Low-e matchable coated articles, and methods of making the same

The present invention relates to a method for producing a coated article and the article obtained by this method.

The present invention provides low-emissivity coated articles which, when viewed with the naked eye, have approximately the same color characteristics both before and after thermal tempering, and their method of manufacture. Such articles in some implementations combine: (1) high visible transmission characteristics, (2) good durability before and / or after heat treatment (HT), and / or a low ΔΕ * value, which is an indicator of color stability at heat treatment (HT). Such coated articles can be used monolithically, in insulating IG units, laminated window units, road vehicle windshields, and / or other road and construction vehicle applications.

DESCRIPTION OF THE CURRENT STATE OF TECHNOLOGY

Low emissivity (low E) coating systems are known in the art. For example, co-proprietary patent US 5,376,455 discloses the system: glass / Si3N4 / NiCr / Ag / NiCr / Si3N4. Unfortunately, after heat treatment, the low E coating system of US Pat. No. 5,376,455 is not sufficiently color matched to its untreated counterpart.

WO 01/40131 discloses a layer system comprising a silver layer sandwiched between two silicon nitride layers. On the other hand, the NiCr layers are placed between the silicon nitride and silver layers. However, there is room for improvement over the disclosure of this document. This document does not disclose or suggest a nitrided NiCr (NiCrNx) layer under nitrogen gas flow to provide a combination of good strength, high visible transmission, and color stability after heat treatment.

Patent documents EP 567735 and EP 796825 disclose silver-based coatings with dielectric silicon nitride layers, but do not disclose or suggest a nitrided NiCr (NiCrNx) layer under nitrogen gas flow to provide a combination of good strength, high visible light transmittance, and color stability after heat treatment.

The need for significant matchability (before heat treatment versus heat treatment) is known. Glass substrates are often produced in large sizes and cut to size to meet the needs of special economic times, such as the needs of new multi-window and door office buildings, road vehicle windows, and the like. In such applications, it is often desirable that some of these windows and / or doors be heat treated (e.g., heat treated, heat treated or hot bent) while others do not need to be heat treated. Insulating IG units and / or laminates are often used in office buildings for safety and / or thermal regulation purposes. For construction and aesthetic purposes, it is desirable that such assemblies and / or laminates that are heat treated (HT) substantially match their untreated counterparts. In addition, in certain example, but not limiting situations, good post-HT durability (e.g., scratch resistance and / or chemical durability) may reduce the need for edging so as to lower window manufacturing costs.

Co-proprietary Patent No. 5,688,585 discloses a solar regulating coated article comprising glass / Si3N4 / NiCr / Si3N4. One of the objectives of US Patent No. 5,688,585 is to provide a sputter-coated layer system which, after heat treatment (HT), is color-matched to its untreated counterpart. While the coating systems of US Patent No. 5,688,585 are excellent for their intended purpose, they do suffer from some drawbacks. In particular, they tend to have rather high emissivity and / or sheet resistance values ​​(e.g. due to the absence of a silver (Ag) layer in the embodiment of this patent).

Previously, it was possible to achieve matchability in systems other than those disclosed in the above-mentioned US Patent No. 5,688,585, but only between two different layer systems, one of which was heat treated and the other was not. The need to expand and use two different layer systems to achieve matchability causes undesirable additional production costs and inventory requirements.

PL 205 564 B1

Patent documents US 6,014,872 and US 5,800,933 (see example B) disclose a heat treatable low E layer system comprising glass / TiO2 / Si3N4 / NiCr / Ag / NiCr / Si3N4. Unfortunately, when this low E layer system is heat treated, it is not approximately color-matched to its untreated counterpart (viewed from the glass side). This is because in this low-E layer system, the value of ΔΕ * (glass side) is greater than 4.1 (i.e., in Example B, Δa *_G. is 1.49, Δb *_G. is 3.81 and ∆L * (glass side) is not measured; therefore, from equation (1) below, it follows that ∆E * on the glass side must necessarily be greater than 4.1, and possibly much greater than 4.1).

US Patent No. 5,563,734 discloses a low E coating system comprising glass / TiO2 / NiCrNx / Ag / NiCrNx / Si3N4. Unfortunately, it has been found that when high nitrogen (N) flow rates are used during the formation of NiCrNx layers [Table 1 of US Patent No. 5,563,734 indicates a high flow rate N of 143 cm³ (sccm), approximately 22 cm³ (sccm) / kW], the resulting coated articles are not color stable upon heat treatment (ie, they tend to exhibit (glass side) high ΔE * values ​​greater than 6.0). In other words, if the low E layer system of US Patent No. 5,563,734 is heat treated, it may (viewed from the glass side) not be approximately color matched to its untreated counterpart. In addition, since the layer systems of US Patent No. 5,563,734 are prone to scratching due to the high flow of nitrogen gas used in their manufacture, they tend to lack good post-HT durability.

Furthermore, it is sometimes desirable for coated articles to exhibit high visible transmission characteristics and / or good durability (mechanical and / or chemical). Unfortunately, some known measures taken to improve visible transmission characteristics and / or pre-HT durability tend to degrade post-HT durability. Thus, it is often difficult to obtain a combination of high visible radiation transmittance and good durability.

In view of the above, it is obvious to those skilled in the art that there is a need for a low E coating or layer system which after HT (viewed with the naked eye from the glass side) substantially matches in color and / or reflection to its untreated counterpart. . In other words, there is a need for a matching low E coating or layer system. There is also a need for a heat treatable system that can combine: (1) high transmissivity characteristics, (2) good durability before and / or after heat treatment, and / or (3) low ΔE * value, which is an indicator of color stability at heat treatment.

It is an object of the present invention to meet one or more of the above-mentioned needs and / or other needs that will become more apparent to the skilled person from the following description.

DISCLOSURE OF THE SUMMARY OF THE INVENTION

It is an object of the present invention to provide a low E coating or layer system having good color stability upon heat treatment (HT).

Another object of the invention is to provide a matching low E coating or layer system.

Another object of the invention is to provide a low-E coating or layer system that combines the characteristics of high visible transmission, good durability before and / or after heat treatment, and / or a low ΔE * value, which is an indicator of color stability during heat treatment. (HT). This combination may be achieved in certain example non-limiting embodiments of this invention by providing a coating including at least one barrier layer that is at least partially nitrided and that is heat treatable. In this regard, an exemplary coating or layer system may include an IR reflecting layer (e.g., Ag, Au, or the like) sandwiched between first and / or second partially nitrided metal-containing barrier layers (e.g., consisting of or including NiCrNx or other Ni-containing alloy). In some embodiments of the invention, both the first and second barrier layers may be partially nitrided (e.g., NiCrNx), while in other embodiments only one of the barrier layers should be partially nitrided (e.g., the first barrier layer consists of or includes NiCrNx). the other is of or includes NiCr). In the present invention, the term "nitrided" means and includes both total and only partial nitriding.

PL 205 564 B1

Yet another object of the invention is to provide a coating or layer system formed by adjusting the nitriding of at least one barrier layer and adjusting the thickness of the layer (s) to obtain a coating or layer system that has the ability to combine the characteristics of high visible radiation transmission, good durability, and / or low value

ΔΕ *, which is an indicator that this product, when heat treated, is substantially compatible with its untreated counterpart.

