and / or reflection (when viewed at plain view from the glass side) than its non-heat treated counterpart. In other words, there is a need in the art for a comparable low E coating or coating system. There is also a need in the art for a system that can be heat treated and that can combine: (1) characteristics of high visible transmission, (2) good durability before and / or after heat treatment, and / or (3) a value low AE * indicating color stability after heat treatment.

It is an objective of this invention to satisfy one or more of the needs indicated above, and / or other needs that will become more apparent to those skilled in the art once the following description has been given.

This object is solved by the method of manufacturing a coated article according to claim 1.

An advantage of this invention is that a low E coating or layer system is provided which has good heat treatment (HT) color stability.

Another advantage of this invention is that a comparable low E coating or layer system is provided.

Another advantage of this invention is that a low E coating or coating system is provided that combines characteristics of high visible transmission, good durability before and / or after heat treatment and / or a low AE * value indicating stability of the color after heat treatment (HT). This combination can be achieved in certain non-limiting exemplary embodiments of this invention by providing a coating that includes at least one protective layer that is at least partially nitrated, and that can be heat treated. In this regard, an exemplary coating or coating system includes an Ag layer that reflects IR light, interposed between a first and / or second metallic protective layer, including partially nitrated protective layers that are made of or include NiCrN._x. In certain embodiments, both the first and second protective layers can be partially nitrated (eg, NiCrN_x), whereas in other embodiments only one of the protective layers needs to be partially nitrated (for example, the first protective layer is made of or includes NiCrN_xand the second barrier layer is made of or includes NiCr). The term "nitrated" herein means and includes both fully nitrated and only partially nitrated.

Another advantage of this invention is to provide a coating or coating system designed by adjusting the nitration of at least one protective layer and adjusting the thickness or thicknesses of the layers to obtain a coating or coating system that is capable of combining characteristics of high visible transmission, good durability and / or a low AE value *, which is indicative of an article that when heat treated is substantially equivalent to its non-heat treated counterpart.

Another advantage of this invention is to satisfy one or more of the objects indicated above.

This invention will now be described with respect to certain embodiments thereof as illustrated in the following drawings, in which:

In the drawings

Fig. 1 is a partial side view, in cross section, of one embodiment of a layer system manufactured in accordance with this invention.

Fig. 2 is a partial cross-sectional view of an IG unit as contemplated by this invention, in which the layer system of Fig. 1 can be used.

Fig. 3 is a graph depicting nitrogen gas flow for base (i.e. bottom) protective layer versus color stability from glass side after HT (i.e. AE * (glass side) ), which illustrates that color stability degrades with HT causing the AE * value to increase (ie worsen) as nitrogen flux increases.

Fig. 4 is a graph depicting nitrogen gas flow for top (i.e. top) protective layer versus glass side color stability after HT (i.e. AE * (glass side )), which illustrates that color stability with HT degrades causing the AE * value to increase (ie, worse) as nitrogen flux increases.

ES 2 296 982 T3

Detailed Description of Certain Exemplary Embodiments of the Invention

Certain embodiments of this invention provide a coating or coating system that can be used in applications such as IG or monolithic window units, architectural windows, vehicle windows (eg, windshields, backlites, etc.) and / or other suitable applications. . Certain embodiments of this invention provide a layer system that combines high visible transmission, good durability (mechanical and / or chemical) before and / or after HT, and good color stability after heat treatment. In this document it will be demonstrated how certain stacks of layers surprisingly allow this unique combination.

With respect to color stability, certain embodiments of this invention have excellent color stability (i.e. low AE * value and / or low Aa * value; where Δ indicates change in view of heat treatment) with heat treatment (eg heat tempering, curvature or heat reinforcement) monolithically and / or in the context of double glazing environments such as IG units or windshields. These heat treatments (HT) often need to heat the coated substrate to temperatures of at least about 1100 ° F (593 ° C) to 1450 ° F (788 ° C) [more preferably, about 1100 to 1200 degrees F, and still more preferably 1150 to 1200 degrees F] for a period of time sufficient to ensure the final result (eg, tempering, curvature and / or heat reinforcement). Certain embodiments of this invention combine (i) color stability with heat treatment and (ii) the use of a layer including silver to achieve selective IR reflection. Certain embodiments of this invention combine (i) and (ii) together with (iii) high visible transmission, (iv) good durability, and / or (v) color in the blue-green quadrant (i.e., the third quadrant). of the CIE LAB color chart when applied to a clear and / or green glass substrate, although this invention can certainly be used in the context of other colors. Certain embodiments of this invention combine (i) through (v), along with (vi) low emissivity characteristics.

Figure 1 is a side cross-sectional view of a coated article made in accordance with one embodiment of this invention. The coated article includes substrate 1 (for example, clear, green, bronze, gray, blue or blue-green glass substrate with a thickness of about 1.0 to 12.0 mm), a first dielectric layer 3 (for example , which is made of or includes silicon nitride (for example Si₃N₄), titanium dioxide, tantalum pentoxide, zirconium oxide, silicon zirconium nitride, tin oxide, silicon oxide, silicon dioxide or silicon oxynitride), a partially nitrated first protective layer 5 including a NiCrN metal_xand / or CrN_x, a layer 7 of Ag that reflects IR light, a second protective layer 9 or overlay protective layer that includes a metal, which optionally can be at least partially nitrated (which is made of or includes Ni, NiCr, Cr, NiCrN_x and / or CrN_x) and a second dielectric layer 11th upper dielectric layer (for example, which is made of or including silicon nitride (for example, Si₃N₄), titanium dioxide, tantalum pentoxide, silicon zirconium nitride, zirconium oxide, tin oxide, silicon oxide, silicon dioxide or silicon oxynitride). One or more other layers may also be provided below or above the illustrated liner system. In this way, although the coating or layer system is "on top of" or "supported by" the substrate 1 (directly or indirectly), one or more other layers can be provided in between. Thus, for example, the layer system of Fig. 1 can be considered "on top of" the substrate 1 even though one or more other layers are provided in between (for example, a layer of TiO₂ between substrate 1 and dielectric layer 3 when layer 3 comprises silicon nitride). In addition, those skilled in the art will recognize that the coating or layer system 3-11 of Fig. 1 may be provided as illustrated, or alternatively it may be repeated on top one or more times to form a stack of two or more. three layers of silver.

The IR light reflecting layer 7 is made of or includes Ag metal, although a small amount of oxidation is possible due to this. Thus, in certain embodiments of this invention, layer 7 is oxidized no more than about 10%, more preferably no more than about 1%, and even more preferably no more than 0.5%.