The present invention relates to a method of making a coated article comprising depositing at least one first dielectric layer on a glass substrate by depositing an array of layers on the first dielectric layer, the layer array comprising an infrared (IR) reflecting metal layer disposed between and in contact with the first dielectric layer. , first and second, layers including metal, wherein the at least one metal inclusive layer comprises NiCrN x and is at least partially nitrided, and the flow of nitrogen gas is controlled during sputtering of the metal inclusive NiCrN x layer such that the nitrogen gas flow is 4-12 cm³ (sccm) / kW, and depositing at least one second dielectric layer over the layer system, in which, before heat treatment, the glass substrate with the layer system deposited thereon has a layered resistance Rs of not more than 20 ohms / unit area, and the substrate with the deposited on it, the system of layers is subjected to heat treatment so that, as a result of the heat treatment, the substrate with the layer system deposited thereon has a ΔE * - on the glass side - not greater than 3.5.

Preferably, the heat treatment comprises heat-treating the substrate with a layer system deposited thereon, and the deposition comprises sputtering.

According to a preferred embodiment of the method according to the invention, the layer system comprises, viewed from the substrate, layers having the following thicknesses:

a) a first layer containing silicon nitride:

b) NiCrNx layer - the first layer containing metal:

c) silver layer - IR reflecting layer:

d) NiCrNx layer - the second layer containing metal:

e) a second layer containing silicon nitride:

however, as a result of heat treatment, the obtained substrate with a layer system deposited thereon has a ΔΕ * - from the glass side - not greater than 3.0 and Δa * - from the glass side - not greater than 2.0.

According to the invention, preferably each of the first and second metal-containing layers includes CrNx, or each of the first and second metal-containing layers includes Ni and N, at least one metal-containing layer being nitrided, but not more than 75% nitrided. , more preferably no more than 50%.

In an alternative embodiment of this invention, a method of making a coated article comprising depositing on a glass substrate a layer system comprising an IR reflecting metal layer interposed between and in contact with the first and second barrier layers comprises depositing the barrier layers such that they are at least partially nitrided, the flow of nitrogen gas is controlled during sputtering of at least one of the barrier layers, so that the nitrogen gas flow was 4-12 cm³ (sccm) / kW, and the substrate with the layer system deposited on it is heat treated in such a way that the substrate obtained as a result of heat treatment with the layer system deposited thereon has ΔE * - on the glass side - not greater than 3.5, with whether a nitrogen gas flow of 6-10 cm is preferably used³ (sccm) / kW.

Another object of the invention is a coated article produced by a method as defined above.

EXPLANATION OF DRAWING FIGURES

30-70 nm (300-700 A), 0.5-1.5 nm (5-15 A), 4-12 nm (40-120 A), 0.3-1.2 nm (3-12 A ), 3.5-70 nm (350-700 A),

The subject of the invention in its exemplary embodiments is shown in the drawing in which

Fig. 1 shows a partial cross-sectional side view of a layer system according to the invention.

Fig. 2 is a cross-sectional view of an insulating IG unit according to the invention in which the layer arrangement of Fig. 1 is applied.

Fig. 3 is a graph of nitrogen flow for a backing (i.e., bottom) barrier layer versus glass side color stability due to HT (i.e. ΔΕ * (glass side)) illustrating that color stability when HT is applied is lowered due to ΔΕ * increases (ie, gets worse) as the nitrogen flow increases.

PL 205 564 B1

Fig. 4 is a graph of nitrogen flow for the top (i.e. top) barrier layer versus glass side color stability due to HT (i.e. ∆Ε * (glass side)) illustrating that color stability with HT application is lowered due to ΔE * increases (ie, gets worse) as the nitrogen flow increases.

DETAILED DESCRIPTION OF CERTAIN EXAMPLE EMBODIMENTS OF THE INVENTION

Some embodiments of the present invention include a coating or layer system that may be used in applications such as insulating (IG) or monolithic insulating glass units, building windows, road vehicle windows (i.e., windshields, rear windows, etc.), and / or others. relevant applications. Some embodiments of the present 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 upon heat treatment. It has been shown how some stacks of layers make it possible to achieve this unique combination unexpectedly.

Regarding color stability, some embodiments of the present invention exhibit excellent color stability (i.e., a low ΔE * value and / or a low Δa * value, where Δ is the change due to heat treatment) upon heat treatment (e.g., tempering, bending, or thermal processing). heat strengthening), both monolithically and / or in the context of a two-panel environment such as insulating IG units or road vehicle windshields. Such heat treatments (HTs) often require the substrate to be coated to be heated to a temperature from at least about 1100 ° F (593 ° C) up to 1450 ° F (788 ° C) (more preferably from about 593 ° C to 788 ° C (1100 to 1200 ° F). ), and most preferably from 621 to 788 ° C (1150 to 1200 degrees F) for a period of time sufficient to achieve the end result (e.g., tweak, bend, and / or heat strengthen). Some embodiments of the invention combine (i) color stability upon heat treatment, and (ii) the use of a silver-inclusive layer for selective IR reflection. Some embodiments of the invention combine (i) and (ii), together with (iii) high visible transmission, (iv) good durability and / or (v) blue-green quadrant color (i.e. of the third quadrant) of the CIE LAB color atlas when a clear and / or green glass substrate is used, although the invention may, of course, be used in the context of other colors. Some embodiments of the invention combine (i) through (v), together with (iv) the low emissivity feature.

Figure 1 is a partial cross sectional side view of a coated article of this invention. The coated article comprises a substrate 1 (e.g., a clear, green, brown, gray, blue, or blue-green glass substrate from about 1.0 to 12.0 mm thick), a first dielectric layer 3 (e.g., consisting of or including nitride silicon (i.e. Si₃N₄), titanium dioxide, tantalum pentoxide, zirconium oxide, silicirconium nitride, tin oxide, silicon oxide, silicon dioxide, or silicon oxynitride), a first partially nitrided metal-containing barrier layer (e.g., consisting of or including NiCrN_x and / or CrN_x), an infrared (IR) reflecting layer 7 (e.g., consisting of or including Ag, Au or the like), a second or upstream metal-containing barrier layer 9, which optionally may also be at least partially nitrided (e.g. or containing Ni, NiCr, NiCrN_x and / or CrN_x), and a second or top dielectric layer 11 (e.g., consisting of or including silicon nitride (e.g., Si3N4), titanium dioxide, tantalum pentoxide, silicon nitride, zirconium oxide, tin oxide, silicon oxide, silicon dioxide, or silicon oxynitride) . Other layer (s) may also be used below or above the depicted coating system. Thus, when the coating or layer system is "on" or "supported by" substrate 1 (directly or indirectly), other layer (s) may be interposed therebetween. Thus, for example, the layer arrangement of Fig. 1 may be considered "on" substrate 1 even though other layer (s) are interposed therebetween (for example, when layer 3 comprises silicon nitride, between substrate 1 and dielectric layer 3 may be layer of TiO2). Additionally, it will be apparent to those skilled in the art that the coating or layer system 3-11 of Fig. 1 may be as shown or, alternatively, may be repeated on itself one or more times so as to form a double or triple silver layer stack.

The IR reflecting layer 7 preferably consists of or includes Ag, although it is accepted that some small amounts of oxidation may be present therein. Thus, in some embodiments of this invention, layer 7 is oxidized to no more than about 10%, more preferably no more than 1%, and most preferably no more than 0.5%.

It has surprisingly been found that by controlling the nitrogen (N) flow used during the cathodic sputtering of the barrier layer (s) 5 and / or 9, and / or controlling the thickness of the layer 5 and / or 9, a resultant coated article can be obtained which combines high transmittance.

Visible radiation, good durability before and / or after HT, and good color stability when applied with heat treatment (HT). For example, by controlling the degree of nitriding of barrier layer (s) 5 and / or 9 (due to N gas flow during sputtering) at low to moderate level (s) and / or their thickness at low to moderate gas flow level (s), the resultant coated article with a lower ΔE * value. The following examples illustrate, by way of example and not limitation, the unexpectedly unsuccessful findings that at high N2 gas flows for the barrier layer (s) the color stability is lowered (ie, ∆E * increases) and / or the post-HT durability is lowered. However, it has surprisingly been found that by partially nitriding one or more barrier layers (e.g. for resistance purposes, such as improving scratch resistance and / or chemical durability) at lower N-gas flows₂, much lower and therefore better ∆E * values ​​(for example, as shown in Figs. 3-4) and / or better post-HT stability are obtained. In some embodiments of the invention, both barrier layers 5,9 may be partially nitrided (symmetrically or asymmetrically), while in other embodiments one of the barrier layers may be partially nitrided while the other barrier layer is not nitrided (i.e. essentially metallic).

When the barrier layers 5,9 include NiCr (nitrided or unnitrided), the respective amounts of Ni and Cr may be, as a weight percent, 80/20 nickel / chromium, 90/10 nickel / chromium, 50/50 nickel / chromium, or whatever. other appropriate amounts. It is obvious to those skilled in the art that other materials may be used for the barrier layers 5, 9 (e.g. other Ni-containing alloys may be used, niobium or niobium oxide may be used, etc.). For example, a conventional sputter cathodic sputtering assembly such as the G-49 multi-chamber sputtering cathodic sputtering device manufactured by Airco, Inc. may be used to form the coating layer systems of the invention.

Furthermore, when barrier layers 5 and 9 contain NiCr (nitrided or unnitrided), the metals of these layers may contain Ni and / or Cr, or alternatively, the sputter anticathode used to form layers 5 and / or 9 may be an inconel or Haynes 214 alloy with basic weight composition (as a nominal composition):

<td>Element</td><td>Weight%</td>

<td>Ni</td><td> 75,45</td>

<td>Fe</td><td> 4,00</td>

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

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

<td>Al</td><td> 4,40</td>

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

Fig. 2 shows the coating or layer system 22 of Fig. 1 applied to surface # 2 of an IG window unit. In order to distinguish the "inner side" of the IG unit from its "outer side", the sun 19 is schematically shown on the outside. On the outside, the IG insulating glass unit has a glass plate or pane 21, and on the inner side a glass plate or pane 23. Thus, coated articles herein may consist of one of two IG units (i.e., one coated) or, alternatively, of a complete IG unit including both panes. The two glass substrates (for example, 1 mm to 12 mm thick float glass) are sealed at the outer rim with conventional sealant 25 and provided with a conventional drying tape 27. The panes are then secured in a conventional window or door frame 29 (shown in fragmentary schematic form). By sealing the outer periphery of the glass panes and replacing the air in the insulating space (or chamber) with a gas such as argon, a conventional high insulating IG insulating glass unit is formed. Optionally, in some alternative embodiments of the invention, a sub-atmospheric pressure may be present in the insulating space 30, although, of course, this is not necessary in all implementations. Either the inner walls 24 or 26 (or both) may be provided with the layer system or coatings of the invention (as for example shown in Fig. 1). In the embodiment shown in Fig. 2, the inner wall 24 (i.e. the surface # 2) of the outer glass pane 21 is provided with the arrangement of layers according to Fig. 1, coated by sputtering.

PL 205 564 B1

Returning to Fig. 1, where various thicknesses may be used to meet one or more of the purposes and / or needs discussed herein, in accordance with certain example embodiments of this invention, the preferred thicknesses and materials for the respective layers on the glass substrate 1 are provided below.

Table 1: (Thickness)

<td>Layer material</td><td>Favorable range nm (A)</td><td>More preferred nm (A)</td><td>Most preferred nm (A)</td>

<td rowspan="2">Si3N4 (layer 3)</td><td>30-70 nm</td><td>40-55 nm</td><td>45-55 nm</td>

<td>(300-700 A)</td><td>(400-550 A)</td><td>(450-550 A)</td>

<td rowspan="2">NiCrNx (layer 5)</td><td>0.3-3 nm</td><td>0.5-1.5 nm</td><td>0.8-0.9 nm</td>

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

<td rowspan="2">Ag (layer 7)</td><td>4-12 nm</td><td>5-10 nm</td><td>6-8 nm</td>

<td>(40-120 A)</td><td>(50-100 A)</td><td>(60-80 A)</td>

<td>NiCr or NiCrN_x (layer 9)</td><td>0.3-3 nm (3-30 A)</td><td>0.3-1.2 nm (3-12 A)</td><td>0.6-0.7 nm (6-7 A)</td>

<td rowspan="2">Si3N4 (layer 11)</td><td>35-70 nm</td><td>40-60 nm</td><td>45-55 nm</td>

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

As shown above in Table 1, the underlying barrier layer 5 may or may not be nitrided in various embodiments of the invention. It has been surprisingly found that controlling the amount of nitriding of the barrier layer (s) 5 and / or 9 at low to moderate levels can result in a significant improvement in the color stability of the coating due to heat treatment (i.e. a lower ΔE * value) (as for example shown in Fig. 3-4). Such nitriding can also improve post-HT stability. Additionally, in one exemplary embodiment, certain thicknesses of the upstream dielectric layer 11 have been found to improve the ∆E * value when the downstream dielectric layer 3 is about 0-25% thinner than the upstream dielectric layer 11, more preferably about 5-15%. thinner, and most preferably about 8-10% thinner. It is believed that one or more of these characteristics contribute to the matchability or lower ΔE * values ​​(as described below) associated with some embodiments of the invention (i.e., improved stability using heat treatment). Each of the above-mentioned combinations of low-E system with good stability (color and / or durability) to heat treatment is considered to be novel and inventive.

In some exemplary embodiments, the stability to heat treatment contributes to substantial compatibility between the heat treated and non-heat treated versions of the coating or layer system. In other words, in monolithic and / or composite insulating (IG) applications, in some embodiments of this invention, two glass substrates having the same coating system thereon (one post-deposited heat-treated and the other not heat-treated) when viewed with the naked eye as viewed from the side. the glass of the article (i.e. when viewed through at least one glass substrate prior to viewing the coating), look substantially the same. It has also been found in other embodiments of the present invention that the compatibility (achievable in monolithic applications) may be even better in IG composite applications and / or laminate applications.

The value of ∆Ε * is significant in determining whether, when applying heat treatment (HT) in the context of the present invention, there is or no match or substantial match. Color is defined herein with reference to conventional a *, b * quantities, which in some embodiments of the present invention are both negative in order to provide color in a desired, substantially neutral, color space tending to the blue-green quadrant. For example, the term ∆a * simply indicates how much the color value of a * changes due to heat treatment.