Surprisingly, it has been discovered that by controlling the flow of nitrogen (N) used during sputtering of the barrier layer (s) 5 and / or 9, and / or by controlling the thickness (s) of the layers 5 and / or 9, a coated article can be achieved that combines high visible transmission, good durability before and / or after HT, and good color stability after heat treatment (HT). For example, by controlling the amount of nitration of the protective layer (s) 5 and / or 9 (due to the flow of N gas during sputtering) at low to moderate levels and / or its thickness at flow levels of low to moderate gas, a resulting coated article can be achieved with a lower ΔΕ * value. The examples provided below illustrate, for example and without limitation, the surprising unfortunate findings that color stability degrades (i.e. increases ΔΕ *) and / or also post-HT durability degrades at high N2 gas flows for barrier layers. However, it was surprisingly found that by means of partial nitration of one or more protective layers (for example, to improve durability, such as to improve scratch resistance and / or chemical durability) at lower N gas fluxes₂, much lower and thus better ΔΕ * values ​​can be obtained (eg see Figs. 3-4) and / or better durability can be obtained after HT. In certain embodiments of this invention, both the protective layer 5 and the protective layer 9 can be partially nitrated (symmetrically or asymmetrically), while in other embodiments one of the protective layers can be partially nitrated while the other protective layer cannot (ie. that is, the other protective layer includes a substantially metallic part).

ES 2 296 982 T3

When the protective layers 5, 9 include NiCr (nitrated or not), the respective amounts of Ni and Cr can be, in weight percentages, 80/20 nickel / chromium, 90/10 Ni / Cr, 50/50 Ni / Cr or any other suitable amount. Those skilled in the art will recognize that other materials can be used for the protective layers 5, 9 (for example, other alloys including Ni, niobium or niobium oxide, etc. can be used). An illustrative apparatus that can be used to form the layer coating systems of this invention is a conventional sputter coating system, such as the G-49 multi-chamber large area flat glass sputtering apparatus produced by Airco. Inc.

Furthermore, when protective layers 5 and 9 include NiCr (whether or not nitrated), the metals in these layers may consist of Ni and / or Cr, or alternatively, the sputtering target used in the formation of layers 5 and / or 9 may be Inconel or Haynes 214 alloy which, by weight, consists essentially of the following (as nominal composition):

Element% by weight

<td>Neither</td><td> 75,45</td>

<td>Faith</td><td> 4,00</td>

<td>Cr</td><td> 16,00</td>

<td>C</td><td> 0,04</td>

<td>To the</td><td> 4,50</td>

<td>Y</td><td> 0,01</td>

Fig. 2 illustrates the coating or layer system 22 of Fig. 1 used on surface number 2 of an IG window unit. To differentiate the "inside" of the IG unit from its "outside", the sun 19 is shown schematically on the outside. The IG unit includes an outer glass pane or sheet 21 and an inner glass pane or sheet 23. Thus, the coated articles here can consist of one of the two sheets of the IG unit (ie the coated one) or, alternatively, the entire IG unit including the two sheets. These two glass substrates (eg float glass 1mm to 12mm thick) are sealed at their peripheral edges by means of a conventional sealant 25 and provided with a conventional desiccant strip 27. The panes are then secured in a conventional window or door retaining frame 29 (shown partially schematically). By sealing the peripheral edges of the glass sheets and replacing the air in the insulating space (or chamber) 30 with a gas such as argon, a typical IG unit with a high insulating value is formed. Optionally, the insulating space 30 may be at a pressure lower than atmospheric pressure in certain alternative embodiments, although of course this is not necessary in all embodiments. The inner wall 24 or 26 (or both) may be provided with a layer or cladding system (eg, see Fig. 1) of this invention. In this illustrated embodiment of Fig. 2, the inner wall 24 (ie, surface # 2) of the outer glass sheet 21 is provided with a sputter coated layer system of Fig. 1.

Returning again to Fig. 1, although various thicknesses may be used consistent with one or more of the objects and / or needs described herein, in accordance with certain exemplary embodiments of this invention, the preferred thicknesses and materials for the respective layers on the glass substrate 1 are as follows:

TABLE 1

Thicknesses

<td>Layer Material</td><td>Interval Preferred (A)</td><td>Most preferred (A)</td><td>Even more preferred (A)</td>

<td>YES3N4 (layer 3)</td><td>......... 300-700 A</td><td>...... 400-550 A ~</td><td>450-550 A</td>

<td>NiCrN_x (layer 5)</td><td>3-30 A</td><td>5-15 A</td><td>8-9 A</td>

<td>Ag (layer 7)</td><td>40-120 A</td><td>50-100 A</td><td>60-50 A</td>

<td>NiCr or NiCrNx</td><td>3-30 A</td><td>3-12 A</td><td>6-7 A</td>

<td>YES3N4 (layer 11)</td><td>350-700 A</td><td>400-600 A</td><td>450-550 A</td>

ES 2 296 982 T3

As can be seen from Table 1 above, the underlying protective layer 5 has been nitrated and the overlying protective layer 9 may or may not be nitrated in different embodiments of this invention. Unexpectedly, it has been discovered that by controlling the amount of nitration for the protective layers 5 and / or 9 at low to moderate levels, a coating with much better color stability after heat treatment (i.e., a lower value of AE *) (for example, see Fig. 3-4). This nitration can also improve durability after HT. Furthermore, in certain non-limiting exemplary embodiments, it has been found that particular thicknesses of the superimposed dielectric layer 11 result in better AE * values ​​when the underlying dielectric layer 3 is approximately 0-25% thinner than the superimposed dielectric layer 11. , more preferably about 5 to 15% finer and even more preferably about 8 to 10% finer. One or more of these characteristics is believed to result in equivalence or lower AE * values ​​(as will be described below) associated with certain embodiments of this invention (ie, better stability with heat treatment). Any aforementioned combination of a low E system with good stability (color and / or durability) with heat treatment is considered novel and inventive.

In certain exemplary embodiments, stability with heat treatment results in substantial equivalence between the heat-treated and non-heat-treated versions of the coating or layer system. In other words, in monolithic and / or IG applications, in certain embodiments of this invention two glass substrates that have the same coating system on them (one heat treated after deposition and the other not heat treated) appear substantially the same as The naked eye when viewed from the glass side of the product (i.e. when looking through at least one glass substrate before viewing the coating). In certain embodiments of this invention, it has also been discovered that equivalency (although achievable in monolithic applications) can be even better in IG and / or laminate applications.

The AE * value is important in determining whether or not after optional heat treatment (HT) there is equivalence or substantial equivalence in the context of this invention. In this document, color is described with reference to conventional a *, b * values ​​which, in certain embodiments of this invention, are negative to provide color in the desired substantially neutral color range tending to the blue-green quadrant. For example purposes, the term Aa * simply indicates the amount of the a * value that changes due to heat treatment.

The term AE * (and AE) is well understood in the art and is presented, along with various techniques for determining it, in ASTM 2244-93, in addition to being presented in Hunter et al., The Measurement of Appearance, 2^to ed. chap. 9, page 162 and following [Jonh Wiley &amp; Sons, 1987]. As used in the art, AE * (and AE) is a way of adequately expressing the change (or its absence) in reflectance and / or transmittance (and thus also the appearance of color) in an article from after or due to HT. AE can be calculated by the "ab" technique or by the Hunter technique (named using the subscript "H"). AE corresponds to Hunter's Lab L, a, b scale (or L_h, to_h, bh). Similarly, AE * corresponds to the L *, a *, b * scale of ClE LAB. The two are considered useful and equivalent for the purposes of this invention. For example, as noted in Hunter et al., Mentioned above, the rectangular coordinate / scale technique (CIE LAB 1976) known as the L *, a *, b * scale can be used, where:

L * is (CIE 1976) brightness units a * is (CIE 1976) red-green units b * is (CIE 1976) yellow-blue units and the distance AE * between L *₀ to*₀b *₀ it is:

<img file="ES2296982T3_D0001.tif" />

where:

ÁL * = L *! - L *₀ (2)

Áa * = a *₁-to*₀ (3)

<img file="ES2296982T3_D0002.tif" />

where the subscript "0" represents the coating (the coated article) before the heat treatment and the subscript "1" represents the coating (the coated article) after the heat treatment; and the numbers used (for example, a *, b *, L *) are those calculated by the L *, a *, b * coordinate technique (CIE LAB 1976) mentioned above. In a similar way, AE can be calculated using equation (1) by replacing a *, b *, L * with the Hunter Lab values ​​a_h, b_h, L_h. Also within the scope of this invention and the AE * quantization are equivalent numbers if converted to those calculated by any other technique employing the same AE * concept as defined above.

ES 2 296 982 T3

In certain embodiments of this invention, the layer systems provided herein on clear monolithic glass substrates (e.g., 4mm thick glass substrates for example reference purposes) have the following color prior to heat treatment, when viewed from the glass side of the coated article (R_G %):

TABLE 2

Color (R_g) Before Heat Treatment

General Preferred a * '0.0 a -5.0' 0.0 a -2.0 b * -1.0 a-10.0 -5.0 a-9.0

After heat treatment, in certain embodiments of this invention the coating systems provided on transparent monolithic glass substrates of this invention have the color characteristics AE * and Aa * listed below, when viewed from the glass side ( G) (instead of from the layer side) of the coated article:

TABLE 3

Color Characteristics (AE *_g) After Heat Treatment

General Most Preferred Even More Preferred

AE *_g &lt;3,5 &lt;3,0 &lt;2,6

Aa *_G &lt;2,0 &lt;1,0 &lt;0,7

Accordingly, as shown in Table 3 above, articles coated in accordance with certain embodiments of this invention have an AE * value (on the glass side) of no more than 3.5, more preferably no more than 3, 0 and even more preferably not more than 2.6 (and even more preferably &lt;2.0). When this wider interval is achieved, equivalence is obtained.

Examples 1-15

Nitration of Protective Layer (s)

Some of the following fifteen exemplary coated articles (each tempered and heat treated) were made in accordance with this invention.

These examples are hereinafter referred to as examples of the invention and are examples 1, 2, 12-13 and 15. Other examples 3-10 and 14 are only reference examples, which are not included in the claims. In examples 1-8 and 15 the layer system was: glass / Si₃N₄NiCrN_x/ Ag / NiCrN_x/Yes₃N₄ (for example see Fig. 1; N gas flow during sputtering of the two protective layers 5 and 9 to nitrate them), although this invention is obviously not limited to this. For each of Examples 12-14, the layer system was glass / Si₃N₄/ NiCrN_x/ Ag / NiCr / Si₃N₄ (eg see Fig. 1; but no N gas flow during sputtering of upper protective layer 9). Meanwhile, for each of Examples 9-10, the layer system was glass / Si₃N₄/ NiCr / Ag / NiCr / Si₃N₄ (eg see Fig. 1; but no N gas flow during sputtering of barrier layer 5 or 9). Examples 9-10 (no N gas flow for layers 5, 9) will be shown below to lack durability over examples where N gas flow was used during sputtering of one or more of the protective layers. Furthermore, it will be demonstrated that by controlling the flow of N gas during sputtering of one or both protective layers, the AE * value of the resulting coating or layer system can be improved (ie lowered). In each of these examples, the substrate was substantially transparent 4mm thick sodium silicate glass, and each example was monolithic (non-IG). Coater / method preparations, using a BOC series sputter coater (BOC ILS) for the examples, were as follows.

The IR light reflective layer 7 and the dielectric layers 3, 11 were constant in the 15 Examples. In each of Examples 1-15, the Ag layer7 was metallic (sputtered using a metallic flat Ag target), approximately 79 A (angstroms) thick, sputtered at a power of approximately 2.95 kW, 465 V, using an Ar gas flow of 30 sccm / kW and a pressure of approximately 2.7 mTorr, and a linear velocity of 100IPM (one pass) with the target masked at an aperture of 0.75 ”, and had a sheet resistance value of about R₅ = 16 ohms / square. In each of Examples 1-15, the 3 layer of Si₃N₄ had a thickness of approximately 470 A, it was sputtered using a

ES 2 296 982 T3 Si C-Mag target (Al content approximately 10%), sputtered at a power of approximately 1 kW, 485 V, using a gas flow of 40 sccm / kW Ar and 40 sccm / kW of N and a pressure of approximately 2.5 m Torr, at a linear speed of 55 IPM (eight passes). In each of Examples 1-15, layer 11 of Si₃N₄ superimposed had a thickness of about 510 A, it was sputtered using a Si C-Mag target (Al content of about 10%), it was sputtered at a power of about 1 kW, 485 V, using a gas flow of 40 sccm of Ar and 40 sccm of N at a linear velocity of 50 IPM (eight passes).

Thus, Examples 1-15 differ in that the protective layers 5 and / or 9 were deposited / sputtered in different ways (eg with different N fluxes and / or different thicknesses). In the sputtering barrier layers 5 and 9 of Examples 1-15, flat Ni: Cr (80/20) sputtering targets were used and an Ar gas flow of 30 sccm was used. However, the flow of nitrogen gas (N) (sccm / kW of power), the linear speed and the power were varied in the different Examples 1-15 to achieve the different thicknesses of the protective layers 5, 9 indicated below . It should be noted that, in Table 4 below, "Bar." refers to the protective layer (eg, Bar. 5 indicates the underlying protective layer 5, while Bar. 9 indicates the second protective layer 9 or superimposed protective layer in Fig. 1). Also, in Table 4, "Thickness" refers to the thickness at A and "Bar. N₂ F1. " refers to the nitrogen gas flow (sccm / kW power) during the sputtering process of the relevant protective layer.