The term ∆E * (and ∆E) is well understood in the art and discussed, along with various techniques for its definition, in ASTM 2244-93, as well as in Hunter et al., The Measurement of Appearance, 2^{n / a} Ed. Cptr. 9, page 162 et seq. [John Wiley &amp; Sons, 1987]. As used in the art, ∆Ε * (and ∆Ε) is a way of adequately expressing the change (or lack thereof) in reflectance and / or transmittance (and thus, also, color appearance in the article after or due to HT. ", Or the Hunter technique (denoted by using the subscript" H "). ΔE corresponds to the Hunter Lab L, a, b (or L_h, a_h, b_h). Similarly, ΔE * corresponds to the CIE LAB L *, a *, b * scale. Both techniques are considered useful and equivalent for the purposes of the present invention. At the 8

For example, as described in Hunter et. al., a rectangular coordinate / scale technique (CIE LAB 1976) known as the L *, a *, b * scale can be used, where:

L * is the amount of lightness (CIE 1976), and * is the amount of red-green (CIE 1976), b * is the amount of yellow-blue (CIE 1976), and the color difference ΔΕ * between L *₀and*₀b *₀ and L *₁and*₁b *₁ is calculated using the formula:

ΔΕ * = [(AL *)² + (Δα *)² + [^ b *)²]^1/2 (1) in which:

AL * = L * 1 - L * 0 (2)

Δa * = a *₁ - a *₀ (3)

Ab * = b * i - b * o (4) where the subscript "0" is the coating (coated article) before heat treatment and the subscript "1" is the coating (coated article) after heat treatment; the notations used (for example L *, a *, b *) are calculated by the above-mentioned L *, a *, b * coordinate technique (CIE LAB 1976). In a similar way, ΔΕ can be calculated using equation (1) by replacing L *, a *, b * with the quantities L_h, a_h, b_h, according to Hunter Lab. Within the scope of the present invention and the quantification of ∆Ε *, there are also equivalent designations as long as they are converted to those calculated by any other technique applicable to the same ∆Ε * concepts as defined above.

In some embodiments of this invention, the layer systems applied to transparent monolithic glass substrates (e.g., 4 mm thick glass substrates, for exemplary reference purposes) prior to heat treatment, as viewed from the glass side of the coated article, have the following color (RG%).

Table 2: Color (R_G.) before heat treatment

<td></td><td>Ordinary</td><td>Profitable</td>

<td>and*</td><td>0.0 to -5.0</td><td>0.0 to -2.0</td>

<td>b *</td><td>-1.0 to -10.0</td><td>-5.0 to -9.0</td>

After heat treatment, in some embodiments of this invention, the layer systems applied to transparent monolithic glass substrates as viewed from the glass side (G) (as opposed to the layer side) of the coated article have the following color characteristics ∆Ε * and ∆a *.

Table 3: Color characteristics AE * g after heat treatment

<td rowspan="2"></td><td>Ordinary</td><td>More favorable</td><td>The most advantageous</td>

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

<td>AE * g</td><td> &lt; = 3,5</td><td> &lt; = 3,0</td><td> &lt; = 2,6</td>

<td>Aa * G</td><td> &lt; = 2,0</td><td> &lt; = 1,0</td><td> &lt; = 0,7</td>

Accordingly, as shown in Table 3, coated articles according to some embodiments of this invention exhibit a ∆Ε * (glass side) of no greater than 3.5, more preferably no greater than 3.0, even more preferably no greater than 2.6 (and most preferably &lt;= 2.0). When this wider range is obtained, the result is matchability.

Examples 1-15 (Nitriding barrier layer (s))

The following fifteen example coated articles of the present invention were made (each annealed and heat treated). In each of Examples 1-8, 11, and 15, the layer system was glass / Si3N4 / NiCrNx / Ag / NiCrNx / Si3N4 (as exemplified in Fig. 1, with N gas flowing during the sputtering of both barrier layers 5 and 9, nitriding them), although the present invention is not expressly limited thereto. In each of Examples 12-14, the layer system was: glass / Si3N4 / NiCrNx / Ag / NiCr / Si3N4 (as exemplified in Fig. 1, but no N gas was flowing during sputtering the upper barrier layer 9). In contrast, in each of Examples 9-10, the layer system was glass / Si3N₄/ NiCr / Ag / NiCr / Si3N₄ (as exemplified in Fig. 1, but no N gas flowed during the sputtering of each barrier layer 5, 9). It is shown below in Examples 9-10 (there was no N-gas flow for layers 5, 9) that there is no durability compared to the examples where N-gas flow was used while sputtering one

Or more barrier layers. Moreover, it has been shown that by controlling the N-gas flow while sputtering one or both of the barrier layers, the ΔE * value of the resulting coating or layer system can be improved (i.e. reduced). In each of these examples, the substrate was 4mm thick substantially clear soda-lime-silicate glass, and each example was monolithic (not IG). The settings for the coating process in which a BOC inline continuous coater (BOC ILS) was used were, for example, as follows.

The reflection layer 7 and the dielectric layers 3, 11 were the same in all fifteen examples. In each of Examples 1-15, silver layer 7 was metallic (sputtered using a metallic silver flat anti-cathode), approximately 7.9 nm (79 A) thick, with layer 7 sputtered at approximately 2.95 kW, voltage 465 V, 30 cm of Ar gas flow³ (sccm) / kW and a pressure of about 0.3599 N / m² (2.7 mTorr) and at a line speed setting of 100 IPM (one pass) with anti-cathode masking to the opening of 1.9 cm (0.75), and had sheet resistance Rs of about 16 ohms / unit surface. In each of Examples 1-15, the underlying Si3N4 layer 3 was about 47 nm (470 Å) thick, and was sputtered using a SiC-Mag anti-cathode (about 10% Al), power of about 1 kW, voltage of 485 V, the flow of Ar gas in the amount of 40 cm³ (sccm) / kW and N in the amount of 40 cm³ (sccm) / kW and a pressure of about 0.3333 N / m² (2.5 mTorr) cm³ (sccm) / kW, with line speed setting of 55 IPM (eight passes). In each of examples 1-15, layer 11 of Si₃N₄the upper one was about 51 nm (510 A) thick, it was sputtered using a SiC-Mag anti-cathode (with an Al content of about 10%), using a power of about 1 kW, a voltage of 485 V, a gas flow of 40 cm Ar³ (sccm) and N in the amount of 40 cm³ (sccm), and at a linear speed setting of 50 IPM (eight passes).

Thus, examples 1-15 differed in that the barrier layer (s) 5 and / or 9 were deposited / sputtered differently (e.g. with different N flows and / or to different thicknesses). In Examples 1-15, when sputtering the barrier layers 5 and 9, planar sputtering anticathodes of Ni: Cr (80/20) composition and 30 cm of Ar gas flow were used.³ (sccm). Instead, in order to obtain the different thicknesses of the barrier layers 5, 9 mentioned below, the flow of nitrogen gas (N) [cm³(sccm) / kW power], linear speed and power were different in different examples 1-15. In the table 4 below, "Bar." means a barrier layer (for example, Bar. 5 means an overlying barrier layer 5, while Bar. 9 means an overlying barrier layer 9 or the second one in Fig. 1). Besides, in Table 4, "Grub." is the thickness in nm (A) and "Bar. Flow N₂"Is the nitrogen gas flow [cm³ (sccm) / kW power] when spraying the appropriate barrier layer.