TABLE 4

Examples 1-15 (Sputtered)

<td>Ex.</td><td>Mat. of</td><td>Thickness of</td><td>N₂FI of</td><td>Mat. of</td><td>Thickness of</td><td>N₂FI of</td>

<td>No.</td><td>Bar. 5</td><td>Bar. 5</td><td>Bar. 5</td><td>Bar. 9</td><td>Bar. 9</td><td>Bar. 9</td>

<td> 1</td><td>NiCrNx</td><td></td><td> 8</td><td>NiCrN_x</td><td></td><td> 8</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 2</td><td>NiCrNx</td><td>9A</td><td> 8</td><td>NiCrN_x</td><td>6 A</td><td> 8</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 3</td><td>NiCrNx</td><td>6 A</td><td> 16</td><td>NiCrN_x</td><td>3 A</td><td> 16</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 4</td><td>NiCrNx</td><td>9 A</td><td> 16</td><td>NiCrNx</td><td>6 A</td><td> 16</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 5</td><td>NiCrNx</td><td>9 A</td><td> 32</td><td>NiCrN_x</td><td>9 A</td><td> 32</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 6</td><td>NiCrNx</td><td>12A</td><td> 32</td><td>NiCrN_x</td><td>3A</td><td> 32</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 7</td><td>NiCrNX_x</td><td>6 A</td><td> 32</td><td>NiCrN_x</td><td>9A</td><td> 32</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 8</td><td>NiCrNx</td><td>12 A</td><td> 16</td><td>NiCrNx</td><td>3A</td><td> 16</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 9</td><td>NiCr</td><td>6 A</td><td> 0</td><td>NiCr</td><td>6 A</td><td> 0</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 10</td><td>NiCr</td><td>9A</td><td> 0</td><td>NiCr</td><td>6A</td><td> 0</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 12</td><td>NiCrN_x</td><td>9A</td><td> 8</td><td>NiCr</td><td>6 A</td><td> 0</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

<td> 13</td><td>NiCrNx</td><td>9A</td><td> 8</td><td>NiCr</td><td>6A</td><td> 0</td>

<td></td><td></td><td></td><td>sccm / kW</td><td></td><td></td><td>sccm / kW</td>

ES 2 296 982 T3

<td> 14</td><td>NiCrN_x</td><td>9 A</td><td>16 sccm / kW</td><td>NiCr</td><td>6 A</td><td>0 sccm / kW</td>

<td> 15</td><td>NiCrN_x</td><td>6 A</td><td>8 sccm / kW</td><td>NiCrNx</td><td>6A</td><td>8 sccm / kW</td>

After being sputtered onto a glass substrate as above, Examples 1-15 were tested both before and after heat treatment (HT) and found to have the following characteristics monolithically (not in a IG unit), where the HT was a thermal tempering of the monolithic product in a conventional oven at approximately 1150 ° F for 10 minutes (note: in Table 5 and in this document, the a * and b * color coordinate values ​​are in accordance with the CIE LAB 1976 III technique. ICD-C, observer 2 degrees. The pattern of III was also used. C, 2 degrees for visible transmission, etc. It should also be noted that the "adhesive tape test" was performed according to the military standard, MIL-AA-113, incorporated herein by reference, to test adhesion. The acid boil test was performed for one hour to check chemical durability. With respect to the acid boil test, the adhesive tape test, the brush test and the scratch test, the results are shown on a progressive scale from 0 to 5, with 0 being the best result and 5 being the worst. In particular, 0 means there is no change or injury (all this is based on visual observations), 1 means a barely visible change, 2 means a minor change, 3 means a more obvious injury than 2 but still limited in scope, 4 means a visible injury more serious than 3 but limited in area and 5 means a very serious injury up to complete failure / disintegration.

TABLE 5

Characteristics of Examples 1-15 (Monolithic)

Invention Example No. 1

Value / Measurement

Transmission (TY)%:

to*_T:

bV

Reflectance observed from the glass side (G): RgY (%):

L *_g:

to*_G:

b *_G:

ΔΕ * (i.e. from the glass side (G)):

Aa *_G (absolute value)

Reflectance observed from film / coating side (F): R_FY (%):

to*_F:

b *_F:

R_s (sheet resistance in ohms / square)

Adhesive tape test:

Brush test:

Boiling in acid:

Scratch test:

<td>Before heat treatment</td><td>After heat treatment</td>

<td> 73,57</td><td> 77,12</td>

<td> -2,35</td><td> -2,74</td>

<td> -0,97</td><td> -1,78</td>

<td> 8,04</td><td> 6,86</td>

<td> 34,06</td><td> 31,48</td>

<td> -0,96</td><td> -0,60</td>

<td> -7,92</td><td> -8,06</td>

<td></td><td> 2,6</td>

<td></td><td> 0,36</td>

<td> 3,62</td><td> 3,53</td>

<td> 5,30</td><td> 3,38</td>

<td> -6,00</td><td> -6,52</td>

<td> 15,50</td><td> 12,60</td>

<td> 0</td><td> 0</td>

<td> 1</td><td> 0</td>

<td> 0</td><td> 0</td>

<td> 2</td><td> 1</td>

ES 2 296 982 T3

Invention Example No. 2

<td>Value / Measurement</td><td>Before the</td><td>After the</td>

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

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

Transmission (TY)%: a *_T: b *_T:

75,12 -2,25 -0,81

Glass Observed Reflectance (G): R_GY (%):

<img file="ES2296982T3_D0003.tif" />

<img file="ES2296982T3_D0004.tif" />

<img file="ES2296982T3_D0005.tif" />

<img file="ES2296982T3_D0006.tif" />

<img file="ES2296982T3_D0007.tif" />

7,97

33,92

-1,11

-7,38

<img file="ES2296982T3_D0008.tif" />

(G)):

glass

79,52

-2,53

-0,78

7,05

31,92

-1,10

-7,79

2,0

Aa * G (absolute value) Observed reflectance from film / coating (F): (%) ·· a *_F:

b *_F:

R_s (sheet resistance ohms / square)

Adhesive tape test:

Brush test: Boiling in acid:

Scratch test:

<td>side r_FY</td><td> 3,89</td><td> 0,01 3,58</td>

<td></td><td> 4,24</td><td> 1,45</td>

<td></td><td> -6,16</td><td> -8,05</td>

<td>in</td><td> 16,70</td><td> 12,90</td>

<td></td><td> 0</td><td> 0</td>

<td></td><td> 1</td><td> 1</td>

<td></td><td> 0</td><td> 0</td>

<td></td><td> 2</td><td> 2</td>

ES 2 296 982 T3

Reference example No. 3

Before heat treatment

After heat treatment

Value / Measurement

Transmission (TY)%: a *_T: ό * τ:

Observed reflectance of glass (G): R_GY (%): L *_g: to*_G: b *_G:

ΔΕ * (that is, from (G)):

Aa * G (absolute value) Observed film / coating reflectance (F): (%):

to*_F:

b *_F:

R_s (sheet resistance ohms / square) from the glass side side from the RfY side in

79,33

-2,07

-0,17

7,72

33,39

-1,32

-6,43

4,59

2,19 -5,80 17,20

Adhesive tape test:

Brush test:

Boiling in acid:

Scratch test:

2,5

81,96

-1,90

-0,44

7,31

32,50

-1,72

-6,80

1,0

0,4

4,77

0,31 -7,33 14,30

ES 2 296 982 T3

Reference example No. 4

<td>Value / Measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>Transmission (TY)%:</td><td> 75,91</td><td> 76,81</td>

<td>to*_T:</td><td> -2,03</td><td> -2,52</td>

<td>b *_T:</td><td> -0,75</td><td> -2,32</td>

<td>Reflectance observed from the side</td><td> 8,21</td><td> 8,68</td>

<td>glass (G): R_GY (%):</td><td></td><td></td>

<td>L *_g:</td><td> 34,42</td><td> 35,36</td>

<td>to*_G:</td><td> -1,71</td><td> -1,84</td>

<td>b *_G:</td><td> -6,60</td><td> -4,48</td>

<td>ΔΕ * (i.e. from the glass side</td><td></td><td> 2,3</td>

<td>(G)):</td><td></td><td></td>

<td>Aa *_G (absolute value)</td><td></td><td> 0,13</td>

<td>Reflectance observed from the side</td><td> -4,20</td><td> 4,20</td>

<td>Film / Coating (F): R_FY</td><td></td><td></td>

<td> (%)’·</td><td></td><td></td>

<td>to*_F:</td><td> 2,79</td><td> 0,73</td>

<td>b *_F:</td><td> -5,31</td><td> -4,80</td>

<td>R_s (sheet resistance in</td><td> 16,50</td><td> 18,20</td>

<td>ohms / square)</td><td></td><td></td>

<td>Adhesive tape test:</td><td> 0</td><td> 0</td>

<td>Brush test:</td><td> 0</td><td> 1</td>

<td>Boiling in acid:</td><td> 0</td><td> 5</td>

<td>Scratch test:</td><td> 2</td><td> 2</td>

ES 2 296 982 T3

Reference example No. 5

<td>Value / Measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>Transmission (TY)%:</td><td> 76,42</td><td> 62,90</td>

<td>to*_T:</td><td> -2,23</td><td> -1,56</td>

<td>b * -j &lt;</td><td> -0,02</td><td> -0,85</td>

<td>Reflectance observed from the side</td><td> 8,29</td><td> 21,69</td>

<td>of glass (G): RgY (%):</td><td></td><td></td>

<td>L *_g:</td><td> 34,57</td><td> 53,70</td>

<td>to*_G:</td><td> -0,96</td><td> -0,96</td>

<td>b *_G:</td><td> -7,80</td><td> -7,80</td>

<td>ΔΕ * (i.e. from the glass side</td><td></td><td> 19,1</td>

<td>(G)):</td><td></td><td></td>

<td>Aa * G (absolute value)</td><td></td><td> 0</td>

<td>Reflectance observed from the side</td><td> 3,96</td><td> 17,83</td>

<td>Film / Coating (F): R_FY</td><td></td><td></td>

<td> (%):</td><td></td><td></td>

<td>to*_F:</td><td> 4,38</td><td> 4,38</td>

<td>b *_F:</td><td> -8,64</td><td> -8,64</td>

<td>R_s (sheet resistance in</td><td> 17,20</td><td>n / a</td>

<td>ohms / square)</td><td></td><td></td>

<td>Adhesive tape test:</td><td> 0</td><td> 5</td>

<td>Brush test:</td><td> 1</td><td> 5</td>

<td>Boiling in acid:</td><td> 0</td><td> 5</td>

<td>Scratch test:</td><td> 0</td><td> 5</td>

ES 2 296 982 T3

Reference example 6

<td>Value / Measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>Transmission (TY)%:</td><td> 74,35</td><td> 69,44</td>

<td>to*_T:</td><td> -2,22</td><td> -2,09</td>

<td>b *_T:</td><td> -0,78</td><td> -4,55</td>

Reflectance observed from the glass side (G): R_GY (%):

L *_g:

to*_G:

b *_G:

ΔΕ * (i.e. from the glass side (G)):

Aa *_G (absolute value)

Reflectance observed from film / coating side (F): R_FAlready*_F: b *_F:

R_s (sheet resistance in ohms / square)

Adhesive tape test:

Brush test:

Boiling in acid:

Scratch test

8,46

34,91

-1,41

-6,97

3,85

4,46

-6,7

16,30

14,35

44,74

-0,97

3,40

14,3

0,44

10,70

2,70

5.45 n / a

ES 2 296 982 T3

Reference example No. 7

Before heat treatment

Value / Measurement

Transmission (TY)%: a *_T:

b * T · '

Observed reflectance of glass (G): R_GY (%): L * g ·· a *_G:

b * G · '

ΔΕ * (that is, from (G)):

Aa *_G (absolute value) from the glass side

79,08

-1,72

-0,44

7,81

33,59

-2,38

-5,88

After heat treatment 77.88 -2.27 -2.16 10.17

38,14 -2,19 -1,72

6,2

0,19

Reflectance observed from film / coating (F): (%):

to*_F:

b *_F:

R_s (sheet resistance ohms / square)

Adhesive tape test:

Brush test:

Boiling in acid:

Scratch test

<td>RfY side</td><td> 4,83</td><td> 6,97</td>

<td></td><td> 0,14</td><td> -0,46</td>

<td></td><td> -4,20</td><td> -2,68</td>

<td>in</td><td> 16,70</td><td> 22,70</td>

<td></td><td> 0</td><td> 0</td>

<td></td><td> 0</td><td> 4</td>

<td></td><td> 0</td><td> 5</td>

<td></td><td> 2</td><td> 2</td>

ES 2 296 982 T3

Reference example No. 8

Value / Measurement '' 'Before heat treatment

Transmission (TY)%:

to*_T:

b * T '

Reflectance observed from the glass side (G): R_GY (%):

L *_g:

to*_G:

b *_G:

ΔΕ * (i.e. from the glass side (G)):

Aa *_G (absolute value)

Reflectance observed from film / coating side (F): R_FY (%):

to*_F:

b *_F:

R_s (sheet resistance in ohms / square)

Adhesive tape test:

Brush test:

Boiling in acid:

Scratch test:

74,04

-2,29

-0,67

8,36

34,72 -1,01 -7,62

3,72

5,26

-7,58

15,50

After heat treatment 7E55 -2.27 -3.36 10.73

39,12 -1,46 -1,14

7,9

0,45

6,92

2,06

0,84

25,80

ES 2 296 982 T3

Reference example No. 9

<td>Value / Measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>Transmission (TY)%:</td><td> 78,92</td><td> 81,94</td>

<td>to*_T:</td><td> -2,10</td><td> -2,27</td>

<td>b *_T:</td><td> -0,13</td><td> 0,07</td>

<td>Reflectance observed from the side</td><td> 7,82</td><td> 7,37</td>

<td>glass (G): R_GY (%):</td><td></td><td></td>

<td>L *_g:</td><td> 33,61</td><td> 32,63</td>

<td>to*_G:</td><td> -1,25</td><td> -1,33</td>

<td>b *_G:</td><td> -6,53</td><td> -6,68</td>

<td>ΔΕ * (i.e. from the glass side</td><td></td><td> 1,0</td>

<td>(G)):</td><td></td><td></td>

<td>Aa *_G (absolute value)</td><td></td><td> 0,08</td>

<td>Reflectance observed from the side</td><td> 4,58</td><td> 4,91</td>

<td>Film / Coating (F): R_FY</td><td></td><td></td>

<td> (%)·’</td><td></td><td></td>

<td>to'_F:</td><td> 2,51</td><td> -0,35</td>

<td>b *_F:</td><td> -6,55</td><td> -6,74</td>

<td>R_s (sheet resistance in</td><td> 17,40</td><td> 10,30</td>

<td>ohms / square)</td><td></td><td></td>

<td>Adhesive tape test:</td><td> 0</td><td> 0</td>

<td>Brush test:</td><td> 1</td><td> 5</td>

<td>Boiling in acid:</td><td> 0</td><td> 5</td>

<td>Scratch test</td><td> 0,5</td><td> 2,5</td>

ES 2 296 982 T3

Reference example No. 10

<td>Value / Measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>Transmission (TY)%:</td><td> 76,00</td><td> 78,81</td>

<td>to*_T:</td><td> -2,27</td><td> -2,42</td>

<td>b *_T:</td><td> 0,07</td><td> -0,94</td>

<td>Reflectance observed from the side</td><td> 8,74</td><td> 7,28</td>

<td>glass (G): R_GY (%):</td><td></td><td></td>

<td>L * g ··</td><td> 35,49</td><td> 32,43</td>

<td>to*_G:</td><td> -1,42</td><td> -1,38</td>

<td>b *_G:</td><td> -7,00</td><td> -7,23</td>

<td>ΔΕ * (i.e. from the glass side</td><td></td><td> 3,1</td>

<td>(G)):</td><td></td><td></td>

<td>Aa *_G (absolute value)</td><td></td><td> 0,04</td>

<td>Reflectance observed from the side</td><td> 4,02</td><td> 4,28</td>

<td>Film / Coating (F): R_FY</td><td></td><td></td>

<td> (%):</td><td></td><td></td>

<td>to*_F:</td><td> 4,11</td><td> 0,74</td>

<td>b *_F:</td><td> -10,71</td><td> -6,76</td>

<td>R_s (sheet resistance in</td><td> 16,40</td><td> 12,80</td>

<td>ohms / square)</td><td></td><td></td>

<td>Adhesive tape test.</td><td> 0</td><td> 0</td>

<td>Brush test:</td><td> 0</td><td> 4</td>

<td>Boiling in acid:</td><td> 0</td><td> 5</td>

<td>Scratch test:</td><td> 2</td><td> 2</td>

ES 2 296 982 T3

Reference example No. 12

<td>Value / Measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>Transmission (TY)%:</td><td> 76,4</td><td> 79,9</td>

<td>to*_T:</td><td> -2,5</td><td> -2,8</td>

<td>b *_T:</td><td> 0,3</td><td> -0,6</td>

Reflectance observed from the glass side (G): R_GY (%)·'

L *_g:

to*_G:

b *_G:

ΔΕ * (i.e. from the glass side (G)):

Aa *_G (absolute value)

Reflectance observed from film / coating side (F): R_FY (%):

to*_F:

b *_F:

R_s (sheet resistance in ohms / square)

Adhesive tape test:

Brush test:

Boiling in acid:

Scratch test

8,5

35,0

-0,6

-8,3

3,9

7.4

32,7 -0,8 -7,9

2.4

0,2

3,9

5.7 -12,2

16.7

2,5

1,8 -10,8 13,2

1,5

ES 2 296 982 T3

Reference example No. 13

Before heat treatment

After heat treatment

Value / Measurement

Transmission (ΤΎ)%: a *_T: b * T · '

Observed reflectance of glass (G): R_GY (%): L *_g:

to*_G:

b *_G:

ΔΕ * (that is, from (G)):

Aa *_G (absolute value) from the side of the glass from the

Observed film / coating reflectance (F): (%) 'RfY side

76,7 -2,7 0,5 8,0

34,0

-0,2

-8,2

3,9

79,4 -3,0 -0,7 7,5

32,9 -0,4 -8,1

1.2

0,2

3,9

<td>to*_F:</td><td> 6,1</td><td> 2,7</td>

<td>b *_F:</td><td> -8,6</td><td> -11,2</td>

<td>R_s (sheet resistance in</td><td> 17,1</td><td>n / a</td>

<td>ohms / square)</td><td></td><td></td>

<td>Adhesive tape test:</td><td>n / a</td><td>n / a</td>

<td>Brush test:</td><td>n / a</td><td>n / a</td>

<td>Boiling in acid:</td><td>n / a</td><td>n / a</td>

<td>Scratch test:</td><td>n / a</td><td>n / a</td>

ES 2 296 982 T3

Reference example No. 14

Value / Measurement 'Before heat treatment

Transmission (TY)%:

to*_T:

b * y:

Reflectance observed from the glass side (G): R_GY (%):

L *_g:

to'_G:

b *_G:

ΔΕ * (that is, from the glass side (θ)):

Aa *_G (absolute value)

Reflectance observed from film / coating side (F): R_FY (%):

to*_F:

b *_F:

R_s (sheet resistance in ohms / square)

Adhesive tape test:

Brush test: Acid boil: Scratch test:

75.5

-2,3 -0,5

8,3

34.6 -1,2 -7,5

3,9

4.6

-8,6

16.6

After heat treatment 7971 -2.6 -1.2 7.4

32,8 -1,3 -7,0

1,9

0,1

4,2

1,2

-7,6

13,5

3,5

ES 2 296 982 T3

Reference example No. 15

<td>Value / Measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>Transmission (TY)%:</td><td> 77,7</td><td> 81,4</td>