Table 4: Examples 1-15 (sputter deposited)

<td>Example #</td><td>Bar. 5 Mat '1</td><td>Bar. 5 Thick.</td><td>Bar. 5 N2 flow</td><td>Bar. 9 Mat '1</td><td>Bar. 9 Thick.</td><td>Bar. 9 N2 flow</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>

<td> 1</td><td>NiCrNx</td><td>1.2 nm (12 A)</td><td>8 cm³ / kW (sccm) / kW</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>8 cm³ / kW (sccm) / kW</td>

<td> 2</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>8 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.6 nm (6 A)</td><td>8 cm³/ kW (sccm) / kW</td>

<td> 3</td><td>NiCrNx</td><td>0.6 nm (6 A)</td><td>16 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.3 nm (3 A)</td><td>16 cm³/ kW (sccm) / kW</td>

<td> 4</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>16 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.6 nm (6 A)</td><td>16 cm³/ kW (sccm) / kW</td>

<td> 5</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>32 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.6 nm (6 A)</td><td>32 cm³/ kW (sccm) / kW</td>

<td> 6</td><td>NiCrNx</td><td>1.2 nm (12 A)</td><td>32 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>32 cm³(sccm) / kW</td>

<td> 7</td><td>NiCrNx</td><td>0.6 nm (6 A)</td><td>32 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.3 nm (3 A)</td><td>32 cm³/ kW (sccm) / kW</td>

<td> 8</td><td>NiCrNx</td><td>1.2 nm (12 A)</td><td>16 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>16 cm³/ kW (sccm) / kW</td>

PL 205 564 B1 cont. table 4

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>

<td> 9</td><td>NiCr</td><td>0.6 nm (6 A)</td><td>0 cm³/ kW (sccm) / kW</td><td>NiCr</td><td>0.3 nm (3 A)</td><td>0 cm³/ kW (sccm) / kW</td>

<td> 10</td><td>NiCr</td><td>0.9 nm (9 A)</td><td>0 cm³/ kW (sccm) / kW</td><td>NiCr</td><td>0.6 nm (6 A)</td><td>0 cm³/ kW (sccm) / kW</td>

<td> 11</td><td>NiCrNx</td><td>0.6 nm (6 A)</td><td>8 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.3 nm (3 A)</td><td>8 cm³/ kW (sccm) / kW</td>

<td> 12</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>8 cm³/ kW (sccm) / kW</td><td>NiCr</td><td>0.6 nm (6 A)</td><td>0 cm³/ kW (sccm) / kW</td>

<td> 13</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>8 cm³/ kW (sccm) / kW</td><td>NiCr</td><td>0.6 nm (6 A)</td><td>0 cm³/ kW (sccm) / kW</td>

<td> 14</td><td>NiCrNx</td><td>0.9 nm (9 A)</td><td>16 cm³/ kW (sccm) / kW</td><td>NiCr</td><td>0.6 nm (6 A)</td><td>0 cm³(sccm) / kW</td>

<td> 15</td><td>NiCrNx</td><td>0.6 nm (6 A)</td><td>8 cm³/ kW (sccm) / kW</td><td>NiCrNx</td><td>0.6 nm (6 A)</td><td>8 cm³(sccm) / kW</td>

After spraying onto a glass substrate as outlined above, Examples 1-15 were tested both before and after heat treatment (HT) and found to have, monolithically (not IG glazing) the following characteristics, the heat treatment being heat toughening monolithic product in a conventional oven at approximately 621 ° C (1,150 ° F) for ten minutes (Note: in Table 5 and below, the values ​​of the a * and b * color coordinates correspond to a two degree technical observer according to CIE LAB 1976, I11. CIE-C, 2 degree observer technique). A two-degree normal observer (I11.C, 2 degree standard) was also used to determine the radiation transmissivity in the visible range, etc. It should also be noted that to test adhesion, a "tape test was performed in accordance with the military standard, MIL-AA-113, incorporated herein." An acid boil test for 1 hour was performed to test the chemical stability. For the acid boil test, tape test, brush test and scratch test, the results are presented on an increasing scale from 0 to 5, with 0 being the best result and 5 being the worst result. Specifically, 0 means no change or damage (all based on visual observation), 1 means barely visible changes, 2 means slight changes, 3 means more obvious changes than 2, but still to a limited extent, 4 means visible damage more severe than 3 , but in a limited area, a 5 indicates very serious damage to the point of complete destruction / decay.

Table 5: Characteristics of examples 1-15 (monolithic)

EXAMPLE 1

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

<td> 1</td><td> 2</td><td> 3</td>

<td>Transmission (TY)%:</td><td> 73,57</td><td> 77,12</td>

<td>and\:</td><td> -2,35</td><td> -2,74</td>

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

<td>Reflectance when viewed from glass (G): R._G.Y (%):</td><td> 8,04</td><td> 6,86</td>

<td>L g:</td><td> 34,06</td><td> 31,48</td>

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

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

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 2,6</td>

<td>Δa *_G. (absolute value):</td><td></td><td> 0,36</td>

PL 205 564 B1 cont. example 1

<td> 1</td><td> 2</td><td> 3</td>

<td>Reflectance as seen from the film / coating side (F): RFY (%):</td><td> 3,62</td><td> 3,53</td>

<td>a * F:</td><td> 5,30</td><td> 3,38</td>

<td>b * F:</td><td> -6,00</td><td> -6,52</td>

<td>R_s: (layer resistance ohm / unit area)</td><td> 15,50</td><td> 12,60</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 0</td>

<td>Scratch test:</td><td> 2</td><td> 1</td>

EXAMPLE 2

<td colspan="3"></td>

<td rowspan="2">Size / Measure</td><td>Before processing</td><td>After processing</td>

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

<td>Transmission (TY)%:</td><td> 75,12</td><td> 79,52</td>

<td>and\:</td><td> -2,25</td><td> -2,53</td>

<td>b * T:</td><td> -0,81</td><td> -0,78</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 7,97</td><td> 7,05</td>

<td>L g:</td><td> 33,92</td><td> 31,92</td>

<td>a * G:</td><td> -1,11</td><td> -1,10</td>

<td>bg:</td><td> -7,38</td><td> -7,79</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 2,0</td>

<td>Aa * G (absolute value):</td><td></td><td> 0,01</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 3,89</td><td> 3,88</td>

<td>a * F:</td><td> 4,24</td><td> 1,45</td>

<td>b * F:</td><td> -6,16</td><td> -8,05</td>

<td>Rs: (layer resistance ohm / unit area)</td><td> 16,70</td><td> 12,90</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 0</td>

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

<td>EXAMPLE 3</td><td></td><td></td>

<td rowspan="2">Size / Measure</td><td>Before processing</td><td>After processing</td>

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

<td> 1</td><td> 2</td><td> 3</td>

<td>Transmission (TY)%:</td><td> 79,35</td><td> 81,96</td>

<td>a * T:</td><td> -2,07</td><td> -1,90</td>

<td>b * T:</td><td> -0,17</td><td> -0,44</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 7,72</td><td> 7,31</td>

PL 205 564 B1 cont. example 3

<td> 1</td><td> 2</td><td> 3</td>

<td>L g:</td><td> 33,39</td><td> 32,50</td>

<td>a * G:</td><td> -1,32</td><td> -1,72</td>

<td>bg:</td><td> -6,43</td><td> -6,80</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 1,0</td>

<td>Δa *_G. (absolute value):</td><td></td><td> 0,4</td>

<td>Reflectance from film / repeat side (F): R._F.Y (%):</td><td> 4,59</td><td> 4,77</td>

<td>af:</td><td> 2,19</td><td> 0,31</td>

<td>b * F:</td><td> -5,80</td><td> -7,33</td>

<td>R_s: (layer resistance ohm / unit area)</td><td> 17,20</td><td> 14,30</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