<td>to*_T:</td><td> -2,3</td><td> -2,8</td>

<td>bV</td><td> 0,1</td><td> -0,7</td>

<td>Reflectance observed from the side</td><td> 7,9</td><td> 6,8</td>

<td>glass (G): R_GY (%):</td><td></td><td></td>

<td>L *_g:</td><td> 33,7</td><td> 31.4</td>

<td>to*_G:</td><td> -0,5</td><td> -0,5</td>

<td>b *_G:</td><td> -8,0</td><td> -7,9</td>

<td>ΔΕ * (i.e. from the glass side</td><td></td><td> 2,4</td>

<td>(G)):</td><td></td><td></td>

<td>Aa *_G (absolute value)</td><td></td><td> 0,0</td>

<td>Reflectance observed from the side</td><td> 4,2</td><td> 4,1</td>

<td>Film / Coating (F): R_FY</td><td></td><td></td>

<td> (%):</td><td></td><td></td>

<td>to*_F:</td><td> 4,4</td><td> 1.3</td>

<td>b *_F:</td><td> -8,7</td><td> -8,7</td>

<td>R_s (sheet resistance in</td><td> 17,0</td><td> 13,3</td>

<td>ohms / square)</td><td></td><td></td>

<td>Adhesive tape test:</td><td> 0</td><td> 0</td>

<td>Brush test:</td><td> 0</td><td> 2</td>

<td>Boiling in acid:</td><td> 0</td><td> 3</td>

<td>Scratch test:</td><td> 2</td><td> 2</td>

As can be seen from the above, it can be seen that each of Examples 1-4 and 12-15 had good results in terms of each of the following points: (a) good equivalence because, when viewed from the side of the glass (G) of the respective articles, the AE * value was not more than 2.5, and preferably not more than 2.0; (b) a high visible transmission of at least 70% (even more preferably at least 74% in certain embodiments); and (c) good durability in terms of overall results of the adhesive tape test, brush test, acid boil test and / or scratch test both before and after HT. It is most desirable to have coated articles that are satisfactory in all three areas (a) - (c). In addition, each of Examples 1-4 and 12-15 was considered heat treatable as the coating was not damaged by HT (eg, no peeling, no holes, cracks, or dull areas). Unfortunately, Examples 5-8 had poor results in terms of equivalence (ie, very high AE * values ​​from the glass side). The poor equivalence results (before vs. after HT) associated with Examples 5-8 are considered a result of (i) the thicknesses of the protective layer (s) and / or (ii) the high flow of nitrogen gas (N ) using during deposition of the protective layer (s). For example, Examples 1-2 (best overall combination of durability and equivalence before HT vs. post HT) used a nitrogen flux of 8 sccm / kW in sputtering the protective layer (s), while Examples 5-7 (poor equivalence before HT vs. after HT) used a much higher nitrogen gas flow, 32 sccm / kW, during deposition of the protective layer (s). A comparison between Examples 3-4 versus Example 8 illustrates that the thickness of the protective layer (s) is also important (i.e., given a N flow rate of 16 sccm / kW, the lower thicknesses of the protective layer (s)

The protective ES 2 296 982 T3 of Examples 3-4 makes these coated articles equivalent before HT versus after HT, while the greater thicknesses of the protective layer or layers of Example 8 make this back coated article have a AE * value too high, 7.9, and thus a bad equivalence). Examples 9-10 had good equivalency but poor durability (eg, poor brush test results); This is believed to be due to the fact that there was no N flow during sputtering of the protective layers. However, Examples 12-14 (N flux during sputtering of lower protective layer 5, but not upper protective layer 9) illustrate that good results can be obtained with regard to equivalence and durability when only intentionally nitrating one of the protective layers (eg the lower one) (ie, according to this invention, the flux of N for the opposing protective layers 5, 9 can be symmetric or asymmetric). Consequently, it can be seen that by controlling the nitrogen flow during sputtering of one or the two protective layers 5, 9, a combination of high transmission, equivalence and / or good durability can be obtained which is a significant improvement over to the prior art. Control of the thickness of the protective layer is also shown to be an important factor in reducing AE * values ​​and thus providing good equivalency.

For example, and without limitation, a good equivalency combined with high visible transmission and / or good durability can be obtained both before and after HT when the flux of N during sputtering of the lower protective layer 5 is 0 to 16 sccm / kW, more preferably 4 to 12 sccm / kW (still more preferably 6 to 10 sccm / kW) and the N flux during sputtering of the upper protective layer 9 is 0 to 16 sccm / kW, more preferably 0 to 8 sccm / kW, and even more preferably 0 to 4 sccm / kW. Surprisingly, it has been found that moderate N2 flux during sputtering of the protective layer (s) produces the longest lasting coated articles along with good equivalency. In some embodiments of this invention, the two protective layers 5, 9 can be subjected to a sputtering process using a flow of N, while in other embodiments of this invention, the lower protective layer 5 can be subjected to a sputtering process using a flux of N while the upper layer 9 is not (ie the upper protective layer 9 can be metallic, eg NiCr, in certain embodiments). Furthermore, the two protective layers 5, 9 may have approximately the same thickness in certain embodiments, while in other embodiments they may have different thicknesses (for example, the upper protective layer 9 may be thinner and / or less nitrated).

Surprisingly, it has also been found that controlling the thickness of the dielectric layer (s) 3 and / or 11 can contribute to good equivalence and / or durability. In particular, it has been found that good equivalence (i.e. post-HT color stability) is achieved when the upper dielectric layer (when silicon nitride) 11 has a thickness of about 510 A, or slightly less greater than this. Then, the lower dielectric layer (when it is silicon nitride) 3 is provided at a thickness of about 5-20%, more preferably about 10% less than that of the upper dielectric layer 11. Although, of course, other thicknesses of these layers can be used in different embodiments of this invention, these particular thicknesses have been found to be especially good. Furthermore, it has been found that when silicon nitride is present, fully nitrated silicon nitride layers 3,11 produce more stable coatings. However, in other embodiments, Si-rich silicon nitride, and / or other stoichiometries with respect to these dielectric layers can be used.