<td>Brush test:</td><td> 1</td><td> 3</td>

<td>Cooking in kvass:</td><td> 0</td><td> 1</td>

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

EXAMPLE 4

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

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

<td>at:</td><td> -2,03</td><td> -2,52</td>

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

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 8,21</td><td> 8,86</td>

<td>L g:</td><td> 34,42</td><td> 35,36</td>

<td>a * G:</td><td> -1,71</td><td> -1,84</td>

<td>bg:</td><td> -6,60</td><td> -4,48</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 2,3</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,13</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 4,20</td><td> 4,20</td>

<td>a * F:</td><td> 2,79</td><td> 0,73</td>

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

<td>Rs: (layer resistance ohm / unit area)</td><td> 16,50</td><td> 18,20</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 5</td>

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

PL 205 564 B1

EXAMPLE 5

<td colspan="3"></td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

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

<td>a * T:</td><td> -2,23</td><td> -1,56</td>

<td>bV</td><td> -0,02</td><td> -0,85</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 8,29</td><td> 21,69</td>

<td>L g:</td><td> 34,57</td><td> 53,70</td>

<td>a * G:</td><td> -0,96</td><td> -0,96</td>

<td>bg:</td><td> -7,80</td><td> -7,80</td>

<td>ΔE * (i.e. glass side (G)):</td><td></td><td> 19,1</td>

<td>Δa * G (absolute value):</td><td></td><td> 0</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 3,96</td><td> 17,83</td>

<td>a * F:</td><td> 4,38</td><td> 4,38</td>

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

<td>Rs: (layer resistance ohm / unit area)</td><td> 17,20</td><td>on</td>

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

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

<td>Cooking in kvass:</td><td> 0</td><td> 5</td>

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

<td colspan="3">EXAMPLE 6</td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

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

<td>a * T:</td><td> -2,22</td><td> -2,09</td>

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

<td>Reflectance when viewed from glass (G): R._G.Y (%):</td><td> 8,46</td><td> 14,35</td>

<td>L g:</td><td> 34,91</td><td> 44,74</td>

<td>a * G:</td><td> -1,41</td><td> -0,97</td>

<td>bg:</td><td> -6,97</td><td> 3,40</td>

<td>ΔE * (i.e. glass side (G)):</td><td></td><td> 14,3</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,44</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 3,85</td><td> 10,70</td>

<td>a * F:</td><td> 4,46</td><td> 2,70</td>

<td>b * F:</td><td> -6,7</td><td> 5,45</td>

<td>R_s: (layer resistance ohm / unit area)</td><td> 16,30</td><td>on</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 5</td>

<td>Scratch test:</td><td> 3</td><td> 2</td>

PL 205 564 B1

EXAMPLE 7

<td colspan="3"></td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

<td>Transmission (TY)%:</td><td> 79,08</td><td> 77,88</td>

<td>a * T:</td><td> -1,72</td><td> -2,27</td>

<td>bV</td><td> -0,44</td><td> -2,16</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 7,81</td><td> 10,17</td>

<td>L g:</td><td> 33,59</td><td> 38,14</td>

<td>a * G:</td><td> -2,38</td><td> -2,19</td>

<td>bg:</td><td> -5,88</td><td> -1,72</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 6,2</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,19</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 4,83</td><td> 6,97</td>

<td>a * F:</td><td> 0,14</td><td> -0,46</td>

<td>b * F:</td><td> -4,20</td><td> -2,68</td>

<td>R_s: (layer resistance ohm / unit area)</td><td> 16,70</td><td> 22,70</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 5</td>

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

<td colspan="3">EXAMPLE 8</td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

<td>Transmission (TY)%:</td><td> 74,04</td><td> 71,55</td>

<td>a * T:</td><td> -2,29</td><td> -2,27</td>

<td>b * T:</td><td> -0,67</td><td> -3,36</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 8,36</td><td> 10,73</td>

<td>L g:</td><td> 34,72</td><td> 39,12</td>

<td>a * G:</td><td> -1,01</td><td> -1,46</td>

<td>bg:</td><td> -7,67</td><td> -1,14</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 7,9</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,45</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 3,72</td><td> 6,92</td>

<td>af:</td><td> 5,26</td><td> 2,06</td>

<td>b * F:</td><td> -7,58</td><td> 0,84</td>

<td>Rs: (layer resistance ohm / unit area)</td><td> 15,50</td><td> 25,80</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 4</td>

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

PL 205 564 B1

EXAMPLE 9

<td colspan="3"></td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

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

<td>and\:</td><td> -2,10</td><td> -2,27</td>

<td>bV</td><td> -0,13</td><td> 0,07</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 7,82</td><td> 7,37</td>

<td>L g:</td><td> 33,61</td><td> 32,63</td>

<td>a * G:</td><td> -1,25</td><td> -1,33</td>

<td>bg:</td><td> -6,53</td><td> -6,68</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 1,0</td>

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

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 4,58</td><td> 4,91</td>

<td>a * 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: (layer resistance ohm / unit area)</td><td> 17,40</td><td> 10,30</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

<td>Brush test:</td><td> 1</td><td> 05</td>

<td>Cooking in kvass:</td><td> 0</td><td> 5</td>

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

<td colspan="3">EXAMPLE 10</td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

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

<td>and\:</td><td> -2,27</td><td> -2,42</td>

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

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 8,74</td><td> 7,28</td>

<td>L g:</td><td> 35,49</td><td> 32,43</td>

<td>a * G:</td><td> -1,42</td><td> -1,38</td>

<td>bg:</td><td> -7,00</td><td> -7,23</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 3,1</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,04</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 4,02</td><td> 4,28</td>

<td>af:</td><td> 4,11</td><td> 0,74</td>

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

<td>Rs: (layer resistance ohm / unit area)</td><td> 16,40</td><td> 12,80</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 5</td>

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

PL 205 564 B1

EXAMPLE 11

<td colspan="3"></td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

<td>Transmission (TY)%:</td><td> 79,12</td><td> 81,72</td>

<td>a * T:</td><td> -1,91</td><td> -2,62</td>

<td>b * T:</td><td> -0,27</td><td> -0,89</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 7,77</td><td> 7,10</td>

<td>L g:</td><td> 33,49</td><td> 32,04</td>

<td>a * G:</td><td> -1,95</td><td> -1,95</td>

<td>bg:</td><td> -6,10</td><td> -6,10</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 1,5</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,0</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 4,62</td><td> 4,62</td>

<td>a * F:</td><td> 1,20</td><td> 1,20</td>

<td>b * F:</td><td> -5,34</td><td> -5,34</td>

<td>R_s: (layer resistance ohm / unit area)</td><td> 17,70</td><td> 12,90</td>

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

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

<td>Cooking in kvass:</td><td> 0</td><td> 5</td>

<td>Scratch test:</td><td> 2</td><td> 3</td>

<td colspan="3">EXAMPLE 12</td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

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

<td>a * T:</td><td> -2,5</td><td> -2,8</td>

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

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 8,5</td><td> 7,4</td>

<td>L g:</td><td> 35,0</td><td> 32,7</td>

<td>a * G:</td><td> -0,6</td><td> -0,8</td>

<td>bg:</td><td> -8,3</td><td> -7,9</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 2,4</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,2</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 3,9</td><td> 3,9</td>

<td>af:</td><td> 5,7</td><td> 1,8</td>

<td>b * F:</td><td> -12,2</td><td> -10,8</td>

<td>Rs: (layer resistance ohm / unit area)</td><td> 16,7</td><td> 13,2</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 3</td>

<td>Scratch test:</td><td> 2,5</td><td> 1,5</td>

PL 205 564 B1

EXAMPLE 13

<td colspan="3"></td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

<td>Transmission (TY)%:</td><td> 76,7</td><td> 79,4</td>

<td>a * T:</td><td> -2,7</td><td> -3,0</td>

<td>b * T:</td><td> 0,5</td><td> -0,7</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 8,0</td><td> 7,5</td>

<td>L g:</td><td> 34,0</td><td> 32,9</td>

<td>a * G:</td><td> -0,2</td><td> -0,4</td>

<td>bg:</td><td> -8,2</td><td> -8,1</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 1,2</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,2</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 3,9</td><td> 3,9</td>

<td>a * 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: (layer resistance ohm / unit area)</td><td> 17,1</td><td>on</td>

<td>Tape test:</td><td>on</td><td>on</td>

<td>Brush test:</td><td>on</td><td>on</td>

<td>Cooking in kvass:</td><td>on</td><td>on</td>

<td>Scratch test:</td><td>on</td><td>on</td>

<td colspan="3">EXAMPLE 14</td>

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

<td>Transmission (TY)%:</td><td> 75,5</td><td> 79,1</td>

<td>a * T:</td><td> -2,3</td><td> -2,6</td>

<td>b * T:</td><td> -0,5</td><td> -1,2</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 8,3</td><td> 7,4</td>

<td>L g:</td><td> 34,6</td><td> 32,8</td>

<td>a * G:</td><td> -1,2</td><td> -1,3</td>

<td>bg:</td><td> -7,5</td><td> -7,0</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 1,9</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,1</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 3,9</td><td> 4,2</td>

<td>af:</td><td> 4,6</td><td> 1,2</td>

<td>b * F:</td><td> -8,6</td><td> -7,6</td>

<td>Rs: (layer resistance ohm / unit area)</td><td> 16,6</td><td> 13,5</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 3</td>

<td>Scratch test:</td><td> 2</td><td> 3,5</td>

PL 205 564 B1

EXAMPLE 15

<td>Size / Measure</td><td>Before processing</td><td>After processing</td>

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

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

<td>a * T:</td><td> -2,3</td><td> -2,8</td>

<td>b * T:</td><td> -0,1</td><td> -0,7</td>

<td>Reflectance as seen from the glass side (G): RgY (%):</td><td> 7,9</td><td> 6,8</td>

<td>L g:</td><td> 33,7</td><td> 31,4</td>

<td>a * G:</td><td> -0,5</td><td> -0,5</td>

<td>bg:</td><td> -8,0</td><td> -7,9</td>

<td>ΔΕ * (i.e. glass side (G)):</td><td></td><td> 2,4</td>

<td>Δa * G (absolute value):</td><td></td><td> 0,0</td>

<td>Reflectance as seen from the film / coating side (F): RfY (%):</td><td> 4,2</td><td> 4,1</td>

<td>a * 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: (layer resistance ohm / unit area)</td><td> 17,0</td><td> 13,3</td>

<td>Tape test:</td><td> 0</td><td> 0</td>

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

<td>Cooking in kvass:</td><td> 0</td><td> 3</td>

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

As can be seen from the above, each of Examples 1-4 and 12-15 performed well in determining each of the characteristics (a) of good matchability because, viewed from the glass side (G) of the respective article, ΔΕ * was not more than 2. 5, preferably no more than 2.0, (b) a high visible transmission of at least 70% (and even, more preferably, at least 74% in some embodiments). and (c) good durability with determinations covering the totality of the tape test, brush test, acid boil test and / or scratch test results, both before and after HT. It is most desirable that coated articles be satisfactory in all three (a) - (c) areas. In addition, each of Examples 1-4 and 12-15 were considered to be heat treatable such that the coating would not be damaged during HT (e.g., had no peeling, pores, cracks, or haze). Unfortunately, Examples 5-8 showed bad results in determining the matchability (i.e. very high ∆Ε * value on the glass side). The bad match results (before vs. after HT) associated with Examples 5-8 are assumed to be a result of (i) the thickness of the barrier layers and / or (ii) the high flow of nitrogen (N) gas during the deposition of the barrier layer (s). For example, for Examples 1-2 (the most complete combination of durability and matchability before versus post-HT), each of Examples 1-2 used a nitrogen flow of 8 cm when sputtering the barrier layer (s).³ (sccm) / kW, while in Examples 5-7 (poor pre-match versus post-HT) a much higher nitrogen gas flow of 32 cm was used during the deposition of the barrier layer³(sccm) / kW. The comparison between examples 3-4 and example 8 illustrates that the thickness of the barrier layer (s) is also significant (i.e., the applied flow rate N of 16 cm³(sccm) / kW, the lower thickness / thicknesses of the barrier layers in examples 3-4 render these coated articles pre-conformable compared to post-HT, while the greater / greater layer / layer thicknesses in example 8 make the latter the coated article has such a high ∆Ε * value of 7.9, hence poor matchability). Examples 9-10 showed good matchability but bad durability (e.g., bad brush test); this is supposed to be due to the fact that there was no N flow during the sputtering of the barrier layers. Examples 1214 (N-flow when sputtering the lower barrier layer 5 but no N-flow when sputtering the upper barrier layer 9) illustrate, however, that the good matchability results

And durability can be achieved when only one (i.e., lower) of the barrier layers is intentionally nitrided (i.e., according to the present invention, the N-flow for opposing barrier layers may be symmetric or asymmetric). Accordingly, it can be seen that by controlling the nitrogen flow during the sputtering of one or both of the barrier layers 5, 9, a combination of high transmissivity, matchability and / or good durability can be achieved which is a significant improvement over the prior art. Controlling the thickness of the barrier layer has also been shown to be a significant factor in reducing the ∆Ε * value and thus ensuring good matchability.

For example, but not limited to, good matchability combined with high visible transmission and / or good durability both before and after HT can be achieved when the N-flow is from 0-16 cm when sputtering the lower barrier layer.³(sccm) / kW, more preferably from 4-12 cm³ (sccm) / kW (more preferably 6-10 cm³ (sccm) / kW), and when sputtering the upper barrier layer 9, the flow N is from 0-16 cm³ (sccm) / kW, more preferably from 0-8 cm³ (sccm) / kW and most preferably from 0-4 cm³ (sccm) / kW. It has been surprisingly found that the most durable coated articles combined with matchability are obtained with a moderate N2 flow during the sputtering of the barrier layer (s). In several embodiments of the present invention, both barrier layers 5,9 were sprayed using N-flow, while in other embodiments, the lower barrier layer 5 was sprayed using N-flow, while the upper barrier layer 9 was non-flow (i.e., in some embodiments, the upper barrier layer 9 can be, for example, metallic NiCr). Moreover, in some embodiments, the two barrier layers 5,9 are approximately the same thickness, while in other embodiments they may be of different thicknesses (for example, the upper barrier layer 9 may be thinner and / or less nitrided).

It has surprisingly been found that controlling the thickness of the dielectric layer (s) 3 and / or 11 can contribute to good matchability and / or durability. In particular, it has been found that good matchability (i.e., color stability using HT) is obtained when the upper dielectric layer 11 (when made of silicon nitride) is about 51 nm (510 Å) or slightly greater. The lower dielectric layer 3 (when made of silicon nitride) then has a thickness of about 5-20%, more preferably about 10%, than the top dielectric layer 11. Although other thicknesses of these layers may, of course, be used in various embodiments of this invention, these particular thicknesses have been found to be particularly good. Moreover, it has been found that, in the case of silicon nitride, more stable coatings are obtained with fully nitrided silicon nitride layers 3, 11. It goes without saying, however, that in other embodiments the dielectric layers may be made of silicon-enriched silicon nitride and / or other stoichiometry.