From the above Examples, it can be seen that monolithic coated articles according to certain embodiments of this invention preferably have a visible transmittance (TY%) of at least about 65% before and / or after HT, more preferably at least about 70% before and / or after HT, and even more preferably at least about 75% after HT. IG units have similar transmittance according to certain embodiments of this invention. Furthermore, monolithic coated articles according to certain embodiments of this invention preferably have a glass side reflectance value (R_GY%) not more than 10%, and more preferably not more than 8% before and / or after HT. Furthermore, coatings according to certain embodiments of this invention have a sheet resistance R_Sno more than about 25 ohms / square before and / or after HT, more preferably no more than about 20 ohms / square before and / or after HT, and even more preferably no more than about 15 ohms / square after HT ( low emissivity / emittance values ​​are related to this). Furthermore, in certain embodiments of this invention, the protective layers 5 and / or 9 are not more than 75% nitrated, more preferably they are not more than 50% nitrated.

Figs. 3-4 depict the results of certain Examples in terms of nitrogen gas flow for a protective layer against HT stability (ie AE * (glass side)). In particular, Fig. 3 represents the nitrogen gas flow for the protective layer 5 base (i.e. lower) versus the color stability on the glass side after HT (i.e. AE * (glass side)), illus illustrating that the color stability with HT it worsens (that is, the value of AE * increases) as the flow of nitrogen gas increases during sputtering of the protective layer 5. In a similar way, Fig. 4 represents nitrogen gas flow for upper barrier layer 9 versus glass side color stability after HT (i.e. AE * (glass side)), illustrating that color stability with HT worsens (that is, the value of AE * increases) as the nitrogen gas flow increases during sputtering of the protective layer 9. Consequently, it can be seen that extremely high nitrogen gas flows may be undesirable in certain cases if they produce an undesirably high AE *.

ES 2 296 982 T3

Certain terms are prevalently used in the glass coating art, particularly when defining the properties and sunlight performance characteristics of coated glass. These terms are used in this document according to their well-known meaning. For example, as used in this document:

Light intensity of the visible wavelength, that is, "reflectance", is defined by its percentage and is presented as R_xY or R_x (ie, the value of Y quoted later in ASTM E-308-85), where "X" is "G" for the glass side or "F" for the film side. "Glass side" (eg "G") means, viewed from the side of the glass substrate opposite the substrate on which the coating resides, while "film side" (ie "F" ) means viewed from the side of the glass substrate on which the coating resides.

Color characteristics are measured and presented in this document using CIE LAB a *, b * scale and coordinates (ie, CIE a * b * diagram, III. CIE-C, 2 degree observer). Equivalently, other similar coordinates such as by means of the subscript "h" may be used to refer to the conventional use of Hunter's Lab scale, or III. CIE-C, 10 ° observer, or the u * v * coordinates of CIE LUV. These scales are defined in this document according to ASTM D-2244-93 "Standard Test Method for Calculation of Color Differences From Instrumentally Measured Color Coordinates". Instrumentally Measured Color ”) 9/15/93 in accordance with ASTM E-308-85, Annual Book of ASTM Standards, Vol. 06.01 “Standard Method for Computing the Colors of Objects by 10 Using the CIE Systems” and / or as presented in the reference volume IES LIGHTING HANDBOOK 1981.

The terms "emittance" and "transmittance" are well understood in the art and used herein in accordance with their well-known meaning. Thus, for example, herein the term "transmittance" means solar transmittance, which is constituted by visible light transmittance (TY), infrared radiation transmittance, and ultraviolet radiation transmittance. The total solar energy transmittance (TS) is then typically characterized as a weighted average of these other values. With respect to these transmittances, visible transmittance, as indicated in this document, is characterized by the conventional CIE Illuminant technique, C, 2 degree observer, at 380-720 nm; the near infrared range is 720-2500 nm; the ultraviolet is 300-800 nm and the total solar radiation is 300-2500 nm. However, for emittance purposes, a particular infrared range (ie 2,500-40,000 nm) is employed.

Visible transmittance can be measured using known conventional techniques. For example, using a spectrophotometer, such as a Perkin Elmer Lambda 900 or Hitachi U4001, a transmission spectral curve is obtained. The visible transmission is then calculated using the ASTM 308 / 2244-93 methodology mentioned above. A smaller number of wavelength points can be used than indicated, if desired. Another technique for measuring visible transmittance is to employ a spectrometer such as a commercially available Spectrogard spectrometer manufactured by Pacific Scientific Corporation. This device measures and displays visible transmittance directly. As presented and measured in this document, visible transmittance (i.e., the value of Y in the CIE tristimulus system, ASTM E-308-85) uses III. C., observer 2 degrees.

Another term used in this document is "sheet strength". Sheet resistance (R_S) is a term well known in the art and is used herein in accordance with its well-known meaning. Here it is presented in ohms per square units. In general terms, this term refers to the resistance in ohms for any square of a layer system on a glass substrate to an electrical current passing through the layer system. Sheet resistance is an indication of how the layer or layer system is reflecting infrared energy, and in this way is often used in conjunction with emittance as a measure of its characteristics. The "sheet resistance" can be conveniently measured, for example, using a 4-point probe ohmmeter, such as a 4-point resistivity probe expendable with a head from Magnetron Instruments Corp., Model M-800, produced by Signatone Corp. . of Santa Clara, California.

"Chemical durability" or "chemically durable" are used herein synonymously with the art expression "chemically resistant" or "chemical stability." Chemical durability is determined by boiling a 2 "x 5" (5.08 x 12.70 cm) sample of a coated glass substrate in approximately 500 cc of 5% HCl for one hour (i.e., at approximately 200 ° F) (ie acid boil test above); The sample is considered to pass this test (and thus the layer system is "chemically resistant" or is considered "chemically durable" or has "chemical durability") if the sample layer system achieves a score of 3 or better and no holes larger than about 0.003 ”(0.1mm) in diameter appear after one hour of boiling.

"Mechanical durability", as used herein, is defined by the following tests. The test uses a Pacific Scientific (or equivalent) abrasion tester where a 2 ”x 4” x 1 ”(5.08 x 10.16 x 2.54 cm) nylon brush is cyclically passed over the system. layers in 500 cycles employing 150 grams of weight, applied to a 6 "x17" (15.24 x 17.78 cm) sample (ie, the above brush test). In this test, if no substantial detectable scratches appear when viewed with the naked eye in visible light, the test is deemed to have passed and the article is said to be "mechanically durable" or to have "mechanical durability" (ie, a score of 2 or better as stated above).

ES 2 296 982 T3

The terms "heat treating" and "heat treating", as used herein, mean heating the article to a temperature sufficient to allow thermal tempering, bending, or thermal reinforcement of the glass-including article. This definition includes, for example, heating a coated article to a temperature of at least about 1,100 degrees F (for example, at a temperature of about 550 degrees C to 900 degrees C) for a period sufficient to allow for tempering or cooling. curvature with heat).

Once the foregoing description is provided, many other features, modifications, and improvements will be apparent to the person skilled in the art. These other features, modifications, and improvements, therefore, are considered part of this invention, the scope of which is determined by the following claims.