The above examples show that monolithic coated articles according to certain embodiments of the invention exhibit visible transmittance (TY%) of preferably at least about 65% before and / or after HT, more preferably at least about 70% before and / or after. HT, and most preferably at least about 75% post HT. In some embodiments of the invention, IG units exhibit similar transmittance. Additionally, monolithic coated articles according to certain embodiments of the invention have, on the glass side, a reflectance (RGY%) preferably not greater than 10%, more preferably not greater than 8%, before and / or after HT. In addition, coatings according to some embodiments of this invention exhibit a layered resistance Rs of no greater than about 25 ohms per unit area before and / or after HT, more preferably no more than about 20 ohms per unit area before and / or after HT, and most preferably no more. greater than about 15 ohms per unit area post HT (the low emissivity / emittance values ​​are appropriate for this). Additionally, in some embodiments of this invention, barrier layer 5 and / or 9 are not more than 75% nitrided, more preferably not more than 50% nitrided.

Figures 3-4 plot the results of some examples in determining nitrogen gas flow for a barrier layer as a function of stability using HT (i.e., ΔΕ * (glass side)). In particular, in Fig. 3 the nitrogen gas flow for the backing (i.e., bottom) barrier layer 5 is plotted against the glass side color stability using HT (i.e., ΔΕ * (glass side)), illustrating that HT color stability deteriorates (i.e. ., ∆Ε * increases) as the nitrogen gas flow increases during the sputtering of the barrier layer 5. In a similar manner, in Fig. 4 plots the nitrogen gas flow for the top barrier layer 9 as a function of the glass side color stability using HT (i.e., ΔΕ * (glass side)), illustrating that HT color stability deteriorates (i.e., ΔΕ * increases) as the nitrogen gas flow increases during sputtering

Accordingly, it can be seen that extremely high nitrogen gas flows may be undesirable in some instances as they result in an undesirably high ΔE *.

Certain terms are commonly used in the glass coating technique, especially when they define the properties and use of the solar characteristics of coated glass. Such terms are used herein in accordance with their well-known meaning.

For example:

The intensity of the reflected light at visible wavelengths, ie "reflectance", is defined as its percentage and is denoted as RxY or Rx (ie, the quantity Y quoted below in ASTM E-308-85) where "X" is either " G "for the glass side or" F "for the film / coating side. The side of the glass (e.g., "G") is understood to be viewed from the side of the glass substrate which is opposite to that on which the coating is deposited, while the "film side (i.e. "F") is understood as viewed from the side of the glass substrate on which the coating is deposited.

Color characteristics were assessed and reported herein using the a * and b * coordinates and the CIE LAB scale (i.e. CIE a * b * diagram, I11 CIE-C, 2 degree observer). Other similar coordinates may be equivalently used, such as a subscript "h" to denote the conventional use of the Hunter Lab Scale, or the I11.CIE-C, 10 ° observer, or the CIE LUV u * v * coordinates. These scales are defined herein in accordance with ASTM D-2244-93 "Standard Test Method for Calculation of Color Differences From Instrumentally Measured Color Coordinates", extended by ASTM E-30885 , Annual Book of ASTM Standards, Vol.06.01 "Standard Method for Computing the Colors of Objects by 10 Using the CIE System" and / or as stated in IES LIGHTING HANDBOOK 1981 Reference Volume.

The terms "emittance" and "transmittance" are well understood in the art and are used herein in accordance with their well-known meanings. Thus, for example, the term "transmittance" as used herein means solar transmittance, consisting of visible light transmittance (TY), infrared radiation transmittance, and ultraviolet radiation transmittance. Total solar energy transmittance (TS) is usually characterized as a weighted average of these quantities. With regard to these transmittances, the visible transmittance as mentioned herein is defined by the CIE Illuminant C, 2 degree observer standard, being technical in the range 380-720 nm; near infrared in the range 720-2500 nm; ultraviolet in the range of 300-800 nm; and total solar in the range of 300-500 nm. However, a specific infrared range (ie 2,500-40,000 nm) is used for emittance purposes.

Known, conventional techniques can be used to measure visible transmittance. For example, using a spectrophotometer such as a Perkin Elmer Lambda 900 or Hitachi U4001, a spectral transmission curve is obtained. Then, using the above-mentioned ASTM 308 / 2244-93 methodology, the visible radiation transmission is calculated. If desired, a lower number of wavelength points than recommended may be used. Another technique for measuring visible transmittance is to use a spectrometer, such as the commercially available Spectrogard spectrophotometer manufactured by Pacific Scientific Corporation. This device directly measures and indicates visible transmittance. As stated and measured herein, when measuring visible radiation transmittance (i.e. Y values ​​in the CIE tristimulus system, ASTM E-308-85) uses the 2 degree observer specified in I11.C, 2 degree observer.

Another term as used herein is "sheet resistance". Layered resistance (Rs) is a term well known in the art and used herein in accordance with its well understood meaning. It is given in ohms per unit area. Generally speaking, this term refers to the resistance in ohms of any surface of the layer system on the glass substrate when electric current flows through the layer system. Layer resistance is an indicator of how well a layer or layer system is reflecting infrared energy, and is therefore often used along with emittance as a measure of this feature. For example, "laminar resistance" may be conventionally measured using a 4 point probe ohmmeter such as a Magnetron Instruments Corp. 4 point resistivity probe, Model M-800 manufactured by Signatore Corp. of Santa Clara, California.

The terms "chemical stability" or "chemically stable" are used synonymously with the terms "chemically resistant" or "chemical stability" in the art. Chemical durability is determined by boiling a 5.08 x 12.7 cm (2 x 5) sample of a coated glass substrate.

The height of the surface is about 500 cm³ 5% HCl [i.e. at about 104 ° C (220 ° F)] for one hour (ie, using the acid boil test mentioned above). If, after this 1 hour of cooking, the sample plies have scratches of 3 or better and no pinholes greater than 0.0076 cm (0.003) in diameter, the specimen is considered to have passed this test (and therefore the ply system is "chemically resistant" or considered to be "chemically stable" or having "chemical stability").

The term "mechanical stability" as used in the present invention is determined by the following test. This test (i.e., the brush test mentioned above) uses the Pacific Scientific Abrasion Tester (or equivalent) in which a nylon brush of 5.08 cm x 10.16 cm x 2.54 cm (2 x 4 x 1), applied to a sample measuring 15.24 cm x 43.18 cm (6 x 17), cyclically passes over the layering 500 cycles with a load of 150 g, If in this test, when looking with the naked eye in visible light no significant, noticeable scratches appear, the test is deemed to have been performed and the article is said to be "mechanically durable" or to have "mechanical durability" (ie, has a scratch rating of 2 or better).

The term "heat treatment" or "heat treatment" is understood to mean heating an article to a temperature sufficient to allow the glass-containing article to be tempered, bent, or thermally hardened. This term includes, for example, heating a coated article to a temperature of at least about 1100 degrees F (593 degrees C) (e.g., to a temperature of about 550 degrees C to 900 degrees C) for a period of time sufficient to allow tempering or heat bending.

It is apparent to those skilled in the art that many other features, modifications and improvements to the present invention may be made. Such other features, modifications and improvements are therefore considered part of the present invention, the scope of which is defined by the following claims.